TWI534208B - A process for producing a pigment dispersion, a pigmented resin composition for a pigment dispersion and a color filter - Google Patents

Description

Method for producing pigment dispersion, pigment dispersion and colored resin composition for color filter

The present invention relates to a method for producing a pigment dispersion liquid, a pigment dispersion liquid which can be produced by the production method, and further relates to a pigment dispersion liquid characterized by wet dispersion of a pigment (a) having an S/N of 90 or less. Production method.

In color displays, CCDs, color prints, color paints, and the like, there is a demand for high contrast, high definition, high luminance, high color reproducibility, high dispersion, dispersion stability, etc., and it is desired to have such Improved performance of pigment dispersions.

Especially in recent years, the demand for liquid crystal displays or organic EL displays has increased due to the development of computer displays and the like. Accordingly, in the performance of such displays, high image quality such as contrast or improvement in color reproducibility is strongly desired.

In such a situation, there is an increasing demand for high contrast, high luminance, and improved color reproducibility in terms of a color filter having a function of color-displaying a display.

In addition, other than the use of the display, such as gravure ink, lithographic ink, flexographic ink, screen ink, inkjet ink, etc.; various coatings; various resists, etc., the above-mentioned superior pigment dispersion is also expected .

Here, for example, a color filter used for a display generally has a transparent substrate, a colored layer, a light shielding portion, and the like. As a method of forming the colored layer, a pigment dispersion method, a dyeing method, an electroforming method, and a printing method are known. In the above, the pigment dispersion method is widely used from the viewpoints of spectral characteristics, durability, pattern shape, precision, and the like (Patent Documents 1 and 2).

However, a color filter in which a pigment is generally dispersed is a case in which a polarized light penetrating a liquid crystal substance is removed by a dispersed pigment, and a contrast between an ON state and an OFF state is lowered, and a parallel luminance is relatively positive. The problem that the ratio of cross-brightness becomes smaller. Further, due to the reduction in power consumption of the backlight and the characteristics of the LED backlight, the requirements for high luminance and high contrast of the color filter are improved.

The conventional dry pulverization method is difficult to reduce the particle size of the pigment according to the uniform size, and the technique of reducing the particle size by the grinding method and improving the contrast has become the mainstream.

As a method for producing a pigment, for example, pigmentation of grinding is carried out, and dry dispersion is mostly used. However, since only the steps are not sufficiently fined, or aggregation or pigment particle unevenness occurs, water is often combined with a solvent treatment, a solvent treatment, an aqueous emulsion treatment, or the like.

As the grinding method, in addition to dry dispersion, there are, for example, solvent grinding, dry salt grinding, solvent salt grinding, and the like. In particular, in the case of a pigment used for a color filter application or a pigment used for an inkjet ink, since it is required to have a high degree of miniaturization and uniformity of crystal particles, it is often ground by a solvent salt.

On the other hand, in order to improve the dispersibility or dispersion stability of the pigment, various dispersants or pigment modifiers are also reviewed. For example, Patent Document 3 describes grafted oligomers as dispersants; A pigment derivative having an acidic group is described in 4.

However, especially in the case of color filters for displays, the above-mentioned techniques are not sufficient in terms of pigments used in fields requiring high dispersion, and further development is desired in response to demands for high contrast and high dispersion. improve.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-133131

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-244617

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-339949

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2006-206737

Although dry dispersion has been carried out since the prior art, the fineness is not sufficient, aggregation occurs, or pigment particles are not uniform. Therefore, in the use of a color filter which is particularly required to be fine-grained, The step is to use the idea that the S/N is 90 or less.

The present invention has been made in view of the above-described background art, and an object thereof is to provide a display material, a CCD material, or an inkjet which has excellent dispersibility and dispersion stability and is used as a liquid crystal display material, an organic EL display material, or the like. In the case of an ink material or the like, a pigment dispersion liquid exhibiting superior optical properties and superior pigment dispersion stability; and a pigment dispersion liquid which can obtain a color filter which is particularly high in contrast can be provided.

Further, a colored resin composition, a photosensitive colored resin composition, a color filter, a liquid crystal display, an organic EL display, a CCD, and an inkjet ink using the pigment dispersion are provided.

In order to achieve the above object, the inventors of the present invention have found that by dispersing the pigment (a) having an S/N of 90 or less and performing wet dispersion, the dispersibility and dispersion stability are good, and in particular, it is used. The method for producing a pigment dispersion which is excellent in contrast when used in a color filter, has completed the present invention.

That is, the present invention is a method for producing a pigment dispersion liquid, which is a method for producing a pigment dispersion liquid containing at least (A) a pigment, (B) a dispersant, and (C) a solvent, characterized in that it contains an X-ray diffraction spectrum. The main peak intensity (S) divided by the background noise intensity (N) value (S/N) of 90 or less (A) pigment (a) as the (A) pigment is wet-dispersed.

Further, the (A) pigment having a S/N of 90 or less in the (A) pigment used in the present invention may be referred to as "(A) pigment (a)".

Further, the present invention provides a pigment dispersion liquid produced by the method for producing a pigment dispersion liquid described above.

Further, the present invention provides a colored resin composition for a color filter comprising the above pigment dispersion liquid.

Further, the present invention provides a color filter obtained by using the colored resin composition for a color filter described above.

Further, the present invention provides a display display device having the above-described color filter.

According to the present invention, it is possible to provide a method for producing a pigment dispersion liquid having excellent dispersibility and dispersion stability in a color display, a color print, a color paint or the like, and a method for solving the above problems A novel pigment dispersion produced.

The pigment system used in the pigment dispersion liquid of the present invention has a S/N of 90 or less. A pigment having an S/N of 90 or less is considered to have a lower crystallinity than a pigment having an S/N of more than 90, and the solidity of the pigment is lowered, so that it is considered to be more finely dispersed. For example, in particular, in the case where the final dispersion is wet dispersion or the like, extremely fine dispersion can be performed.

Therefore, a color display and a color print obtained by using such a pigment dispersion Brushes and color coatings are excellent optical properties.

Further, in particular, a color display such as a liquid crystal display or an organic EL display obtained by using such a pigment dispersion liquid is a display having high contrast, high light transmittance, and high luminance. Specifically, the parallel luminance is relatively large with respect to the orthogonal luminance, the degree of elimination of the polarization is small, and the contrast between the ON state and the OFF state can be increased.

The pigment dispersion liquid obtained by the method for producing a pigment dispersion liquid of the present invention exhibits the above-described superior optical performance when a display material such as a liquid crystal display material or an organic EL display material is used.

In particular, the color filter for a liquid crystal display obtained by using the pigment dispersion of the present invention is such that the pigment is finely dispersed, so that the polarized light obtained by the liquid crystal material is eliminated, and if such a color filter is used, Provides a liquid crystal display with high contrast, high transmittance, and high luminance.

(1) ‧‧‧main peak intensity (S)

(2) ‧‧‧ Background noise intensity (N)

Fig. 1 is a schematic diagram for explaining the main peak intensity (S) of the X-ray diffraction spectrum and the background noise intensity (N), and shows an X-ray diffraction spectrum which is depicted by removing the background using the Sonnevelt-Visser method.

The present invention will be described below, but the present invention is not limited to the specific embodiments described below, and may be arbitrarily modified within the scope of the technical idea.

Pigment dispersion

The present invention provides a method for producing a pigment dispersion liquid, which is a method for producing a pigment dispersion liquid containing at least (A) a pigment, (B) a dispersant, and (C) a solvent, characterized in that The (A) pigment (a) containing the main peak intensity (S) of the X-ray diffraction spectrum divided by the background noise intensity (N) (S/N) of 90 or less is used as the (A) pigment, and is subjected to wet type. dispersion.

1-1. (A) Pigment 1-1-1. S/N

In the pigment (A) of the present invention, the main peak intensity (S) of the X-ray diffraction spectrum must be divided by the background noise intensity (N) (hereinafter sometimes abbreviated as "S/N") to be 90 or less. S/N is a value indicating the degree of crystallinity.

The X-ray diffraction spectrum is a powder X-ray diffraction apparatus belonging to a concentrated optical system using CuKα rays as an X-ray source, for example, "RINT-TTR III" manufactured by Rigaku Co., Ltd., and the measurement conditions are set to scan area 2θ=3 to 55. °, sample width 0.02 °, scanning speed 5 ° / min, divergence slit 1/4, scattering slit 1/4, light receiving slit 0.45 mm.

The main peak intensity (S) and the background noise intensity (N) are obtained by removing the background from the X-ray diffraction spectrum. The removal of the background uses the Sonnevelt-Visser method. At this time, the peak width limit is set to 0.10, and the intensity threshold is set to 0.01.

Here, the "main peak of the X-ray diffraction spectrum" refers to a peak in which the height of the diffraction peak is the largest among the diffraction peaks of the crystallinity of the pigment (A) contained in the pigment dispersion liquid of the present invention. The term "main peak intensity (S)" refers to the height of the main peak of the X-ray diffraction spectrum.

In addition, the "background noise intensity (N)" means the average spectral intensity in the scanning range (for example, 2θ = 47.5 ° - 48.0 °) of the undetected peak of the X-ray diffraction spectrum of the (A) pigment. And refers to the height of background noise caused by (A) the average crystallinity of the pigment obtained by the following method.

The calculation method and definition of "background noise intensity (N)" are as follows. The height of the peak from the noise in the scanning range 2θ=47.5°~48.0° is detected as 26 points per 0.02°. In the 26 points, the sum of the average of 12 points of the upper and lower points is removed. It is regarded as "background noise intensity (N)".

Further, when the peak of the X-ray diffraction spectrum of the (A) pigment is detected in the scanning range 2θ=47.5° to 48.0°, the range is changed from the scanning range 2θ=45.0° to 55.0°, and is avoided. The peak of the peak was detected in the range of 0.5° of 2θ continuous, and 26 points were similarly detected.

As described above, the main peak intensity (S) and the background noise intensity (N) are obtained by removing the background from the X-ray diffraction spectrum. Here, the "background" is not caused by the diffraction peak of crystallinity or The bottom of the diffraction peak is a tailing portion, but is caused by an upd portion of a Conduit scattering or the like. Figure 1 is an X-ray diffraction spectrum of the background removed by the above method.

The numerical value (concept) of the "S/N" is a calibration of the fluctuation of the main peak intensity (S) due to the measurement conditions, and the "material" of the raw material belonging to the pigment dispersion liquid. (A) The pigment is a value (concept) of "S/N" by the method of introducing the eigenvalue.

Further, in the present invention, the main peak itself or the intensity (S) of the main peak is prepared by the method described in the examples, and S/N is defined as such a measurement.

The upper limit of S/N must be 90 or less, preferably less than 90, more preferably 70 or less, particularly preferably 60 or less, still more preferably 50 or less, and most preferably 30 or less.

The preferred value of the upper limit varies depending on the type of the pigment (A). When the upper limit is at most the above, the crystallinity is low, and (A) the pigment has low firmness, that is, it is easily pulverized, dispersed, etc., and when the pigment dispersion is prepared. The microdispersion by dispersion is easy. Also, the score can be shortened Scattered time. When the upper limit of S/N is made to be less than or equal to the above by the dry dispersion, it is particularly preferable in terms of microdispersion.

In particular, when the above pigment is subjected to wet dispersion to prepare a pigment dispersion liquid, it is preferable from the viewpoint of easy microdispersion. As a result, the color display, the color print, the color coat, and the like obtained by using the pigment dispersion have excellent dispersibility, and the color display such as a liquid crystal display or an organic EL display has high contrast and high light transmittance. High brightness display.

Here, the "luminance" and the "contrast" are measured by the method described in the examples, and are defined as such. The "contrast" is as follows.

"Contrast" = [parallel luminance (cd/m ² )] / [orthogonal luminance (cd/m ² )]

The lower limit of S/N is not particularly limited, and is preferably as small as 1.4 or more, more preferably 1.6 or more, and particularly preferably 1.8 or more.

When the lower limit is less than or equal to the above, the manufacturing cost is increased, and physical properties such as dispersibility, dispersion stability, contrast, transmittance, and luminance are not obtained, and the physical properties are improved in accordance with the increase in the production cost in order to set the lower limit to the above. There are cases where you cannot expect further improvement.

The inventors of the present invention reviewed the particle size of the (A) pigment added to the (B) dispersant and the solvent (C) when the pigment dispersion was produced by dispersing the pigment (A), and the pigment dispersion or the pigment dispersion or There is no correlation between the performances of the color display, the color print, the color paint, and the like obtained by using the pigment dispersion.

In the production of the pigment dispersion liquid, the (A) pigment is subjected to a dispersion treatment, and by performing the dispersion treatment, the particle diameter and crystallinity of the pigment particles after the dispersion treatment are changed. In general, in the case of wet dispersion, the dispersed particle size becomes small, and the crystallinity is improved, that is, the peak intensity of the X-ray diffraction is increased.

When the S/N is 90 or less and the S/N is 90 or less in comparison with the pigment (A) as the raw material, the S (N) pigment is used as a raw material. When /N is 90 or less, the average dispersed particle diameter of the pigment in the pigment dispersion liquid after the final dispersion treatment can be reduced. Therefore, regarding the physical properties such as the contrast, the transmittance, and the luminance of the color filter, a superior product can be obtained by setting the S/N to 90 or less before the stage of the (A) pigment as the raw material.

In the case where it is assumed that the microdispersion can be made to be the same, the average dispersion particle size is the same. When the S/N is 90 or less in the stage of the (A) pigment as the raw material, the time until the arbitrary average dispersed particle diameter is reached can be greatly shortened. . Further, a pigment dispersion liquid having excellent dispersibility and dispersion stability which has the effects of the present invention can be obtained, and the use (utilization) of the pigment dispersion liquid obtained at this time (for example, a photosensitive colored resin composition, a color filter, and a spray) can be obtained. In the ink, etc., the brightness or contrast is improved. On the other hand, regarding the firmness, for example, chemical resistance or light resistance, when the average dispersed particle diameter is the same, almost no difference in performance is observed.

The (A) pigment (a) having an S/N of 90 or less in the present invention is a method for producing a pigment dispersion liquid, and is subjected to a wet dispersion treatment to be contained in the pigment dispersion liquid immediately before the dispersion treatment. Stager.

The present invention relates to a method for producing a pigment dispersion liquid comprising (A) a pigment and a dispersion treatment together with at least (B) a dispersant and (C) a solvent, characterized in that S/N is 90 or less (A) The pigment (a) is subjected to a wet dispersion treatment to be contained in the pigment dispersion.

1-1-2. Types of pigments

The pigment (A) of the present invention, which includes achromatic color such as white, black, gray or the like, is not particularly limited as long as it is a colored solid and can be dispersed, and is preferably a so-called coloring pigment.

The material for forming the (A) pigment is not particularly limited as long as it satisfies the above requirements of the pigment (A), and is preferably a coloring pigment used for a display, a printed matter, a paint, or the like, and is preferably used for a color filter. Coloring pigments.

Here, the coloring pigment also includes an achromatic pigment such as white, black, or gray, and specifically, a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, a black pigment, or the like can be used. Various colors of pigments.

In consideration of the case where the pigment dispersion liquid of the present invention is used as a color filter material, among the above, blue pigment, green pigment, red pigment, yellow are considered from the viewpoint that the comparison is generally lower or that high contrast is required. Pigments, purple pigments and the like are suitably used in the present invention.

Specific examples of the pigments exemplified as the substance forming the (A) pigment are shown below by the pigment number. Further, the following "C.I." refers to a color index.

Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37. 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53: 1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81: 1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271 .

Among them, preferred are C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., particularly preferably C.I. Pigment Red 177, 209, 224, 254 and the like.

As the blue pigment, for example, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79, etc.

Among them, preferred are C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, etc., particularly preferably C.I. Pigment Blue 15:6 and the like.

Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. 58 and so on.

Among them, preferred are, for example, C.I. Pigment Green 7, 7, and the like.

Examples of the yellow pigment include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, and 35. 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196 199, 200, 202, 203, 204, 205, 206, 207, 208, 213, and the like.

Among these, preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, 213, etc., particularly preferably C.I. Pigment Yellow 83, 138, 139, 150, 180, 213 and the like.

Examples of the orange pigment include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49. 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, and the like.

Among them, preferred are C.I. Pigment Orange 38, 71 and the like.

Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

Among them, C.I. Pigment Violet 19, 23 and the like are preferable, and C.I. Pigment Violet 23 and the like are particularly preferable.

In the present invention, one type of the above pigments may be used, or two or more types may be used.

Further, when the pigment dispersion liquid of the present invention is a pigment dispersion liquid for a black matrix of a color filter, a black pigment can be used as a material for forming the (A) pigment. The achromatic (A) pigment such as black may be the achromatic pigment alone or may be mixed with a pigment such as red, green or blue.

The preferred pigment of the pigment (A) of the present invention may, for example, be an anthraquinone pigment such as Pigment Red 177 or a quinophthalone yellow pigment such as Pigment Yellow 138 from the viewpoint of a chemical structure; An azo-based pigment such as a methyl azo pigment; a benzimidazolone pigment such as Pigment Yellow 180; and a quinine such as Pigment Yellow 213 a phthalocyanine pigment; a phthalocyanine pigment such as a pigment blue 15:6; a pigment purple 23; Pigment; pyrrolopyrrole pigment; quinacridone pigment; isoporphyrin pigment; isoindolinone pigment; lanthanide, lanthanide pigment;

In the present invention, the same chemical composition, that is, the above-mentioned pigments are the same, and one type may be used in the system, or two or more types may be used. Further, two or more types may be used in a cross-system.

The pigment having the above chemical structure can easily exhibit the above-described effects when produced by the production method of the present invention, in particular, Pigment Red 177, Pigment Yellow 150, Pigment Yellow 180, Pigment Yellow 213, Pigment Blue 15:6, and Pigment Violet 23. In particular, Pigment Red 177, Pigment Yellow 150, Pigment Blue 15:6, Pigment Violet 23 and the like are preferable from the viewpoints of high contrast of color filters, high luminance, and improvement in color reproducibility.

1-1-3. Acidic pigment derivatives

The pigment (A) of the present invention preferably contains an acidic dye derivative in order to easily exhibit the above effects of the present invention. In particular, microdispersion can be performed, and when it is used for a color filter, a display having high contrast, high dispersion stability, high light transmittance, and/or high luminance can be obtained, which is preferable.

The "acidic dye derivative" refers to a dye derivative having an acidic group in its chemical structure, and preferably has a pigment selected from the group consisting of a phthalocyanine pigment, a quinophthalone pigment, an azo pigment, an anthraquinone pigment, and Oxidized pyrrolopyrrole pigment, two A pigment derivative having at least one pigment skeleton of a pigment group and an isoporphyrin group and having an acidic group.

The acidic group of the above pigment derivative is preferably at least one selected from the group consisting of a sulfonic acid group, a sulfonylamino group, a carboxyl group, and a metal salt or an ammonium salt of the functional group.

The average amount of the acidic group to the molecule of the pigment is not particularly limited, but is preferably 0.5 to 5. More preferably 0.6~4, especially 0.7~3.5.

By the introduction of an acidic group, it can be microdispersed, especially when used in a color filter, which can obtain a display with high contrast, high dispersion stability, high light transmittance, and/or high luminance. It is better, etc.

The pigment (A) of the present invention preferably contains a pigment and an acid dye derivative. The acid dye derivative interacts with the pigment, and when the pigment particles are produced, it is adsorbed on the surface of the pigment or taken in, and the pigment particles or (A) the particle size and crystallinity of the pigment are defined.

Further, by adsorbing the acidic dye derivative interacting with the alkaline dispersant on the surface of the pigment, the alkaline dispersant can be efficiently located on the surface of the pigment. Therefore, when "S/N is 90 or less" in the dry dispersion treatment to be described later, the "(A) pigment (a)" having an S/N of 90 or less is microdispersible thereafter. Stabilization or dispersion stabilization, especially when used in color filters, can be highly contrasted.

In the whole of the (A) pigment of the present invention, the content of the acidic dye derivative is not particularly limited, and is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass, particularly preferably 2 to 10 parts by mass based on 100 parts by mass of the pigment. Parts by mass.

When it is set to the above lower limit value, stable dispersion or fine dispersion can be performed during wet dispersion, and by setting it as the above upper limit or less, it is possible to prevent a decrease in color price due to excess of the acid dye derivative.

In the present invention, one or two or more kinds of the above-mentioned acidic dye derivatives can be used as the pigment (A), and one or two or more kinds of the above-mentioned acidic dye derivatives can be used for one type of pigment.

The acidic dye derivative may be added to the dispersion of the pigment particles at any stage, but may be added to the pigment in the step of producing the pigment in consideration of adsorbing the acidic dye derivative on the surface of the pigment or ingesting it; For example, in the step of synthesizing the pigment, in the step of performing solvent salt milling of the pigment by a kneader or the like, the step of post-treatment, the step of dry pulverizing the pigment by a grinder or the like, and the subsequent treatment The steps are added in medium.

In the reprecipitation method, it may be added to a good solvent or a poor solvent in advance, or may be in a pigment particle. It is added after precipitation or after concentration or redispersion.

That is, the acidic dye derivative may be contained in the (A) pigment before the dry dispersion treatment, or may be formulated when the acid dye derivative is dry-dispersed, or may be wet-formed on the acidic dye derivative. It is formulated during dispersion treatment.

1-1-4. Modulation of pigment (a) with S/N of 90 or less

The preparation method of the (A) pigment (a) having an S/N of 90 or less is not particularly limited, and when the pigment to be synthesized has a S/N of 90 or less at this time, it can be used as it is.

Further, the pigment derivative such as an acid dye derivative is adsorbed on the surface of the pigment or the pigment particles after being ingested, and if the S/N value at this time is 90 or less, it can be used as it is.

Further, it is also possible to use S/N of 90 or less by applying a treatment such as dispersion to the pigment or the pigment particles.

Basically, it is preferable to apply a certain treatment to make it difficult to obtain (almost no) "pigment (a)" having a S/N of 90 or less or "pigment particles containing a pigment derivative". /N is 90 or less.

The "treatment" is not particularly limited, and is preferably a physical treatment such as dispersion treatment, pulverization, and dispersion treatment while pulverizing.

The method of "dispersion treatment" is not particularly limited, and the dry dispersion treatment is preferable because S/N can be easily made 90 or less. As a result, the pigment dispersion can be microdispersed when it is produced, especially for color filters. When used, it can be highly contrasted, so it is better.

Here, the "dry dispersion treatment" refers to a treatment in which a dispersion medium of a liquid is not used, or a treatment in which a small amount of a liquid dispersion medium is added and dispersed.

For example, if pigments such as Pigment Blue 15:6 and Pigment Red 254 are dispersed without using a liquid dispersion medium, crystal transfer occurs, and in the case of Pigment Blue 15:6, the α type is generated. Crystallization is transferred, but dispersion is carried out by adding an organic solvent to prevent crystal transfer. At this time, the state of the dispersion is dry, and in addition to this, it is defined as "dry dispersion treatment" in the present invention. Solvent salt milling is not defined as "dry dispersion treatment".

When the liquid is added to the dry dispersion treatment, the liquid amount is more than 0 parts by mass, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, particularly preferably 50 parts by mass or less, more preferably 100 parts by mass of the pigment. 30 parts by mass or less, preferably 10 parts by mass or less.

In the present invention, the "wet dispersion treatment" is as described above, and the "(A) pigment (a) having an S/N of 90 or less" is finally dispersed in (C) in the presence of the (B) dispersant. In the "wet dispersion treatment" of the present invention, "(C) solvent" which is the final solvent of the pigment dispersion liquid of the present invention is used.

On the other hand, the "dry dispersion treatment" of the present invention is a treatment in which a small amount of a liquid dispersion medium is used for dispersion by the above-mentioned "wet dispersion treatment", and for example, a treatment for adding a liquid to suppress a change in crystal transfer or the like is performed. Or it is not a final dispersion treatment, and is equivalent to a pretreatment for final production of the pigment dispersion of the present invention; further, the liquid to be added thereto is not limited to the (C) solvent which is the final solvent of the pigment dispersion of the present invention.

The liquid dispersion medium may be contained in the range which does not affect as described above, and varies depending on the kind of the pigment, but is preferably not contained.

Further, in the present invention, the "dry dispersion treatment" herein also includes a treatment of dispersing or pulverizing which is subjected to mechanical treatment without using a solid dispersion medium. In addition, the "dry dispersion treatment" also includes a treatment for increasing the particle diameter of the secondary particles or the like by the treatment. The "dry dispersion treatment" in the present invention includes a treatment using a so-called dry dispersion device or a dry pulverization device.

The specific method of the "dry dispersion treatment" is not particularly limited, and it is preferably a media mill using beads, balls, sand, etc.; a sprayer, a jet mill such as a jet mill; a roll mill; a sharpening; a rod grinding; a hammer grinding; Planetary mill; gas-fall mill; tube mill; tower mill; mortar and other methods of grinding.

Among them, it is preferably a media mill such as bead mill, ball mill, sand mill, etc.; various jet mills, etc., especially media mills such as bead mill, ball mill, sand mill, etc., which are subjected to dry dispersion treatment to obtain a particle size suitable for The particle size of the (A) pigment of the present invention or the S/N is easily 90 or less, which is particularly preferable.

When the media mill is used for the dry dispersion treatment, the diameter of the medium such as beads used for the dry dispersion treatment is not particularly limited as long as the S/N ratio is 90 or less, and preferably 0.1 mm to 40 mm, more preferably 0.5 mm. 30mm, especially good 1mm~20mm. When the upper limit of the diameter of the medium is larger than the above value, the total surface area of the medium becomes small and the processing time becomes long. If the lower limit is smaller than the above value, the processing energy by the medium becomes small, so the processing time becomes long.

Further, it is preferable to disperse the media by two or more segments having different diameters. In this case, it is preferred to use a relatively large particle size medium in the first stage.

In the present invention, the time of the dry dispersion treatment is not particularly limited, and in order to make the S/N of the (A) pigment appropriate, it is preferably 0.5 to 200 hours, more preferably 1 to 100 hours, and particularly preferably 2 to 60 hours. When the upper limit of the dry dispersion treatment time is larger than the above value, the energy consumption with respect to the effect becomes large, and when the lower limit is less than the above value, the pigment having low crystallinity cannot be sufficiently obtained.

In the dry dispersion treatment, in particular, by setting the above apparatus (grinding) or dry dispersion treatment conditions, the S/N of the (A) pigment can be reduced, and as a result, a good pigment dispersion liquid can be obtained, and high contrast can be achieved.

The "dry dispersion treatment" is preferably 90 or less, but more preferably 70 or less, more preferably 60 or less, still more preferably 50 or less, and most preferably 30 or less.

The preferred value of the upper limit varies depending on the type of the pigment (A). When the upper limit is less than or equal to the above, the crystallinity is low. Therefore, the solidity of the (A) pigment is low, that is, pulverization, dispersion, and the like, and the pigment dispersion liquid is prepared. The microdispersion by dispersion becomes easy. Moreover, the dispersion time can be shortened. In the case where the S/N upper limit is set to the above or lower by the dry dispersion, in particular, the microdispersion can be performed. The surface is preferred.

By reducing the effect of S/N, if the upper limit is less than or equal to the above, it is easy to be pulverized and dispersed, and the microdispersion can be performed by "final dispersion step in the case of preparing a pigment dispersion liquid", or can be shortened. Disperse time.

In particular, when a pigment dispersion liquid is prepared by performing a wet dispersion treatment or the like as a "finish dispersion step in preparing a pigment dispersion liquid", it is particularly easy to finely disperse, and as a result, a color display obtained by using the pigment dispersion liquid, Color prints, color coatings, etc., not only have superior dispersibility and dispersion stability, but also color displays such as liquid crystal displays and organic EL displays obtained by using the pigment dispersions have high contrast, high light transmittance, and high Brightness display.

In addition, when the S/N of the "pigment" or the "pigmented pigment-containing pigment particles" is more than 90, it is preferred to obtain the (A) pigment having an S/N of 90 or less by performing the above-described dry dispersion treatment ( a).

In the method for producing a pigment dispersion liquid of the present invention, it is preferred that the S/N of the pigment (A) after the dry dispersion treatment is divided by the value of S/N of the pigment (A) before the dry dispersion treatment to be 0.5 or less. In the dry dispersion treatment, the dry dispersion treatment is preferably carried out in a manner of 0.4 or less, and the dry dispersion treatment is carried out in a manner of 0.3 or less. That is, it is preferable to lower the S/N by the above ratio so that the S/N is 90 or less.

In this way, superior optical performance can be exhibited, and the dispersion time in wet dispersion can be drastically shortened. Also, the dispersion can be improved.

The particle size of the (A) pigment may be increased or decreased before and after the above-described "treatment with S/N of 90 or less". In the above-described dry dispersion treatment or the like, the treatment of S/N is 90 or less, and even if the particle diameter of the primary particles or the secondary particles is large, the pigment dispersion liquid is required if the S/N ratio is equal to or less than a certain value. The dispersion in the manufacturing steps is improved, so Say good results.

The effect of lowering the crystallinity of the pigment is to promote microdispersion during wet dispersion, so that the final pigment particle size becomes small.

1-1-5. Particle size of pigment

The particle diameter of the (A) pigment to be used in the "wet dispersion step in preparing a pigment dispersion liquid" to be described later is not particularly limited, but may be preferably 30 nm to 500 nm, more preferably 40 nm to 300 nm. Good 50nm~200nm.

When the particle size is too small, there is almost no correlation between the particle diameter and the final properties, so that it is not necessary to reduce it, and the workability is lowered due to contamination of the fine powder or the like. On the other hand, when the particle diameter is too large, it may take a long time to make S/N become 90 or less.

The specific measurement method is described below. The definition is based on the following measurement method, but the actual measurement is not limited to this method. The particle diameter of the (A) pigment of the present invention means "the diameter distribution (D50)". (A) The particle size of the pigment is based on a field emission scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Co., Ltd., and a dedicated bright-field STEM sample stage and an optional detector are installed, which can be used as a scanning penetration. An electron microscope (hereinafter referred to as "STEM") is used to take a 200,000-fold STEM photograph and load it into the following software. Select 100 pigments on the photograph and measure the diameter (length of the end diameter). The volume was calculated by 50% cumulative particle size.

For the STEM measurement sample, the mixed pigment and toluene are dropped to the rubber film and attached to the mechanical device. In addition, when the particle size distribution or the volume distribution median diameter (D50) of the volume reference was obtained from the STEM photograph, the image analysis particle size distribution measurement software "Mac-View Ver. 4" manufactured by Mountech Co., Ltd. was used.

Hereinafter, the particle size of the (A) pigment obtained by the above measurement is regarded as "the TEM of the (A) pigment. Particle size."

1-2. (B) Dispersant 1-2-1. Polymer dispersant and low molecular weight dispersant

The (B) dispersant of the present invention is not particularly limited, and a polymer dispersant or a low molecular dispersant known in the form of pigment dispersion can be used.

The polymer-based dispersant may, for example, be a random dispersant composed of a random (co)polymer; a block-type dispersant composed of a block copolymer; and a pendant such as a main chain ( A graft-type dispersing agent composed of a graft (co)polymer or the like as a side chain in which a repeating unit is bonded as a branch;

Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid, and (partial) a (co)polymer of a hydroxyl group-containing carboxylic acid ester such as a hydroxyl group-containing polyacrylate or a modified substance thereof; a polyurethane; an unsaturated poly Amidoxime; polyoxyalkylenes; long-chain polyamine guanamine phosphates; guanamine or such salts obtained by the reaction of poly(lower alkylene imine) with a polyester containing a free carboxyl group Classes, etc.

Among them, a poly(meth)acrylate, a sodium maleate-olefin copolymer, a polyester having a terminal carboxyl group (for example, Japanese Patent Publication No. Sho 54-34009, etc.); Alkyldiamine is a polyester having an acidic group and/or a basic group as a starting material (Japanese Patent Laid-Open No. Hei 2-245231, etc.); a macromonomer having a polymerizable unsaturated group at a single terminal a copolymer of a hydroxyl group, a monomer having a hydroxyl group, and a carboxyl group-containing monomer (Japanese Patent Laid-Open No. Hei 8-259876, etc.); a macromonomer (polymerizable unsaturated at a single terminal) A copolymer of a group of oligopolymers and a monomer having a nitrogen atom, which is obtained by copolymerization of a monomer having a nitrogen atom (Japanese Patent Laid-Open No. Hei 10-339949, etc.).

Examples of the low molecular weight dispersant include an anionic property such as a sulfonic acid group or a carboxylic acid group; a cationic compound having a salt of an aliphatic amine or a tertiary ammonium salt; and a nonionic having a hydroxyl group or an oxyethylene chain. Compound; polymer compound; and the like.

Specific examples thereof include sorbitol fatty acid ester, polyoxyethylene alkylamine, alkyl diamine, and alkanolamine derivative (U.S. Patent No. 3,536,510).

Among the dispersing agents, a polymer dispersing agent is preferred; and a polymer dispersing agent is preferably an alkaline block type dispersing agent and/or an alkaline connection from the viewpoint of functional separation between the pigment adsorption site and the solvent affinity site. Branch dispersant.

When the "S/N is 90 or less" is performed in the dry dispersion treatment or the like, the "(A) pigment (a)" having an S/N of 90 or less can be microdispersed, especially When used in color filters, it can be highly contrasted. Further, from the viewpoint of stability over time of the pigment dispersion liquid, an alkali block type dispersant and/or a basic graft type dispersant are preferable.

Further, when the above acidic dye derivative is used in combination, the effects of the present invention described above are easily multiplied.

Here, the "(B) dispersant is an alkaline block type dispersant and/or a basic graft type dispersant" means that the (B) dispersant is an alkaline block type dispersant, and is a base. In the case of a graft-type dispersant, in the case of using a basic block type dispersant and a basic graft type dispersant, a dispersant which is an alkaline block type dispersant and also an alkaline graft type dispersant Any of the situations. Further, the case where a dispersing agent which is not an alkaline block type dispersing agent or a basic graft type dispersing agent is used in combination is not excluded.

1-2-2. Alkaline block type dispersant

The term "alkaline block type dispersant" means having an amine group, a monoalkylamine group, a dialkyl group. a monomer having a basic group such as a sulfhydryl group or a salt thereof (hereinafter referred to simply as "a monomer"), and a monomer other than the monomer (hereinafter referred to as "b monomer") The dispersing agent composed of the segment copolymer may be a divalent copolymer or a trivalent or higher copolymer.

The above-mentioned a monomer is preferably a (meth) acrylate compound containing a quaternary ammonium salt group, a hydrogen atom bonded to nitrogen or a metal salt of a quaternary or tertiary group substituted with a substituent or a salt thereof. Particularly preferred is a 3-grade amine group and/or a 4-stage ammonium salt group.

Specific examples thereof include a dialkylaminoalkyl (meth)acrylate, a diarylaminoalkyl (meth)acrylate, and a diarylalkylaminoalkyl (meth)acrylate. a dialkylaminoalkyl (meth)acrylate, a salt of these, and the like.

Specific examples thereof include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethyl. Aminopropyl (meth) acrylate, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N dimethyl amino ethyl ( Methyl) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide, (meth) propylene decyl propyl trimethyl ammonium chloride, (meth) propylene hydride Hydroxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethylbenzyldimethylammonium chloride, etc. . Particularly preferred are, for example, dimethylaminoethyl (meth) acrylate, (meth) acryl methoxy ethyl benzyl dimethyl ammonium chloride, and the like.

As a reason for selecting the above-mentioned a monomer, it can be microdispersed or dispersed and stabilized, and particularly when used for a color filter, it can be highly contrasted.

Further, in the case where the above-mentioned a monomer is an amine group, a compound which reacts with an amine group, such as a phosphoric acid compound, a sulfonic acid compound, or a carboxy group, may be appropriately copolymerized with another polymerizable monomer. An acid compound such as an acid compound; a halogen compound such as a halogenated aryl group, a halogenated alkyl group or a halogenated aralkyl group; and a part or all of the ammonium salt.

Examples of the b monomer include styrene monomers such as styrene and α-methylstyrene; methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate; , (isopropyl) (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, (A) a (meth) acrylate monomer such as benzyl acrylate or hydroxyethyl (meth) acrylate; vinyl acetate; an allyl compound such as acrylonitrile or allyl alkyl ether;

The reason for selecting the above-mentioned b monomer is microdispersion or dispersion stabilization, and particularly when used for a color filter, it can be highly contrasted.

When the polymer block containing the a monomer or a salt thereof is "A" and the polymer block containing the b monomer is "B", the basic block type dispersant of the present invention may be an AB block. Any of a copolymer, an ABA block copolymer, a BAB block copolymer, an ABAB block copolymer, and the above block copolymer is preferably an AB block copolymer.

The block copolymer containing a monomer or a salt thereof is adsorbed to the (A) pigment by the block portion containing the a monomer or a salt thereof, and the block portion containing no a monomer or a salt thereof has an affinity for the solvent, so that It can improve the dispersibility of (A) pigment.

Specific examples of the constituting salt include a tertiary amine group which is a monomer which forms a block copolymer, and a salt is formed by an acid such as a phosphoric acid compound or a sulfonic acid compound.

Further, for example, a tertiary amino group such as dimethylaminoethyl (meth) acrylate which is a unit which forms a block copolymer, is classified into a grade 4 by a halogenated aryl group, a halogenated aralkyl group or the like. Ammonium salt.

The weight average molecular weight (Mw) of the basic block copolymer of the present invention is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 30,000. Within the range of 3000~20000, the best is 4000~15000.

In the above range, the "wetness of uniformly dispersing the (A) pigment" and the dispersion stability can be achieved. In addition, when the pigment dispersant of the present invention is used as a component of the photosensitive colored resin composition, when the upper limit is at most the above value, developability and resolution are not lowered, and when the lower limit is at least the above value, sufficient Dispersibility.

Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

The weight average molecular weight (Mw) of the basic block copolymer was measured by using HLC-8120GPC manufactured by Tosoh Co., Ltd., and N-methylpyrrolidone added with 0.01 mol/L of lithium bromide as a wash. The solvent was extracted, and the calibration curve was set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (east). The Cao (share) system was carried out by measuring the column with TSK-GEL ALPHA-M×2 (manufactured by Tosoh Corporation).

Further, the amine value is not particularly limited, but is preferably 5 to 250 mgKOH/g, more preferably 20 to 200 mgKOH/g, and particularly preferably 30 to 150 mgKOH/g.

When it is less than the lower limit, sufficient dispersion stability cannot be obtained, and when it is more than the upper limit, the solubility in a solvent is lowered.

The above amine price can be determined by JIS-K7237.

Further, the acid value is not particularly limited, but is preferably 0 mgKOH/g or more than 0 and 100 mgKOH/g or less, particularly preferably 0 mgKOH/g or more than 0 and 50 mgKOH/g or less.

When the acid value is at least the upper limit, the resist pattern peeling easily occurs.

When the molecular weight, the amine value, or the acid value is in the above range, it is easily dispersed, and the "final dispersion step in the case of preparing a pigment dispersion liquid" can be finely dispersed, or the dispersion can be shortened. between. Further, when used in combination with the above-described acidic dye derivative, the effects of the present invention described above are easily multiplied.

As a result, the color display obtained by using the pigment dispersion liquid has a high contrast ratio, a high light transmittance, and a high luminance display.

1-2-3. Alkaline graft type dispersant

The "basic graft-type dispersing agent" refers to a basic dispersing agent composed of a (co)polymer in which a repeating unit of a main chain is bonded as a side chain.

Specifically, for example, a side chain is synthesized in advance, and it is (co)polymerized, that is, a macromonomer having a polymerizable group unsaturated group at a single terminal (having a polymerizable unsaturated group at a single terminal and having A repeating unit oligo or the like) a dispersing agent composed of a (co)polymer as a polymerization component.

Further, for example, a dispersing agent composed of a (co)polymer or the like in which a main chain is synthesized in advance as a main component, and a repeating unit is used as a side chain, such as a pendant (branches), is used.

The basicity of the "basic graft-type dispersing agent" can be imparted by any method, and it is preferred to impart basicity by copolymerizing a basic nitrogen-containing monomer.

The basic monomer to be copolymerized is not particularly limited, and specific examples thereof include the above-mentioned "a monomer" described in the item of the "basic block type dispersant".

The "macromonomer having a polymerizable group-unsaturated group at a single terminal" is not particularly limited, and a known one can be used.

The polymerization component of the repeating unit of the related macromonomer is not particularly limited, and specific examples thereof include a styrene monomer such as styrene or α-methylstyrene; and methyl (meth)acrylate; Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethyl methacrylate Ester (meth)acrylate monomer such as glycidyl acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate; (meth) acrylamide, N-methylol propylene a (meth) acrylamide-based monomer such as decylamine, N,N-dimethylpropenylamine or N,N-dimethylaminoethyl acrylamide; vinyl acetate; acrylonitrile, allylic An allyl compound containing an alkyl ether or the like; As the macromonomer of the present invention, it is preferred to have a unit polymerized by the above polymerization component.

In the "basic graft-type dispersing agent", in addition to the above-mentioned "macromonomer having a polymerizable group-unsaturated group at one end" and "co-polymerized basic monomer", other polymerizable sheets may be used. The body is copolymerized.

The "other polymerizable monomer" is not particularly limited, and specific examples thereof include the above-mentioned "b monomer" described in the item of the above-mentioned "basic block type dispersant".

The introduction rate of the macromonomer is not particularly limited, and is preferably introduced into the repeating unit of the main chain of 100, and is introduced at an average ratio of 0.1 to 20, and the special product is introduced at a ratio of 0.3 to 10.

The molecular weight of the basic graft type dispersing agent of the present invention is not particularly limited, and is usually from 1,000 to 100,000, preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. Good 4000~25000, and even better 5000~20000.

When it is in the above range, it is easy to disperse, and the "final dispersion step in the case of preparing a pigment dispersion liquid" can be finely dispersed or the dispersion time can be shortened. As a result, the color display obtained by using the pigment dispersion liquid has a high contrast ratio, a high light transmittance, and a high luminance display.

1-3. (C) Solvent

The method for producing a pigment dispersion liquid of the present invention is a method for producing a pigment dispersion liquid containing at least (A) a pigment, (B) a dispersant, and (C) a solvent, and the (C) solvent is not particularly limited. A known substance can be used.

The solvent (C) is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and propanol; ethers such as tetrahydrofuran; propylene glycol monomethyl ether, propylene glycol dimethyl ether, and propylene glycol methyl ethyl ether; An alkanediol ether such as propylene glycol monoethyl ether or propylene glycol diethyl ether; dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol monoethyl ether, two Dialkyl glycol ethers such as propylene glycol diethyl ether; tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol diethyl ether, etc. Alkanediol monoether ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl a dialkyl glycol monoalkyl ether acetate such as ether acetate; a trialkyl glycol monoalkyl ether acetate such as tripropylene glycol monomethyl ether acetate or tripropylene glycol monoethyl ether acetate; toluene; Aromatic hydrocarbons such as xylene; methyl ethyl ketone, methyl propyl ketone Ketones such as methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate; -ethyl hydroxy-2-methylpropionate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxyl Methyl 2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, An ester of ethyl acetate, butyl acetate, methyl lactate, ethyl lactate or the like;

These solvents may be used singly or in combination of two or more.

Among them, particularly preferred are propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethoxyethyl propionate, 3-methoxybutyl acetate, 3-methoxy-3-methyl- 1-butyl acetate, methyl 2-hydroxypropionate.

1-4. Proportion of content

The present invention is a method for producing a pigment dispersion liquid containing at least (A) a pigment, (B) a dispersant, and (C) a solvent. Here, the content ratio of the (A) pigment, (B) dispersant, and (C) solvent It is not particularly limited, but is preferably as follows.

The dispersing agent (B) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, particularly preferably 15 to 100 parts by mass, most preferably 20 to 60 parts by mass, based on 100 parts by mass of the (A) pigment.

Further, the pigment (A) is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, particularly preferably 7 to 30 parts by mass, per 100 parts by mass of the pigment dispersion liquid.

In the case of the above-mentioned "(A) pigment and (B) dispersant content ratio", the pigment (A) is easily dispersed, and the "final dispersion step in the case of preparing a pigment dispersion liquid" which will be described later can be finely dispersed or superior. Dispersion stability, or can shorten the dispersion time.

As a result, a display using a color filter obtained by the pigment dispersion is a display having high contrast, high light transmittance, and high luminance.

In addition, the above-mentioned "(A) pigment-to-(C) solvent-containing ratio" is excellent in dispersibility, dispersion stability, and the like, and is adjusted to an appropriate viscosity to contain (D) alkali-soluble in the pigment dispersion liquid of the present invention. When the resin, the (E) polymerizable polyfunctional compound, and/or the (F) photopolymerization initiator are used to obtain a photosensitive colored resin composition, it is preferred to adjust the content ratio to an optimum value.

1-5. Final dispersion method (wet dispersion method)

The above-mentioned "(A) pigment (a) having an S/N of 90 or less" is contained in the presence of the (B) dispersing agent and is wet-dispersed in the solvent (C).

When it is contained in the wet dispersion, the effect of the present invention can be particularly exhibited by setting the S/N of the pigment (A) which is a raw material of the wet dispersion to 90 or less.

If the (A) pigment (a) having an S/N of 90 or less is wet-dispersed, it may be slightly dispersed. The dispersing time can be shortened, and the dispersion stability of the pigment which is difficult to disperse can be improved.

Further, a display using a color filter obtained by wet-dispersing the pigment (a) (a) is a display having high contrast, high light transmittance, and high luminance. .

Examples of the dispersing machine for performing wet dispersion include roll milling such as twin rolls and three rolls; ball milling such as ball milling and vibratory ball milling; pigment shaker using beads; pigment conditioner; continuous dish bead grinding, Bead grinding of continuous ring type bead mill, etc.;

As a preferable dispersion condition using a beaded pigment shaker or bead mill, the bead diameter used is preferably 0.02 to 4 mm, more preferably 0.03 to 2 mm, and particularly preferably 0.05 to 1 mm.

Further, it is preferred to carry out the dispersion by two or more stages by bead milling having different bead diameters. At this time, the bead diameter of the bead mill of the first stage is preferably 0.5 to 4 mm, more preferably 0.7 to 3 mm, and particularly preferably 0.8 to 2 mm. The bead diameter of the bead mill after the second stage is preferably smaller than the bead diameter of the first stage, preferably 0.02 to 1 mm, more preferably 0.04 to 0.6 mm, and particularly preferably 0.05 to 0.3 mm.

The material of the bead is preferably zirconia, alumina, glass, steel, super hard alloy, steel ball, ceramic, or the like. Among them, steel beads, zirconia beads, ceramic beads or glass beads are preferred, and steel beads, zirconia beads or ceramic beads are particularly preferred. Because of its superior wear resistance, chemical resistance, heat resistance, thermal conductivity, etc., and a large proportion.

In the present invention, the dispersion time for dispersion by the dispersing machine is not particularly limited, and is preferably 0.01 to 50 hours, more preferably 0.02 to 30 hours, and particularly preferably 0.05 to 10 hours, in order to appropriately set the dispersed particle diameter of the pigment.

In the wet dispersion, (A) the pigment (a) can be finely dispersed to achieve high contrast, in particular, by using the above disperser or dispersion conditions.

In the method for producing a pigment dispersion liquid of the present invention, it is particularly preferred to continue the dry dispersion treatment, "the above S/N obtained by the dry dispersion treatment is 90 or less (A) In the pigment (a), the above (B) dispersant and the above (C) solvent are blended and wet-dispersed.

By performing the above dry dispersion treatment and performing the above-described wet dispersion, fine dispersion of the pigment can be carried out in the pigment dispersion liquid, and the dispersion time of the wet dispersion can be shortened.

As a result of producing a pigment dispersion liquid in which a pigment is finely dispersed, a display using a color filter obtained by using the pigment dispersion liquid is a display having high contrast, high light transmittance, and high luminance.

Here, the term "continuous dry dispersion treatment" refers to the second step of the production process, followed by the dry dispersion treatment followed by the wet dispersion, and the temporary placement of the (A) pigment (a) having an S/N of 90 or less is excluded. Other containers are stored again after long-term storage (for example, storage for more than one month).

The period from the dry dispersion treatment to the wet dispersion treatment is preferably within one month, more preferably within two weeks, particularly preferably within one week, further preferably within two days, and preferably within one day. In the case where the pigment subjected to the dry dispersion treatment is stored for a long period of time (for example, storage for more than one month), the occurrence of aggregates is small.

Further, after the operation of "dry dispersion treatment for wet dispersion", the salt milling is carried out instead of the dry dispersion treatment before the wet dispersion.

In the above-mentioned "continuous dry dispersion treatment", it is preferred that the (A) pigment which is subjected to dry dispersion treatment is directly (solid or solidified), and is not temporarily stored in another container, that is, the second operation is carried out.

Therefore, compared with the case where the (A) pigment which has been subjected to the dry dispersion treatment is temporarily placed in another container and stored for a long period of time (for example, stored for more than one month), and then the second operation is performed, the occurrence of agglomerates is less. Further, the pigment in the pigment dispersion can be further dispersed to enhance the contrast. Further, the dispersion time of the wet dispersion can be further shortened.

It is used in the above dry dispersion treatment, and there is a In the dry dispersion treatment container of the (A) pigment (a) having the S/N of 90 or less after the dry dispersion treatment, at least the operation of adding the above (C) solvent is carried out, thereby preparing the (A) pigment and the above ( B) a "dispersing agent" and a "method for producing a pigment dispersion" of the above (C) solvent.

After the completion of the dry dispersion treatment, (C) a solvent is added to the (A) pigment (a) present in the dry dispersion-treated container, and the (A) pigment is washed off by the (C) solvent, and the second pigment is placed. It is also preferred to use a container for dispersion.

By performing wet dispersion by the subsequent dry dispersion treatment, re-aggregation, easy microdispersion, time saving, and cost reduction can be prevented.

Further, in the case of performing salt milling instead of the dry dispersion treatment, fine dispersion can be performed in the subsequent wet dispersion, and the entire working time can be shortened. Further, as a result of producing a pigment dispersion liquid in which the pigment is finely dispersed, a display using a color filter obtained by using the pigment dispersion liquid is a display having high contrast, high light transmittance, and high luminance.

In the range of the object of the invention, the (A) pigment (a) may be additionally blended with "S/N more than 90 (A) pigment" and wet-dispersed. (A) The pigment (a) having a S/N of 90 or less is not particularly limited as long as the proportion of the (A) pigment as a whole, and (A) the pigment (a) is preferably 30% by mass based on the total of the pigment (A). The above is more preferably 50% by mass or more, particularly preferably 70% by mass or more, and still more preferably 90% by mass or more.

(A) The pigment (a) and the "(A) pigment having an S/N exceeding 90" may be different types of pigments, and may be the same type of pigment.

In the case of the same type of pigment, since the main peak has the same 2θ, it is preferable that the (A) pigment overall system S/N is 90 or less.

1-6. The state of the pigment dispersion

Pigment in a pigment dispersion produced by the method for producing a pigment dispersion of the present invention The average dispersed particle diameter is not particularly limited, but is preferably 8 nm to 150 nm, more preferably 10 nm to 100 nm, and particularly preferably 12 nm to 70 nm.

Here, the average dispersed particle diameter of the pigment in the pigment dispersion liquid (hereinafter sometimes referred to simply as "average dispersed particle diameter") is a dispersed particle diameter of the pigment particles dispersed in a dispersion medium containing at least a solvent, and is irradiated with laser light. Determined by the scattering particle size distribution meter. As the particle diameter measurement by the laser light scattering particle size distribution meter, the pigment dispersion liquid is appropriately diluted to a concentration (for example, 1000 times or the like) which can be measured by a laser light scattering particle size distribution meter by using a solvent used for the pigment dispersion liquid. The measurement was carried out by a dynamic light scattering method at 23 ° C using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle diameter here is a volume average particle diameter.

If the average dispersed particle size is too small, the light resistance is lowered. On the other hand, if the average dispersed particle size is too large, a display using the color filter obtained by using the pigment dispersion is used, and the contrast is low and the light transmittance is low. Low, can not be a high-intensity display.

After the dispersion, it is usually filtered by a filter of 0.05 μm to 10.0 μm, preferably 0.1 μm to 5.0 μm, to obtain a pigment dispersion liquid of the invention.

1-7. Use of pigment dispersion

As described later, the pigment dispersion liquid of the present invention is a color filter material, a colored resin composition for a color filter, a photosensitive colored resin composition for a color filter, a liquid crystal display material, an organic EL display material, and a printing ink. Materials, coating materials, etc. In particular, it can be used as a colored resin composition for a color filter.

2. Photosensitive colored resin composition

A photosensitive colored resin composition containing (D) an alkali-soluble resin, (E) a polymerizable polyfunctional compound, and (F) a photopolymerization initiator, which is suitable for obtaining color, is used in the pigment dispersion liquid of the present invention. A liquid crystal display having the color filter or an organic EL display having the color filter, such as a filter, can exhibit the effects of the present invention described above.

2-1. (D) Alkali Soluble Resin

Here, the (D) alkali-soluble resin is not particularly limited, and may be used if it is suitable for development in an alkaline developer.

As the (D) alkali-soluble resin, a copolymer having a monomer having an acid group as a copolymerization component is preferable. Further, it may be one in which an acid group is introduced after the polymer.

Here, examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid (methylene succinic acid); 4-hydroxyphenyl maleimide a monomer having a phenolic hydroxyl group; a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride; and the like.

Further, in the (D) alkali-soluble resin of the present invention, from the viewpoint of enhancing the sensitivity, the photosensitive colored resin composition is photocured by image exposure, and the unexposed portion is developed to form a strong image. It is preferred to introduce a radical polymerizable double bond.

When a radically polymerizable double bond is introduced, for example, a monomer capable of introducing a radical polymerizable double bond after polymerization is subjected to (co)polymerization, and then a radical polymerizable double bond described later is introduced into the side chain.

Examples of the "monomer capable of introducing a radically polymerizable double bond after polymerization" include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, maleic anhydride, and itaconic anhydride. a monomer having a carboxylic anhydride group;

Examples of the compound used for the introduction of the radically polymerizable double bond include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho or meta or ethylene. A compound having an "epoxy group and a radical polymerizable double bond" such as a benzyl epoxidized propyl ether.

The acid group of the "monomer capable of introducing a radically polymerizable double bond after polymerization" is reacted with an epoxy group of a compound having an "epoxy group and a radical polymerizable double bond" to obtain a radical polymerizable double. Key (D) alkali soluble resin.

In the (D) alkali-soluble resin, a monomer copolymerizable with the above may be used as the monomer (hereinafter simply referred to as "other monomer"), and for example, it may have ethylenic unsaturation. The monomer of the double bond, specifically, for example, a styrene monomer such as styrene or α-methylstyrene; methyl (meth)acrylate, ethyl (meth)acrylate, or (meth)acrylic acid Propyl ester, isopropyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, a (meth) acrylate monomer such as benzyl (meth) acrylate or hydroxyethyl (meth) acrylate; (meth) acrylamide, N-methylol acrylamide, N, N-di a (meth) acrylamide-based monomer such as methacrylamide or N,N-dimethylaminoethyl acrylamide; vinyl acetate; an olefin such as acrylonitrile or allyl alkyl ether a propyl compound; a maleic acid amine monomer such as benzyl maleic acid amide or N-phenyl maleic acid amide; or the like.

The above-mentioned "monomer having an acid group", "a monomer capable of introducing a radical polymerizable double bond after polymerization", "a compound for introducing a radical polymerizable double bond", and "other monomer" are used. In this case, one type or two or more types may be used for the (co)polymerization.

The acid value of the (D) alkali-soluble resin in the present invention is particularly limited, and is preferably 30 to 200 mgKOH/g, more preferably 40 to 150 mgKOH/g, particularly preferably 50 to 120 mgKOH/g.

If the upper limit of the acid value is less than or equal to the above value, sufficient adhesion to the substrate can be obtained; When the lower limit is at least the above value, sufficient alkali developability can be obtained.

The molecular weight of the (D) alkali-soluble resin in the present invention is not particularly limited, and is usually 3,000 to 25,000, preferably 4,000 to 20,000, and particularly preferably 5,000 to 15,000, in terms of polystyrene-equivalent weight average molecular weight (Mw).

When the upper limit of the weight average molecular weight (Mw) is less than or equal to the above value, the compatibility with other constituent components is improved. When the lower limit is at least the above value, the adhesion to the substrate is improved.

2-2. (E) Polymeric polyfunctional compound

The (E) polymerizable polyfunctional compound is not particularly limited, and a known polymerizable polyfunctional compound can be used.

The "polymerizable polyfunctional compound" is not particularly limited as long as it has two or more polymerizable functional groups in one molecule, and examples thereof include polyether (meth) acrylate and ethyl urethane (meth) acrylate. a polyfunctional (meth) acrylate such as an epoxy group (meth) acrylate; a polyfunctional allylic compound such as diallyl phthalate or triallyl isocyanurate; or the like.

Among them, specific examples of the polyether (meth) acrylate include the following.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Linear alkanediol di(meth)acrylate such as alcohol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene Alcohol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #300 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate , polyethylene glycol #600 di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol #400 two Alkylene glycol di(meth)acrylate such as (meth) acrylate or polypropylene glycol #700 di(meth) acrylate; pentaerythritol di(meth) acrylate, pentaerythritol di (a) a part (meth) acrylate of an alcohol having a valence of 3 or more, such as acrylate monostearate or pentaerythritol di(meth) acrylate monobenzyl benzoate; bisphenol A di(meth) acrylate, EO modified bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, hydrogenated bisphenol A di(meth) acrylate, EO modified hydrogenated bisphenol A II Acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, PO modified bisphenol Bis(meth)acrylate, EO-modified bisphenol-based di(meth)acrylate such as tetrabromobisphenol A di(meth)acrylate; neopentyl glycol di(meth)acrylate, new Pentyl glycol PO modified di(meth) acrylate; hydroxytrimethylacetic acid neopentyl glycol di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol ester caprolactone adduct (meth) acrylate; 1,6-hexanediol bis(2-hydroxy-3-propenyloxypropyl)ether; tricyclodecane dimethylol di(meth) acrylate, heterotrimerization Cyanate EO modified di(meth)acrylate;

Examples of the trifunctional (meth) acrylate include glycerol tri(meth)acrylate, glycerin PO modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trishydroxyl. Propane EO modified tri(meth) acrylate, trimethylolpropane PO modified tri(meth) acrylate, isomeric cyanuric acid EO modified tri(meth) acrylate, iso-cyanuric acid EO modified ε-caprolactone modified tris(meth) acrylate, 1,3,5-tripropylene decyl hexahydro-s-three Pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate tripropionate, and the like.

Examples of the tetrafunctional or higher (meth) acrylate include pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, tetramethylol ethane tetra (meth) acrylate, oligoester tetra (meth) acrylate, and the like.

These may be used alone or in combination of two or more.

Among them, specific examples of the ethyl urethane (meth) acrylate include the following.

For example, (A) a compound containing a (preferably plural) isocyanate group in a molecule, which is obtained by reacting a compound having a hydroxyl group with a (preferably plural) (meth)acryl group in the molecule. a constructor; (B) containing a compound having a plurality of hydroxyl groups to react a diisocyanate compound or a triisocyanate compound, and an unreacted isocyanate group of the obtained compound to have a hydroxyl group in the molecule such as hydroxyethyl (meth)acrylate A structure obtained by reacting a (meth)acrylic compound.

The bifunctional urethane (meth) acrylate may, for example, be a polymer of a hydroxyl group, an amine group or the like at both ends or both ends of the oligomer (c), and react the diisocyanate compound (d). The obtained "polymer or oligomer having an isocyanate group at both ends" further reacts a compound having a hydroxyl group and a (meth)acryl group in the molecule (e) at both ends thereof.

Examples of the polymer or oligomer (c) having a hydroxyl group at both terminals include an ester oligomer, an ester polymer, a urethane oligomer, a urethane polymer, and polyethylene glycol. Polypropylene glycol and the like.

Examples of the diol component of the ester include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, and 2. 2'-thiodiethanol and the like.

Examples of the dicarboxylic acid component of the ester include an alkanedicarboxylic acid such as oxalic acid, succinic acid, maleic acid or adipic acid; and an aromatic dicarboxylic acid such as citric acid or citric acid.

The diisocyanate compound (d) which reacts at both ends of the polymer or oligomer can be the same as the diisocyanate compound described in the item of the above polyvalent isocyanate compound (a).

Further, the "compound (e) having a hydroxyl group and a (meth)acrylic group in the molecule" which reacts at both ends of the polymer or oligomer having an isocyanate group at both ends is not particularly limited. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, etc. are mentioned.

The tribasic or higher urethane (meth) acrylate may, for example, be a compound having one hydroxyl group and one or more (meth)acrylic groups in the molecule, for the isocyanate group of the polyvalent isocyanate compound (a). The hydroxyl group of (b) is reacted.

The polyisocyanate compound (a) at this time is, for example, a compound having two isocyanate groups in the molecule, and examples thereof include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hydrogenated diphenyl group. Methane diisocyanate, 1,3-benzene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine II Isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylene diisocyanate, and the like.

Further, examples of the compound having three isocyanate groups in the molecule include a trimethylol group modified with isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate or the like. Propane adduct, biuret, isomeric cyanate, and the like.

The compound (b) having one hydroxyl group and one or more (meth)acrylic groups in the molecule may, for example, be hydroxyethyl (meth)acrylate; or three or more (p) hydroxyl groups in the molecule. a compound which reacts (p-1) (meth)acrylic acid with a hydroxyl group of the compound (b-1); a compound which causes a ring-opening reaction of (meth)acrylic acid with a (meth)acrylic acid; Wait.

In the compound (b), the compound (b-1) having a p group (p is an integer of 3 or more) in the molecule is reacted with (p-1) (meth)acrylic acid. The compound (b-1) having three or more hydroxyl groups in the molecule may, for example, be glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tetramethylolethane, diglycerin or di(III). Hydroxymethyl)ethane, bis(trimethylol)propane, dipentaerythritol, bis(tetramethylol)ethane; such ethylene oxide upgrading compounds; propylene oxide upgrading compounds; Ethylene oxide modified compound of isomeric cyanurate, propylene oxide modified compound, ε-caprolactone modified compound, oligoester, and the like.

Specific examples of the compound (b-1) include diglycerin, di(trimethylol)ethane, di(trimethylol)propane, dipentaerythritol, and di(tetrahydroxymethyl)ethane.

These may be used alone or in combination of two or more.

In particular, examples of the epoxy (meth) acrylate include p-ethylene glycol diepoxypropyl ether, diethylene glycol diepoxypropyl ether, and triethylene glycol diepoxypropyl ether. a diglycidyl ether of an alkanediol such as propylene glycol diepoxypropyl ether, dipropylene glycol diepoxypropyl ether or tripropylene glycol diepoxypropyl ether; glycerin such as glycerol diepoxypropyl ether Epoxypropyl ethers; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A PO modified diglycidyl ether, bisphenol F digoxypropyl A structure in which (meth)acrylic acid is added to a bisphenol-based compound such as a bisphenol-based compound such as an ether.

Further, for example, a structure having a structure of adding (meth)acrylic acid to the polycondensed epoxy resin may be mentioned.

In addition, for example, an epoxy resin having a structure obtained by reacting a condensed polymer such as a phenol novolac or a cresol novolak, and reacting with, for example, epichlorohydrin, and a (meth)acrylic acid may be added. Or an acid anhydride additive or the like.

These may be used alone or in combination of two or more.

2-3. (F) Photopolymerization initiator

The (F) photopolymerization initiator is not particularly limited, and a known one used for radical polymerization can be used. It is especially preferred for use in general color filter manufacturers.

Specific examples of such a photopolymerization initiator include a compound which generates a radical by ultraviolet energy, and examples thereof include a benzoin derivative and a diphenyl ketone derivative; Ketone, diethyl 9-oxosulfur Isopropyl 9-oxosulfur Wait for Ketone derivative or 9-oxosulfur Derivatives; Irgacure OXE-01, Irgacure OXE-02 (above, manufactured by BASF Japan); decyl ester compounds such as ADEKA OPT-N-1919 (made by Asahi Chemical Co., Ltd.); sulfonium chloride, chloromethyl polynuclear aromatic compound, a halogen-containing compound such as a chloromethyl heterocyclic compound or a chloromethyldiphenyl ketone; Classes; terpenoids; alkali hydrocarbon alkanes; redox couples of photoreducible pigments and reducing agents; organic sulfur compounds; peroxides;

As a photopolymerization initiator, there are mentioned, for example, rice ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl group. Ketone, 2-ethyl fluorenone, aromatic ketones such as phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc., benzoin ethers, methyl benzoin, Benzoin such as ethyl benzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxy) Phenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-tolylphenyl)-4,5-diphenylimidazole dimerization , 2,4,5-triaryl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethyl Amino-1-(4- Phenylphenyl)butanone, 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethylthiazole compound such as oxadiazole, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-three , 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-three 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-three ,2-(naphthalen-1-yl)-4,6-bis-trichloromethyl-s-three , 2-(4-ethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-s-three 2-(4-Butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-s-three Halomethyl-s-three Compound, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Polinylacetone, 1,2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, methyl benzylidene benzoate, 4-benzylidene-4'-methyldiphenyl sulfide, benzyl Methyl ketal, dimethylamino benzoate, p-dimethylamino benzoic acid isoamyl ester, 2-n-butoxyethyl-4-dimethylamino benzoate, 2 -chloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur , Ethylketone, 1-[9-ethyl-6-(2-methylbenzylmethyl)-9H-indazol-3-yl]-1-(o-ethylindenyl), 4-benzylformamidine Methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone, 1,2-octanedione, and the like.

Further, a photopolymerization initiator having a tertiary amine structure can be suitably used. A photopolymerization initiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in a molecule, so that a radical generated by a photopolymerization initiator is not easily deactivated by oxygen, and can be promoted The advantage of sensitivity.

For example, Irgacure 907, Irgacure 369 (above, BASF Japan Co., Ltd.), Hicure ABP (made by Kawaguchi Pharmaceutical Co., Ltd.), and the like are commercially available as a photopolymerization initiator having a ternary amine structure.

The photopolymerization initiator used in the present invention is not limited to one type, and two or more types may be used in combination.

2-4. Proportion

In the photosensitive colored resin composition, the content ratio of the (D) alkali-soluble resin to the (E) polymerizable polyfunctional compound is not particularly limited, and is (D) alkali-soluble, from the viewpoints of sensitivity, resolution, and developability. 100 parts by mass of the resin, the (E) polymerizable polyfunctional compound is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, particularly preferably 30 to 200 parts by mass.

The (D) alkali-soluble resin is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, based on the solid content of the photosensitive color-colored resin composition. Further, the (E) polymerizable polyfunctional compound is preferably 5 to 60% by mass, more preferably 10 to 40% by mass based on the total amount of the solid content.

The content ratio of the above (F) photopolymerization initiator is usually 0.2 to 30 parts by weight, preferably from 0.2 to 30 parts by weight, per 100 parts by weight of the (E) polymerizable polyfunctional compound, from the viewpoint of sensitivity, resolution and developability. 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.

The (F) photopolymerization initiator is preferably from 3 to 40% by mass, from 7 to 35% by mass, particularly preferably from 10 to 30% by mass, based on the solid content of the photosensitive colored resin composition.

The (A) pigment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, based on the solid content of the photosensitive colored resin composition.

If it is this range, coloring power, sensitivity, resolution, and developability will become favorable.

2-5. Other ingredients

Further, the photosensitive colored resin composition may further contain, for example, a surfactant for improving wettability, a leveling agent, a decane coupling agent for improving adhesion, an antifoaming agent, a shrinkage preventing agent, and the like. An antioxidant, an aggregation inhibitor, an ultraviolet absorber, or the like.

2-6. Modulation of photosensitive colored resin composition

The preparation of the photosensitive colored resin composition can be at least adjusted by the pigment dispersion The (D) alkali-soluble resin, (E) a polymerizable polyfunctional compound, and (F) a photopolymerization initiator are prepared by mixing "other components" as needed, and further mixing the solvent as needed.

As the pigment dispersion liquid, the pigment dispersion liquid of the present invention and, if necessary, other pigment dispersion liquids may be mixed at the time of preparation of the photosensitive coloring resin composition.

Since the photosensitive colored resin composition of the present invention is used by previously producing a pigment dispersion liquid, it is possible to effectively prevent the pigment from aggregating and to uniformly disperse it.

3. Color filter

The color filter usually has a transparent substrate, a light shielding portion, and a coloring layer. The color filter obtained by using the pigment dispersion of the present invention or using the above-mentioned photosensitive colored resin composition can achieve high contrast, and therefore, the above pigment dispersion can be used as a color filter material, a color filter. A photosensitive resin composition for a colored resin composition or a color filter is used.

3-1. Colored layer

The colored layer is not particularly limited as long as it is formed by curing the photosensitive colored resin composition of the present invention, and is usually formed on a light-shielding portion on a transparent substrate to be described later, depending on the type of pigment contained in the photosensitive colored resin composition. It is composed of three or more colored patterns.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer is adjusted by a coating method, a coating condition, and a photosensitive coloring. The solid content concentration, viscosity, and the like of the resin composition are appropriately controlled, and it is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.

First, the photosensitive colored resin composition of the present invention is applied onto a transparent substrate to be described later by a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed through a predetermined pattern mask to photopolymerize the (D) alkali-soluble resin and the (E) polymerizable polyfunctional compound.

Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam.

Further, after the exposure, in order to promote the polymerization reaction, heat treatment may be performed.

Next, development processing is carried out using a developing solution, and the unexposed portion is dissolved and removed, whereby a coating film is formed in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used.

After the development treatment, the developer is usually washed and the cured coating film of the resin composition is dried to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film.

3-2. Shading section

The light-shielding portion of the color filter is formed into a pattern on a transparent substrate to be described later.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape.

As the light shielding portion, for example, a black pigment is dispersed or dissolved in a binder resin. Metal film such as chromium or chrome oxide. The metal thin film may be a two-layer laminate of a CrOx film (x is an arbitrary number) and a Cr film, or a CrOx film (x is an arbitrary number), a CrNy film (y is an arbitrary number), and Cr may be further reduced in reflectance. A three-layer laminate of the film.

In the case where the light-shielding portion is formed by dispersing or dissolving the black coloring agent in the binder resin, the method of forming the light-shielding portion is, for example, a photolithography method using a resin composition for a light-shielding portion, a printing method, or an inkjet method. Wait.

In the above case, when a printing method or an inkjet method is used as a method of forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, and polyvinyl alcohol resin. , polyvinylpyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin , polyester resin, maleic acid resin, polyamide resin, and the like.

In the above case, when the photolithography method is used as the method of forming the light-shielding portion, examples of the binder resin include an acrylate type, a methacrylate type, a polyvinyl cinnamate type, or a cyclized rubber type. A photosensitive resin having a reactive vinyl group.

In this case, a photopolymerization initiator, a sensitizer, a coatability improver, and a development improver may be added to the resin composition for a light-shielding portion containing a black pigment such as carbon black or titanium black as a pigment or a photosensitive resin. , crosslinking agent, polymerization inhibitor, plasticizer, flame retardant, etc.

On the other hand, when the light-shielding portion is a metal thin film, as a method of forming the light-shielding portion, for example, a metal thin film formed by vacuum deposition or sputtering or the like can be formed by photolithography to form a metal. A method of performing metal etching by using a resist pattern on a film as a mask.

The film thickness of the light-shielding portion is set to be about 0.05 to 0.4 μm in the case of a metal thin film, and the black colorant is dispersed or dissolved in the binder resin. The situation is set according to 0.5~3μm.

3-3. Transparent substrate

The transparent substrate which is a color filter is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include a flexible transparent hard material such as quartz glass, an alkali-free glass, and a synthetic quartz plate, or a flexible transparent flexible material such as a transparent resin film or an optical resin plate.

The thickness of the transparent substrate is not particularly limited, and for example, a thickness of about 100 μm to 1 mm can be used.

Further, in the color filter of the present invention, in addition to the transparent substrate, the light shielding portion, and the coloring layer, for example, a protective layer or a transparent electrode layer, and further an alignment film or a column spacer may be formed.

4. Liquid crystal display and organic EL display

The color filter obtained by using the photosensitive colored resin composition containing the pigment dispersion liquid of the present invention is used for a display device such as a liquid crystal display or an organic EL display.

The application of the color filter to a liquid crystal display or an organic EL display is carried out by a generally known method.

A color filter obtained by using the photosensitive colored resin composition containing the pigment dispersion liquid of the present invention is a display having a high contrast ratio, a high light transmittance, and a high luminance, which is a liquid crystal display or an organic EL display.

In particular, the color filter for liquid crystal display obtained by using the pigment dispersion of the present invention is such that the pigment is finely dispersed, and the polarized light obtained by the liquid crystal material is eliminated, and if such a color filter is used, Provides high contrast, high penetration, high brightness liquid Crystal display.

The effect and effect of the pigment dispersion of the present invention which exhibits superior dispersibility, contrast, and the like have not been clearly elucidated, but can be considered as follows. However, the present invention is not limited to the scope of the following effects.

In the (A) pigment (a) having (S/N) of 90 or less in the present invention, since the crystallinity is low, it is considered that the (A) pigment has low firmness. Thereby, the (A) pigment (a) is easily finely pulverized and dispersed, that is, the fine dispersion of the pigment becomes easy.

Therefore, the pigment dispersion can exhibit superior dispersibility, contrast, and the like. In particular, by combining with the above (B) dispersant of the present invention, the dispersibility and contrast can be further multiplied.

[Examples]

The present invention will be more specifically described by the following examples, examples and comparative examples. However, the present invention is not limited thereto, and is not limited to the examples.

In the examples, CI Pigment Red 177 or the like may be simply referred to as "PR177", CI Pigment Yellow 150 or the like is simply referred to as "PY150", CI Pigment Yellow 180 or the like is simply referred to as "PY180", etc., CI Pigment Yellow 213, etc. It is abbreviated as "PY213" or the like, and CI Pigment Blue 15:6 or the like is simply referred to as "PB15:6" or the like, and CI Pigment Violet 23 or the like is simply referred to as "PV23".

<(A) Modulation of Pigment> [Modulation Example 1] (Modulation of Dry Dispersion Treatment of Pigment A)

10.0 parts by mass of CI Pigment Red 177 (PR177) having a S/N of 110 as a pigment, and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 9 hours to prepare a dry dispersion-treated pigment A. Dry Dispersion Treatment Pigment A had an S/N of 24.

[Modulation Example 2] (Modulation of dry dispersion treatment of pigment B)

10.0 parts by mass of CI Pigment Yellow 150 (PY150) having a S/N of 122 as a pigment and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 9 hours to prepare a dry dispersion-treated pigment B. The dry dispersion treatment of Pigment B had an S/N of 26.

[Modulation Example 3] (Modulation of dry dispersion treatment of pigment C)

10.0 parts by mass of CI Pigment Yellow 180 (PY180) having a S/N of 198 as a pigment and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 9 hours to prepare a dry dispersion-treated pigment C. The dry dispersion treated pigment C had an S/N of 54.

[Modulation Example 4] (Modulation of dry dispersion treatment of pigment D)

10.0 parts by mass of CI Pigment Yellow 213 (PY213) having a S/N of 259 as a pigment, and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk bottle, and a paint shaker (Asada Iron Works) The system was shaken for 9 hours to prepare a dry dispersion-treated pigment D. The dry dispersion treated pigment D had an S/N of 48.

[Modulation Example 5] (Modulation of dry dispersion treatment of pigment E)

10.0 parts by mass of CI Pigment Blue 15:6 (PB15:6) having a S/N of 102 as a pigment, and 5.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) (hereinafter sometimes abbreviated as "PGMEA"). 200 parts by mass of zirconia beads having a diameter of 10.0 mm were placed in a milk bottle and shaken for 9 hours with a paint shaker (made by Asada Iron Works Co., Ltd.) to prepare a dry dispersion-treated pigment E. The dry dispersion treated pigment E had an S/N of 29.

[Modulation Example 6] (Modulation of dry dispersion treatment pigment F~H)

10.0 parts by mass of CI Pigment Violet 23 (PV23) having a S/N of 221 as a pigment, and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 6, 9, and 12 hours, respectively, to prepare dry dispersion-treated pigments F, G, and H. The dry dispersion treatment pigments F, G, and H have S/N of 25, 10, and 2, respectively.

[Modulation Example 7] (Modulation of Dry Dispersion Treatment Pigment I)

10.0 parts by mass of CI Pigment Violet 23 (PV23) having a S/N of 221 as a pigment, and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 12 hours to prepare a dry dispersion-treated pigment P'. The dry dispersion treated pigment P' has an S/N of 2.

The dry dispersion treated pigment was prepared, transferred to a container, and stored at room temperature for 3 months. The dry dispersion-treated pigment P' which was stored at room temperature for 3 months was used as the dry dispersion-treated pigment I. The dry dispersion treated pigment I had an S/N of 2.

<(B) Synthesis of Dispersant> [Synthesis Example 1] (Synthesis of basic block type dispersant)

In a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and a starter agent were added via an addition funnel. 5.81 parts by mass of methyl ketene methyltrimethylsulfonyl acetal, and nitrogen substitution was sufficiently performed.

Thereafter, 0.5 part by mass of a catalyst of tetrabutylammonium o-chlorobenzoate in 1 mol/L acetonitrile was injected using a syringe, and the mass of the first monomer of methyl methacrylate 100 was measured using an addition funnel. The drip was dropped for 60 minutes. The reaction flask was cooled by an ice bath and the temperature was kept below 40 °C.

After 1 hour, 33.3 parts by mass of dimethylaminoethyl methacrylate of the second monomer was dropped over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to terminate the reaction.

The THF solution of the obtained basic block copolymer was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer A. Further, in the case of use, PGMEA was adjusted to have a solid content of 20% by mass.

The weight average molecular weight (Mw) of the thus obtained basic block copolymer A was confirmed by GPC under the above conditions, and as a result, methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA) were used. The composition ratio MMA/DMAEMA mass ratio was 3/1, the weight average molecular weight (Mw) was 8,120, the number average molecular weight (Mn) was 6,840, and the molecular weight distribution (Mw/Mn) was 1.19. This basic block copolymer A was used as the "basic block type dispersant".

[Synthesis Example 2] (Synthesis of Basic Graft Dispersant) <<Synthesis of Giant Monomer A>>

In a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 80.0 parts by mass of PGMEA was placed, and the mixture was heated to a temperature of 90 ° C while stirring under a nitrogen stream.

50.0 parts by mass of MMA, 30.0 parts by mass of n-butyl methacrylate (BMA), 20.0 parts by mass of benzyl methacrylate (BzMA), 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and α,α'-azo double A mixed solution of 1.0 part by mass of isobutyronitrile (AIBN) was dropped over 1.5 hours, and further reacted for 3 hours.

Then, the nitrogen gas flow was stopped, and the reaction solution was cooled to 80 ° C, and 8.74 parts by mass of 2-isocyanate ethyl methacrylate (manufactured by Karenz MOI (manufactured by Showa Denko Co., Ltd.)) and dibutyltin dilaurate 0.125 g were added. 0.125 parts by mass of p-methoxyphenol and 10 parts by mass of PGMEA were stirred for 3 hours to obtain a 49.5% solution of macromonomer A.

The weight average molecular weight (Mw) of the macromonomer A obtained by GPC was measured by the same method as the basic block copolymer. The macromonomer A had a weight average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw/Mn) of 2.10.

<<Synthesis of Basic Graft Copolymers Using Giant Monomer A>>

In a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 80.0 parts by mass of PGMEA was placed, and the mixture was heated to a temperature of 85 ° C while stirring under a nitrogen stream.

75.76 parts by mass of the macromonomer A solution obtained in Synthesis Example 2 (effective solid fraction 37.5 parts by mass), DMAEMA 12.5 parts by mass, N-dodecyl mercaptan 1.24 parts by mass, PGMEA 20.0 parts by mass, AIBN 0.5 parts by mass The mixed solution was dropped over 1.5 hours, and after heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was aged. After dripping for 10 minutes, it was aged at the same temperature for 1 hour to obtain a basic graft copolymer solution.

The obtained basic graft copolymer solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a basic graft copolymer A. This alkaline graft copolymer A was used as an "alkaline graft type dispersant".

Further, in the case of use, PGMEA was adjusted to have a solid content of 20% by mass.

The weight average molecular weight (Mw) and the like of the thus obtained basic graft copolymer A were measured by GPC in the same manner as in the case of the basic block copolymer. The basic graft copolymer A had a weight average molecular weight (Mw) of 11,480, a number average molecular weight (Mn) of 4,650, and a molecular weight distribution (Mw/Mn) of 2.47.

<Manufacture of Pigment Dispersion> [Manufacturing Example 1] (Manufacture of Pigment Dispersion A)

8 parts by mass of the solution A of the basic block type dispersant synthesized in Synthesis Example 1 as a dispersing agent (solid content: 1.6 parts by mass), dry dispersing-treating pigment A prepared in Preparation Example 1 5 parts by mass, and PGMEA 37 mass 50 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle, and shaken for 1 hour with a paint shaker (made by Asada Iron Works Co., Ltd.) as a preliminary pulverization, and then, a zirconia having a particle diameter of 2.0 mm was taken out. To the beads, 100 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and dispersion was carried out for 3 hours in the same manner as in the coating shaker to form a pigment dispersion liquid A. Further, the dry dispersion-treated pigment A prepared by the preparation example 1 was used within one day after the preparation.

[Manufacturing Example 2] (Manufacture of pigment dispersion B~I)

A pigment dispersion liquid was produced in the same manner as in Production Example 1 except that the dry dispersion-treated pigment A used in Production Example 1 was replaced with the dry dispersion-treated pigment B to I prepared in Preparation Examples 2 to 7, respectively. B~I" is used as the pigment dispersion B~I. Further, the dry dispersion-treated pigments B to H prepared in Preparation Examples 2 to 6 were used within one day after preparation, and the dry dispersion-treated pigment I prepared in Preparation Example 7 was used three months after preparation.

[Manufacturing Example 3] (Manufacture of pigment dispersion J~L)

8 parts by mass of the basic graft copolymer solution A synthesized in Synthesis Example 2 as a dispersing agent (solid content: 1.6 parts by mass), and 5 parts by mass of each of the dry dispersion-treated pigments F to H prepared in Preparation Example 6, PGMEA 37 50 parts by mass of zirconia beads having a particle size of 2.0 mm and a particle size of 2.0 mm were placed in a milk bottle, and oscillated by a paint shaker (made by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then, a particle size of 2.0 mm was taken out. The zirconium beads were added to 100 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and dispersed by a paint shaker for 3 hours in the same manner to form a pigment dispersion liquid J to L. The dry dispersion-treated pigments F to H prepared in Preparation Example 6 were used within 1 day after preparation.

[Modulation Example 8] (Modulation of dry dispersion treatment of pigment M)

10.2 parts by mass of CI Pigment Violet 23 (PV23) having a S/N of 221 as a pigment and 200 parts by mass of zirconia beads having a particle diameter of 10.0 mm were placed in a milk shake bottle to paint a shaker (Asada Iron Works) The system was shaken for 12 hours to prepare a dry dispersion-treated pigment M.

0.2 parts by mass of the dry dispersion-treated pigment M was taken out from the US milk bottle, and the next day, it was measured by an X-ray diffraction apparatus, and the result was S/N of 2.

[Manufacturing Example 4] (Manufacture of pigment dispersion liquid M)

Next, in a milk bottle containing the dry dispersion-treated pigment M used in Preparation Example 8, 74.0 parts by mass of PGMEA was added, and after shaking for 5 minutes with a paint shaker, zirconia beads having a particle diameter of 10.0 mm were removed and recovered. The PGMEA solution of the pigment M was dry-dispersed.

42 parts by mass of the PGMEA solution of the dry dispersion-treated pigment M and 8 parts by mass of the basic block copolymer solution A synthesized in Synthesis Example 1 as a dispersing agent (solid content: 1.6 parts by mass) 50 parts by mass of zirconia beads having a particle diameter of 2.0 mm, which was shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then, zirconia beads having a particle diameter of 2.0 mm were taken out, and a particle diameter of 0.1 mm was added. 100 parts by mass of the zirconia beads were similarly dispersed by a paint shaker for 3 hours to form a pigment dispersion liquid M.

[Manufacturing Example 5] (Manufacture of Pigment Dispersion N)

8 parts by mass of the solution A of the basic block type dispersant synthesized in Synthesis Example 1 as a dispersing agent (solid content: 1.6 parts by mass), and 4.7 parts by mass of the dry dispersion-treated pigment H prepared in Preparation Example 6, as "acidic" 0.3 parts by mass of "sulfuric acid derivative of PV23" synthesized by the method described in JP-A-2005-173459, 37 parts by mass of PGMEA, and 50 parts by mass of zirconia beads having a particle diameter of 2.0 mm are placed in the milk. In the bottle, a coating shaker (manufactured by Asada Iron Works Co., Ltd.) was shaken for 1 hour as a preliminary pulverization, and then zirconia beads having a particle diameter of 2.0 mm were taken out, and 100 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and similarly, Paint oscillation The device was dispersed for 3 hours as a final mash to prepare a pigment dispersion N.

[Comparative Manufacturing Example 1] (Manufacture of pigment dispersion A')

A pigment dispersion liquid was produced as a pigment dispersion by the same method as in Production Example 1, except that the dry dispersion-treated pigment A used in Production Example 1 was replaced with the untreated PR177 (S/N = 1010) used in Preparation Example 1. Liquid A'.

[Comparative Manufacturing Example 2] (Manufacture of pigment dispersion B'~F')

A pigment dispersion liquid was separately produced in the same manner as in Production Example 2, except that the dry dispersion-treated pigments B to E used in Production Example 2 were replaced with the respective untreated pigments of the dry dispersion-treated pigment used in Production Example 2, respectively. Corresponding to the dry dispersion treatment of the pigments B to E, respectively, as the pigment dispersions B' to E'.

In addition, it is produced by the same method as in Production Example 2 except that the dry dispersion treatment pigments F, G, and H (the time of the dry dispersion treatment is different, and the PV23 is common), and the PV23 which is not subjected to the dry dispersion treatment is used. A pigment dispersion as a pigment dispersion F'.

[Comparative Manufacturing Example 3] (Manufacture of pigment dispersion G')

The same procedure as in Production Example 3 except that the dry dispersion-treated pigments F, G, and H (all of which are common to PV23) used in Production Example 3 were replaced with the untreated pigment PV23 of the dry dispersion-treated pigment used in Production Example 3. In the method, a pigment dispersion liquid is produced as a pigment dispersion liquid G'.

[Synthesis Example 3] (Synthesis of alkali soluble resin)

300 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 90 parts by mass of phenoxyethyl methacrylate (PhEMA) and 54 parts by mass of methyl methacrylate (MMA) were obtained. 36 parts by mass of acrylic acid (MAA), 6 parts by mass of PERBUTYL-O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of a chain shifting agent (N-dodecyl mercaptan) were continuously dropped over 1.5 hours.

Thereafter, the reaction was continued at 100 ° C, and after the completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol as a polymerization inhibiting agent was added to stop the polymerization.

Then, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added while blowing air, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto to be added at 110 ° C. After reacting for 15 hours, an alkali-soluble resin A (weight average molecular weight (Mw): 8500, acid value: 75 mgKOH/g, and solid content: 40% by mass) was obtained.

Further, the above-mentioned weight average molecular weight (Mw) of the alkali-soluble resin is determined by using Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070.

[Example 1]

(D) Alkali-soluble resin A: 1.28 parts by mass

(E) Polymerizable polyfunctional compound (trade name: ARONIX M403, manufactured by Toagosei Co., Ltd.): 1.19 parts by mass

(F) Photopolymerization initiator

2-methyl-1[4-(methylthio)phenyl]-2- Lolinylpropan-1-one (trade name: Irgacure 907, manufactured by BASF Corporation): 0.17 parts by mass

2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1 (trade name: Irgacure 369, manufactured by BASF Corporation): 0.13 parts by mass

To the above composition, 5.28 parts by mass of PGMEA was added and stirred to obtain a transparent resist composition. To the obtained transparent resist composition, 11.95 parts by mass of the pigment dispersion liquid A obtained in Production Example 1 was added to obtain a photosensitive colored resin composition belonging to a red resist composition.

[Examples 2 to 4 and Comparative Examples 1 to 4]

The pigment dispersion liquid A used in Example 1 was replaced with the pigment dispersion liquids B to D obtained in Production Example 2 and the pigment dispersion liquids A' to D' obtained in Comparative Production Examples 1 and 2, respectively, in the same manner as in Example 1. In the method, a photosensitive colored resin composition of the colored resist composition was obtained.

[Example 5]

(D) alkali-soluble resin A: 1.78 parts by mass

(E) Polymerizable polyfunctional compound (trade name: ARONIX M403, manufactured by Toagosei Co., Ltd.): 1.66 parts by mass

(F) Photopolymerization initiator

2-methyl-1[4-(methylthio)phenyl]-2- Orolinylpropan-1-one (trade name: Irgacure 907, manufactured by BASF Corporation): 0.23 parts by mass

2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1 (trade name: Irgacure 369, manufactured by BASF Corporation): 0.19 parts by mass

Add 10.16 parts by mass of PGMEA to the above composition and stir to obtain A transparent resist composition. To the obtained transparent resist composition, 5.98 parts by mass of the pigment dispersion liquid E obtained in Production Example 2 was added to obtain a photosensitive colored resin composition belonging to the blue resist composition.

[Examples 6 to 14 and Comparative Examples 5 to 7]

The pigment dispersion liquid E used in Example 5 was replaced with the pigment dispersion liquids F to N obtained in Production Examples 2 to 5 and the pigment dispersion liquids E' to G' obtained in Comparative Production Examples 2 and 3, respectively. In the same manner, a photosensitive colored resin composition of the colored resist composition was obtained in the same manner.

[Evaluation method] <Measurement method of S/N> <<Measurement method of intensity (S) of main peak and background noise intensity (N)>>

The (A) pigment was decomposed by a mortar to remove coarse particles.

In the case of (A) pigment filling, a glass sample plate having a standard bottom which was etched with a sample filling portion of 2.0 mm × 2.0 mm × 0.2 mm was used. As a bottomed glass sample board, a glass sample board made of RIGAKU Co., Ltd. 20×20 base 0.2 was used.

The (A) pigment is placed in the filling portion, and the (A) pigment is pressed and uniformly filled by another glass plate or the like. In order to reduce the error, the pigment surface is made the same as the glass sample plate.

The main peak intensity (S) and the background noise intensity (N) were determined according to the above measurement methods and definitions.

A schematic diagram showing the spectrum of the main peak intensity (S) with the background removed and the background noise intensity (N) of the background removed is shown in Fig. 1.

That is, the above-mentioned "filling portion of the sample" is measured by a powder X-ray diffraction device. A bottomed glass sample plate filled with (A) pigment.

In the X-ray diffraction spectrum, an X-ray diffraction device belonging to a concentrated optical system and a "RINT-TTR III" manufactured by RIGAKU Co., Ltd. using CuKα ray as an X-ray source are used, and measurement conditions are set as a scanning area 2θ=3 to 55. °, sample width 0.02 °, scanning speed 5 ° / min, divergence slit 1/4, scattering slit 1/4, light receiving slit 0.45 mm.

The main peak intensity (S) and the background noise intensity (N) are obtained by subtracting the background from the X-ray diffraction spectrum by the above method.

The calculation method and definition of "background noise intensity (N)" are as described above, and the peak height from the noise in the scanning range 2θ=47.5° to 48.0° is detected at a total of 26 points per 0.02°. At 26 o'clock, the sum of the average of 12 points of 7 points above and below is removed as "background noise intensity (N)".

As an example, Table 1 below shows the background of Comparative Example 1 using the pigment dispersion liquid A in which the PR177 was subjected to dry dispersion treatment and wet dispersion, and the pigment dispersion liquid A' in which the PR177 was directly wet-dispersed. The measured value of the noise intensity (N) and the specific calculation method.

Further, in Example 1, a pigment dispersion liquid A (S/N = 24, N = 107) was used, and in Comparative Example 1, a pigment dispersion liquid A' (S/N = 110, N = 79) was used.

The italicized bold part of Table 1 is a total of 12 points from the upper and lower points of the 26 points, and the numerical value of the average value is obtained.

<"Measurement of TEM particle size of (A) pigment>

The "TEM particle size of the (A) pigment used in the production of the pigment dispersion liquid, that is, the particle diameter of the pigment (the average particle diameter of the pigment before wet dispersion)" was measured and defined as described above. For those who are measured as such.

That is, as described above, a 200,000-times STEM photograph is taken and loaded into the following software. Depending on the photograph, 100 pigments are arbitrarily selected, and the diameter (the length of the end diameter) is measured, and the distribution of the volume basis is determined by the 50% cumulative particle diameter by volume, that is, the diameter of the volume distribution (D50), which is taken as "(A). ) TEM particle size of the pigment.

The measurement results are shown in Table 2.

<Measurement of "average dispersed particle size" >

The measurement of the average particle diameter of the pigment dispersion liquid obtained in each of the examples and the comparative examples was carried out. In the measurement of the average dispersed particle size, the "Nanotrack particle size distribution measuring device UPA-EX150" manufactured by Nikkiso Co., Ltd. was used to dilute the pigment dispersion to 1000 times, and the concentration can be measured by a laser light scattering particle size distribution meter. Determination.

<Comparative evaluation>

In order to evaluate the performance of the color filter, the photosensitive colored resin compositions of the colored resist compositions of Examples 1 to 12 and Comparative Examples 1 to 7 were each placed on a glass substrate having a thickness of 0.7 mm and 10 mm × 10 mm ( It was coated with a spin coater, manufactured by NH Techno Glass Co., Ltd., and then dried using a hot plate at 80 ° C for 3 minutes to form a colored layer having a dry thickness of 2.5 μm .

The colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and post-baking was performed at 230 ° C for 30 minutes, and the parallel luminance and the orthogonal luminance of the obtained colored plate were measured and compared.

The measurement of the luminance was carried out by using the kettle-electrical mechanism comparison measuring device CT-1 (light source: F10 lamp between cold cathodes, luminance meter: LS-100 manufactured by KONICA-MINOLTA, spectrophotometer: CS-1000T manufactured by KONICA-MINOLTA).

Contrast = parallel luminance (cd/m ² ) / orthogonal luminance (cd/m ² )

The results of the comparison, the type and physical properties (crystallinity, etc.) of the (A) pigment used in the production of the pigment dispersion, (B) the dispersant, the time from the dry dispersion to the wet dispersion, and the particles before and after the final dispersion Paths, etc., are shown together in Table 2.

From the results of the above Table 2, it can be clarified that the coloring layers (Examples 1 to 14) obtained by using the pigment dispersions A to N produced by the method for producing a pigment dispersion of the present invention are used in comparison with the use. The pigment dispersions A' to G' produced by the same pigment and the pigment having an S/N of more than 90 were greatly improved in comparison.

This situation is visible regardless of the pigment. This is seen in the dispersant in any of the dispersants evaluated.

Even if the S/N is made into a pigment of 90 or less after the dry dispersion treatment, the TEM particle size of the pigment does not necessarily decrease, and the TEM particle size of the pigment is not small, and the dispersion is better, and the TEM particle size of the pigment. There is no meaningful correlation between the comparison with the final composition.

(industrial availability)

The pigment dispersion liquid produced by the method for producing a pigment dispersion liquid of the present invention has excellent dispersibility and dispersion stability, and a color display such as a liquid crystal display or an organic EL display obtained by using the pigment dispersion liquid of the present invention is high in contrast. It has a high light transmittance and a high-brightness display. It can be widely used in various types of printing inks such as inkjet, gravure, lithography, screen, and letterpress, various coatings, coatings, and color resists. In the field of agents and the like, there are display fields such as liquid crystal displays and organic EL displays, and various component manufacturing fields.

Claims (13)

A method for producing a pigment dispersion liquid, which is a method for producing a pigment dispersion liquid containing at least (A) a pigment, (B) a dispersant, and (C) a solvent, which comprises the step of removing a background by X-ray diffraction spectrum (A) pigment (a) is obtained by dividing the main peak intensity (S) by the value (S/N) of the background noise intensity (N) obtained by removing the background from the X-ray diffraction spectrum to 90 or less. (A) Pigment, which is wet-dispersed. The method for producing a pigment dispersion liquid according to the first aspect of the invention, wherein the (B) dispersant is at least one selected from the group consisting of an alkaline block type dispersant and a basic graft type dispersant. The above dispersant. The method for producing a pigment dispersion liquid according to claim 1, wherein the (A) pigment having the above S/N of 90 or less is obtained by subjecting the pigment of (A) having an S/N of more than 90 to dry dispersion treatment. ). The method for producing a pigment dispersion liquid according to the third aspect of the invention, wherein the S/N of the (A) pigment after the dry dispersion treatment is divided by the S/N value of the (A) pigment before the dry dispersion treatment becomes 0.5. In the following manner, the dry dispersion treatment is carried out to obtain the (A) pigment (a) having the above S/N of 90 or less. The method for producing a pigment dispersion liquid according to the third aspect of the invention, wherein the dry dispersion treatment is carried out to obtain the (A) pigment (a) having an S/N of 90 or less, and the dry dispersion treatment is carried out to prepare the above (B) The dispersant and the above (C) solvent are wet-dispersed. The method for producing a pigment dispersion liquid according to the fifth aspect of the invention, wherein the dry dispersion treatment is carried out, and the (A) pigment having an S/N of 90 or less after the dry dispersion treatment is present therein In the dry dispersion treatment container of (a), at least the above-mentioned (C) solvent is added to prepare the above-mentioned (A) pigment, the above (B) dispersant, and the above (C) solvent. The method for producing a pigment dispersion liquid according to any one of claims 1 to 6, which further comprises an acidic dye derivative. The method for producing a pigment dispersion according to claim 7, wherein the acidic dye derivative is previously contained in the (A) pigment, or the acid dye derivative is formulated during dry dispersion treatment, or is wet. The above acidic dye derivative is blended in the form of dispersion. A pigment dispersion liquid produced by the method for producing a pigment dispersion liquid according to any one of claims 1 to 8. A colored resin composition for a color filter, which comprises the pigment dispersion of claim 9 of the patent application. A colored resin composition for a color filter, characterized in that, in the pigment dispersion of claim 10, further comprising at least (D) an alkali-soluble resin, (E) a polymerizable polyfunctional compound, and (F) Made of photopolymerization initiator. A color filter obtained by using a colored resin composition for a color filter of claim 10 or 11. A display display device having the color filter of claim 12 of the patent application.