JP2017090779A - Manufacturing method for color filter pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a pigment composition which is superior in terms of dispersibility and dispersion stability of a pulverized pigment, contrast ratio, voltage holding ratio, and migration property, and to provide a color filter pigment composition.SOLUTION: The afore-mentioned problem is cleared by employing a color filter pigment composition manufacturing method which involves coating pigment surfaces by adding, to a pigment, a pigment derivative and a kneaded resin obtained by polymerizing a monomer containing an ethylenic unsaturated monomer having a specific structure, and then wet-kneading the mix.SELECTED DRAWING: None

Description

The present invention relates to a pigment composition containing a micronized pigment and a method for producing the same. Furthermore, it is related with the pigment composition for color filters containing the said pigment composition.

The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a photosensitive coloring composition. It is manufactured by forming a colored pattern or a black matrix by a method or an ink jet method.

In recent years, color filters tend to be used for liquid crystal display elements (LCDs as well as monitors as well as televisions (TVs). With this trend of expanding applications, color filters have a high degree of color in contrast and the like. In addition, color filters for use in image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution. .

In response to the above requirements, the pigment contained in the colored composition or the photosensitive colored composition is dispersed in a finer state (good dispersibility), and dispersed in a stable state (good Dispersion stability) is required. When the dispersibility of the pigment is insufficient, the colored pixels formed by the photolithographic method have fringes (jagged edges) and surface irregularities, and there are many development residues (residues) on the substrate. In addition, there are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the photosensitive coloring composition is reduced, or the sensitivity in the exposure process. Or the alkali solubility in the development process is likely to be reduced. Further, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the photosensitive coloring composition are aggregated to increase the viscosity with time and the pot life is extremely shortened.

In order to improve color characteristics such as contrast of color filters, it is effective to reduce the particle diameter of the pigment. However, if the pigment particles are made finer, the cohesive force between the pigment particles becomes stronger, and at a high level. It is often difficult to achieve both dispersibility and dispersion stability.

The following is known regarding the refinement of pigment particles and the improvement of dispersibility. In general, the primary particle size reduction of pigments is well known by a method of kneading a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader (salt milling method). It has been. The mixture of primary particles of the obtained fine pigment is put into water and stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water and dried to obtain a fine pigment as a secondary aggregate which is an aggregate of primary particles of the pigment. The dispersion process in a normal disperser such as a sand mill or a ball mill is a process of obtaining a dispersion in a state close to primary particles by loosening secondary aggregates that are aggregates of primary particles of the pigment.

However, when the primary particles of the pigment are refined, the particles are easily aggregated, and an aggregate (secondary aggregate) is easily generated during slurry or drying. Further, as the primary particles of the pigment become finer, strong secondary aggregation tends to occur. Furthermore, the pigment aggregates are eluted, the voltage holding ratio is remarkably lowered, or the color is transferred to the other color segment, and the other color is contaminated, thereby causing a dye transfer property that causes a decrease in lightness. . For this reason, it is generally very difficult to re-disperse the refined pigment to primary particles. A color filter formed using a dispersion containing a large amount of secondary aggregates has a large light scattering, and the contrast is remarkably lowered and color density unevenness is caused. It is desired that the primary particles are stably dispersed and easy to handle.

In order to suppress the strong secondary aggregation of the finely divided pigment, a rosin or rosin derivative, or a water-insoluble monomer or oligomer is added during the salt milling process to treat the pigment, and the pigment dispersion There has been proposed a technique for obtaining a color filter with high contrast by using (see Patent Documents 1 and 2).

On the other hand, in the case of phthalocyanine pigments, it is known that the kneading process is easily affected by crystal transition due to temperature. For example, when kneading treatment (wet kneading) is performed at a low temperature, a crystal transition from ε-type to α-type occurs, and it is a problem that an ε-type phthalocyanine pigment having a desired hue cannot be obtained. Patent Documents 3 and 4 are known as methods for producing an ε-type phthalocyanine pigment that solves this problem.

However, even with these methods, it is not possible to meet the high demand performance from the market, and more advanced dispersibility and dispersion stability in fine pigments, as well as voltage holding ratio and transferability that causes multicolor contamination. Improvement was also desired.

JP-A-8-179111 JP 2004-233727 A JP 2007-332317 A JP2013-203868A

In the trend that demands for high definition become severe, it is important to make the pigment in the pigment composition of the color filter pigment composition and the color filter photosensitive pigment composition finer. However, when the pigment is refined, the pigments are likely to aggregate with each other, thereby causing problems such as a decrease in dispersibility and a deterioration in viscosity stability.

The present invention has been made in view of the above background, and the object of the present invention is to provide a pigment composition excellent in dispersibility and dispersion stability of a refined pigment and a good contrast ratio using the same. Then, it is providing the pigment composition excellent also in the voltage holding rate and dye transfer property, its manufacturing method, and the pigment composition for color filters.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a pigment composition obtained by coating a pigment surface by using a resin having a specific structure, and have reached the present invention.

［一般式（１）中、
Ｙは、−（ＣＨ_２ＣＨ_２Ｏ）_ｎ−、−（ＣＨ_２ＣＨ_２ＣＨ_２Ｏ）_ｍ−、−（ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_ｌ−、−ＣＨ_２ＣＨ_２Ｃ（＝Ｏ）Ｏ−、または直接結合であり、
ｎ、ｍ、ｌは、１〜１０の整数であり、
Ｒ_１は、水素原子、またはメチル基であり、
Ｒ_２は、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ That is, the present invention is a method for producing a pigment composition in which a pigment, a kneaded resin (A), and a pigment derivative are wet-kneaded,
A color characterized in that the kneaded resin (A) is a kneaded resin (A) obtained by polymerizing a monomer containing the ethylenically unsaturated monomer (a) represented by the general formula (1). The present invention relates to a method for producing a filter pigment composition.

[In general formula (1),
Y represents — (CH ₂ CH ₂ O) _n —, — (CH ₂ CH ₂ CH ₂ O) _m —, — (CH ₂ CH (CH ₃ ) CH ₂ O) ₁ —, —CH ₂ CH ₂ C ( = O) O-, or a direct bond,
n, m, and l are integers of 1 to 10,
R ₁ is a hydrogen atom or a methyl group,
R ₂ represents an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. ]

  The present invention also relates to the method for producing a color filter pigment composition, wherein in the general formula (1), Y is -CH2CH2O-.

In addition, the present invention relates to the method for producing a pigment composition for a color filter, wherein in the general formula (1), R ₂ is a phenyl group.

In the present invention, the kneaded resin (A) comprises an ethylenically unsaturated monomer (a) represented by the general formula (1) and an ethylenically unsaturated group having no aromatic ring or heterocyclic ring in the molecule. The present invention relates to a method for producing a pigment composition for a color filter, wherein the monomer (b) is radically polymerized.

The present invention also relates to the method for producing a pigment composition for a color filter, wherein the kneaded resin (A) is radically polymerized in a water-soluble organic solvent.

The present invention also relates to the method for producing a color filter pigment composition, wherein the pigment is an ε-type phthalocyanine pigment.

The present invention further relates to a method for producing a colored composition for a color filter, further comprising a dispersion resin, a binder resin, and an organic solvent.

The present invention further relates to a method for producing a color composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

Moreover, this invention relates to the manufacturing method of the color filter formed using the coloring composition for color filters manufactured by the said manufacturing method.

According to the present invention, a pigment composition excellent in dispersibility and dispersion stability of a finely divided pigment, a pigment composition having a good contrast ratio using the same, and an excellent voltage holding ratio and transferability, and There is an excellent effect that the production method and the pigment composition for a color filter can be provided.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ". Further, “CI” in the present specification means a color index (CI). Further, “%” in the present specification means mass% unless otherwise specified.

<Pigment>
As the pigment used in the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. As the pigment, an organic pigment is preferable in consideration of the high transmittance when the pigment composition of the present invention is used for a color filter coloring composition, and a pigment having a particle size as small as possible. It is preferable to use it. Considering the handling properties of the coloring composition and the photosensitive coloring composition containing it, the average primary particle diameter of the pigment composition is preferably 100 nm or less, more preferably 30 nm or less, and further preferably 5 to 25 nm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value. In addition, as a particle diameter of the pigment before using for a milling process, it is about 10 micrometers-300 micrometers.

Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 2 7,278,279,280,281,282,283,284,285,286,287 or diketopyrrolopyrrole pigments described in JP-T 2011-523433 discloses,, C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, C. I. Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, etc., zinc phthalocyanine pigments, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH 80, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. Pigment Black 1, 7, aluminum phthalocyanine, aluminum phthalocyanine described in JP-A No. 2004-333817, Japanese Patent No. 4893859, and the like.
However, the present invention is not limited to these.

Among these, pigments that can be preferably used include C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185, C.I. I. Pigment Orange 36, 71, C.I. I. Pigment Red 122, 150, 171, 175, 176, 177, 209, 224, 242, 254, 255, 264, 269, C.I. I. Pigment Violet 19, 23, 32, C.I. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66, C.I. I. Pigment Green 7, 36, 37, 58, C.I. I. Pigment Black 1, 7, aluminum phthalocyanine, and aluminum phthalocyanine described in JP-A No. 2004-333817, Japanese Patent No. 4893859, and the like. Among these, an ε-type phthalocyanine pigment is particularly preferable.

The ε-type phthalocyanine pigment used in the present invention is not particularly limited, but a commercially available ε-type phthalocyanine pigment having a large particle diameter can be used. In addition, the manufacturing method described in JP-A-57-141453, PIGMENTHANDBOOK, Volume 1, page 667 (1988), and “Phthalocyanine—Chemistry and Function” written by Yasuyoshi Shirai and Nagao Kobayashi, pages 55 to 62 ( (1997), phthalocyanine was synthesized by a known production method, and if necessary, an α-type phthalocyanine pigment was produced by an acid pasting method as disclosed in JP-A-48-76925, The α-type phthalocyanine pigment and the crystal stabilizer can be used for crystal transition by milling. The ε-type phthalocyanine pigment can be qualitatively and quantitatively determined by X-ray diffraction. The ε-type copper phthalocyanine pigment has the strongest diffraction peak at a Bragg angle 2θ (allowable range ± 0.2 degrees) = 9.2 degrees according to an X-ray diffraction diagram (CuKα line). The ε-type phthalocyanine pigment used in the present invention is not only a case where the content of the ε-type phthalocyanine pigment is 100% by weight, but also an ε-type phthalocyanine pigment partially containing α-type or β-type is also an ε-type phthalocyanine It is called a pigment. Specifically, the content of the ε-type phthalocyanine pigment as the crude ε-type phthalocyanine pigment is preferably 80% by weight or more, and more preferably 90% by weight or more.

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations of organic pigments are shown below. For example, as a red pigment, an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Alternatively, a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment can be mixed and used. For example, as an anthraquinone pigment, C.I. I. Pigment Red177, and perylene pigments include C.I. I. Pigment Red155, 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red254 and C.I. in terms of color reproducibility. I. Pigment Yellow 83, 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may be lowered. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as the green pigment, a halogenated phthalocyanine pigment is used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. be able to. For example, C.I. I. Pigment Green 7, 36, 37, 58 and C.I. I. Mixture with Pigment Yellow 83, 138, 139, 150, 180, 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. If the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength tends to be a long wavelength, and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As a blue pigment, a phthalocyanine pigment can be used alone or in combination with a dioxazine purple pigment. As a particularly preferred example, C.I. I. Pigment Blue 15: 6 and C.I. I. A mixture with Pigment Violet 23 can be mentioned. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable. The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60.

<Pigment derivative>
Examples of the pigment derivative include compounds obtained by introducing a basic substituent, an acidic substituent or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone or triazine. -305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469 and the like can be used alone. Alternatively, two or more types can be mixed and used. When a pigment derivative is used, those having an azo skeleton, a naphthol azo skeleton, a diketopyrrolopyrrole skeleton, an anthraquinone skeleton, a quinophthalone skeleton, and a perylene skeleton are preferable from the viewpoints of lightness and dispersibility.

The blending amount of the pigment derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100% by mass). 3% by mass or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount (100% by mass).
<Wet kneading>
By the wet kneading of the present invention, the pigment composition can be refined. The wet kneading of the present invention is preferably a salt milling process which is wet kneading and mixing. Salt milling is a process of heating a mixture of pigment, pigment derivative, water-soluble inorganic salt, and water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. In the present invention, the kneaded resin (A) is further added to the above mixture, and wet kneading is performed. The water-soluble inorganic salt works as a crushing aid, and it is considered that the pigment composition is crushed using the high hardness of the inorganic salt during salt milling, resulting in an active surface and crystal growth. It has been. Therefore, the crushing and crystal growth of the pigment composition occur simultaneously during kneading, and the primary particle size of the pigment composition obtained varies depending on the kneading conditions.

The temperature at which the kneaded composition is mechanically kneaded is not particularly limited, but is preferably treated at 20 to 90 ° C, more preferably at 30 to 70 ° C. Under the kneading conditions of 20 ° C. or more and 90 ° C. or less, the organic pigment particles are crushed and refined without reducing the throughput of the kneaded product, reducing the viscosity of the kneaded mixture, or using these operations together. The rate and the crystal growth rate of the organic pigment particles can be easily controlled, and a desired degree of fineness can be obtained.
When the temperature is lower than 20 ° C., crystal growth does not occur sufficiently, and the shape of the pigment composition particles becomes nearly amorphous, and in the case of a phthalocyanine pigment, there is a possibility that crystal transition to α-type may occur. On the other hand, when the kneading temperature exceeds 90 ° C., crystal transition to β-type may occur.

The kneading time is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the pigment composition subjected to the salt milling treatment and the cost required for the salt milling treatment.

By optimizing the conditions for salt milling the pigment composition, the primary particle size is very fine and the range of particle size distribution is not accompanied by crystal transition to α-type or β-type crystal structure. A narrow pigment composition can be obtained.

<Water-soluble inorganic salt>
The water-soluble inorganic salt used in the kneaded composition serves as a crushing aid, and crushes the pigment using the high hardness of the inorganic salt during salt milling, and the primary particles of the pigment are refined. Although it will not specifically limit if it melt | dissolves in water, For example, salt (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, or these mixtures can be mentioned, It is preferable to use sodium chloride from the viewpoint of price.

The amount of the water-soluble inorganic salt in the kneaded composition is not particularly limited, but is preferably in the range of 1 to 30 times by weight, more preferably in the range of 5 to 20 times by weight, It can be selected according to the target particle size. If it is 1 weight times or more, refinement and sizing are easy to proceed, and if it is 30 weight times or less, the amount of the pigment in the kneaded product is large, so that productivity is high and industrially advantageous.

The particle diameter of the water-soluble inorganic salt is not particularly limited, but is preferably 1 to 50 μm in terms of volume-based median particle diameter (D50). When D50 is 50 μm or less, the processing time for making the crude organic pigment fine is short, and when D50 is 1 μm or more, less energy is required to obtain a water-soluble inorganic salt. The particle diameter of the water-soluble inorganic salt can be determined using a dry-type laser diffraction particle size distribution analyzer.
<Water-soluble organic solvent>
As the water-soluble organic solvent used in the kneaded composition, a pigment, a resin and a water-soluble inorganic salt are added so as to form a uniform lump, which is freely mixed with water or not mixed freely but is industrial. In particular, those having a solubility enough to be removed by washing with water are desirable. Moreover, since the temperature of the kneaded composition rises during kneading and the water-soluble organic solvent is easily evaporated, a high boiling point solvent is preferable from the viewpoint of safety.

Preferred examples of the water-soluble organic solvent include diethylene glycol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine, tributyrin, and 2-methylpentane. At least one selected from -2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,2,6-hexanetriol Is mentioned. Moreover, you may mix and use 2 or more types of solvents as needed.

  The amount of the water-soluble organic solvent in the kneaded composition is not particularly limited, but the proportion in the kneaded composition is preferably 3 to 40% by weight, and the amount of the water-soluble inorganic salt and the kneaded composition Can be selected according to the hardness. When the water-soluble organic solvent is insufficient, the kneaded composition is not collected and energy is not applied, so it is difficult to make fine, or the kneaded composition becomes too hard, so that a stable operating state can be maintained. It can be difficult. Moreover, since the kneaded composition becomes too soft when it is excessively added, it may be difficult to obtain a desired degree of refinement and grain size.

［一般式（１）中、
Ｙは、−（ＣＨ_２ＣＨ_２Ｏ）_ｎ−、−（ＣＨ_２ＣＨ_２ＣＨ_２Ｏ）_ｍ−、−（ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_ｌ−、−ＣＨ_２ＣＨ_２Ｃ（＝Ｏ）Ｏ−、または直接結合であり、
ｎ、ｍ、ｌは、１〜１０の整数であり、
Ｒ_１は、水素原子、またはメチル基であり、
Ｒ_２は、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ <Kneaded resin (A)>
Kneading resin (A) will not be limited if it is resin formed by superposing | polymerizing the monomer containing the ethylenically unsaturated monomer (a) represented by General formula (1).

[In general formula (1),
Y represents — (CH ₂ CH ₂ O) _n —, — (CH ₂ CH ₂ CH ₂ O) _m —, — (CH ₂ CH (CH ₃ ) CH ₂ O) ₁ —, —CH ₂ CH ₂ C ( = O) O-, or a direct bond,
n, m, and l are integers of 1 to 10,
R ₁ is a hydrogen atom or a methyl group,
R ₂ represents an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. ]

  In the general formula (1), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.

In the general formula (1), examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline And a ring.

In the general formula (1), examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group; polymerizable functional groups such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group and epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; phenoxy Aryloxy groups such as benzyloxy groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfa Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyls Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; can be nitro group, a cyano group and the like; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

  Examples of the ethylenically unsaturated monomer (a) represented by the general formula (1) include phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethylene oxide modified (meth). Examples include acrylate, paracumylphenoxyethylene oxide modified (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 3-methyloxetanyl (meth) acrylate. Of these, phenoxyethyl (meth) acrylate is preferred.

  The ethylenically unsaturated monomer (a) represented by the general formula (1) is used in a proportion of 5 to 95% by weight based on the total amount of monomer components forming the kneaded resin (A). The ratio of the ethylenically unsaturated monomer (a) represented by the general formula (1) is preferably 30 to 90% by weight, and more preferably 60 to 80% by weight. If the proportion of the ethylenically unsaturated monomer (a) having one or more aromatic rings or heterocyclic rings in the molecule is less than the above range, the amount of resin adsorbed on the pigment is reduced, so that dispersibility and dispersion stability are reduced. Unsatisfied in that it cannot maintain the sex. Further, when the ratio of the ethylenically unsaturated monomer (a) represented by the general formula (1) is larger than the above range, the effect of the adsorptive capacity is preferably reduced due to a decrease in solubility in diethylene glycol as a kneading solvent. Absent.

(2) Ethylenically unsaturated monomer having no aromatic ring or heterocyclic ring in the molecule (b)
Examples of the ethylenically unsaturated monomer (b) having no aromatic ring or heterocyclic ring in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and alkyl (meta) such as lauryl (meth) acrylate ) Acrylates;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2- Alicyclic alkyl (meth) acrylates such as methyl-2-adamantyl (meth) acrylate and 2-2 ethyladamantyl (meth) acrylate;
Carboxyl (meth) acrylates such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid;
Alkoxyalkylene (meth) acrylates such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meth) acrylamide, and N-substituted types such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine ( (Meth) acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
As well as mixtures thereof.

Examples of monomers that can be used in combination with the acrylic monomer include vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
An ethylenically unsaturated monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; and
Examples thereof include an ethylenically unsaturated monomer having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride.
Among these, (meth) acrylic acid, particularly acrylic acid is preferable.

<Method for producing kneaded resin (A)>
The method for producing the kneaded resin (A) obtained by polymerizing the monomer containing the ethylenically unsaturated monomer (a) represented by the general formula (1) used in the present invention is anionic polymerization, living anion. Known methods such as polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 80 to 130 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  As a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol, 2-ethyl-1,3-hexanediol, 2,4- Diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine, tributyrin, 2-methylpentane-2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol and 1,2,6-hexanetriol, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl Ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate or the like is used, but the invention is not particularly limited thereto. Of these, water-soluble organic solvents such as diethylene glycol, 2-ethyl-1,3-hexanediol, monoacetin, diacetin, and triacetin are preferred, and diethylene glycol is particularly preferred from the viewpoint of production processability. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

  The weight average molecular weight of the kneaded resin (A) is preferably 2,000 to 40,000, more preferably 4,000 to 25,000. If the weight average molecular weight is less than 2,000, the stability of the pigment composition may be reduced. Stickiness may occur.

In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

<Coloring composition>
The pigment composition can be used as a coloring composition together with a binder resin and an organic solvent. At that time, in addition to the pigment composition of the present invention, other colorants may be used in combination.

<Other colorants>
In order to adjust the chromaticity and the like, the pigment composition may be used in combination with the dyes shown below as other colorants in addition to the pigment composition as long as the effects of the present invention are not impaired.

Other red dyes that can be used in the colorant include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, anthraquinone series, and the like. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

<Binder resin>
Examples of the binder resin contained in the colored composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of these alkali-soluble resins include acrylic resins having acidic groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, and ethylene / (meth) acrylic acid copolymers. Examples thereof include a polymer, an isobutylene / (anhydrous) maleic acid copolymer, and the like. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, formyl groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly (Meth) acrylates such as tylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether Examples thereof include vinyl ethers, vinyl acetate, and fatty acid vinyls such as vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

On the other hand, examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are two permeation columns “TSK-GELSUPERHZM-N” in series in gel permeation chromatography “HLC-8220GPC” (manufactured by Tosoh Corporation). It is a polystyrene conversion value measured by using tetrahydrofuran (THF) as a mobile phase.

When the binder resin is used as a coloring composition for a color filter, a pigment adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that serves as an affinity group for the coloring composition carrier and solvent, and an aromatic group The balance of groups is important for pigment dispersibility, developability, and durability, and it is preferable to use a binder resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it is difficult to form a fine pattern. On the contrary, if the acid value exceeds 300 mgKOH / g, a fine pattern does not remain by development, which is not preferable.

The binder resin is preferably used in an amount of 20 to 500 parts by mass with respect to 100 parts by mass of the pigment composition.

<Organic solvent>
In the colored composition of the present invention, it is easy to form a filter segment by sufficiently dispersing the pigment composition and applying it onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to do so, an organic solvent is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, since the solubility of each component in the coloring composition and the coating property of the coloring composition are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colored composition in order to adjust the colored composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Is preferred.

<Dispersion of coloring composition>
In the coloring composition of the present invention, the pigment composition is a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular type in a colored composition carrier composed of the binder resin and an organic solvent. It can be produced by finely dispersing using various dispersing means such as a bead mill or an attritor. In the colored composition of the present invention, the pigment composition and other colorants may be simultaneously dispersed in the colored composition carrier, or those separately dispersed in the colored composition carrier may be mixed. The carrier means a composition comprising a binder resin and an organic solvent.

Further, when the pigment composition is dispersed in the colored composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition using the dispersion aid can be expected to improve contrast and viscosity stability.

<Resin type dispersant and surfactant>
The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colored composition and a part compatible with the colored composition carrier, and adsorbs to the pigment composition to disperse in the colored composition. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyls. Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxyl groups, Oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified Li acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfone. Anionic surface activity such as sodium lauryl sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxye Nonionic surfactants such as lenalkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include amphoteric surfactants such as alkylbetaines such as aminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

When adding a resin-type dispersant and a surfactant, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, with respect to 100 parts by weight of the pigment composition.

The colored composition of the present invention can be used as a photosensitive colored composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. Can be used. It is preferable that the compounding quantity of a monomer is 5-400 mass parts with respect to 100 mass parts of coloring compositions, and it is more preferable that it is 10-300 mass parts from a photocurable and developable viewpoint.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
When the colored composition of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator is added to form a photosensitive colored composition. Or it can adjust with the form of an alkali image development type colored resist material.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' Benzophenone compounds such as 1,4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment composition in the coloring composition, and 3 to 150 parts by mass from the viewpoint of photocurability and developability. It is more preferable.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of photoinitiators contained in a coloring composition, and from a viewpoint of photocurability and developability. It is more preferable that it is 5-50 mass parts.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5 parts by mass with respect to 100 parts by mass of the colored composition.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
In order to assist the curing of the thermosetting resin, the coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, it is preferable to use 0.01-15 mass parts with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by mass as a colored composition (100% by mass).

Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropyltriet Sisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition (100% by mass).

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. The at least one filter segment is formed from the colored composition of the present invention.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

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

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

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

A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples according to conventional methods. However, the present invention is not limited to the scope of these examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

<Production of kneaded resin (A)>
A method for producing the kneaded resin (A) of the present invention will be described. Prior to production of the kneaded resin (A), a method for measuring the weight average molecular weight of the resin will be described.

(Measurement method of weight average molecular weight)
The weight average molecular weight is determined by using two separation columns “TSK-GELSUPERHZM-N” connected in series in gel permeation chromatography (GPC) “HLC-8220GPC” (manufactured by Tosoh Corporation) It is the polystyrene conversion value measured using tetrahydrofuran (THF).

Hereinafter, the production method of the kneaded resin (A) will be specifically described with reference to production examples.
[Production Example 1]
Production of kneaded resin (A1) 400 parts of diethylene glycol is placed in a reaction vessel, heated to 110 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is dropped at the same temperature over 2 hours. The reaction was performed.
-Phenoxyethyl methacrylate: 230.0 parts-Acrylic acid: 50.0 parts-tert-butyl-2-ethylperoxyhexanoate: 10.0 parts after dropwise addition and further reacted at 110 ° C for 1 hour, then tert- A solution prepared by dissolving 1.0 part of butyl-2-ethylperoxyhexanoate in 10 parts of diethylene glycol was added, and the reaction was further continued at 100 ° C. for 2 hours. After cooling to room temperature, about 1 g of the resin solution was sampled, dried by heating at 200 ° C. for 20 minutes, and the nonvolatile content was measured to confirm that the conversion rate was 95% or more. After completion of the reaction, diethylene glycol was added so that the nonvolatile content was 50% by mass to obtain a kneaded resin A1 having a weight average molecular weight of 18,500.

[Production Examples 2 to 21, 23 to 25]
Production of kneaded resins (A2 to A21, AC1 to AC3) Except for changing to the raw materials and preparation amounts described in Table 1, the synthesis was performed in the same manner as in Production Example 1, and kneaded resins (A2 to A21, AC1 to 3) were prepared. Got.

[Production Example 22]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 78.5 parts of phenoxyethyl methacrylate and 19.6 parts of acrylic acid and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and 1.9 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile are dissolved in 45.3 parts of diethylene glycol. The solution was added and reacted for 10 hours. The reaction was completed after confirming that 95% had reacted by solid content measurement. After completion of the reaction, diethylene glycol was added so that the nonvolatile content was 50% by mass to obtain Resin A22 having a weight average molecular weight of 18,600.

＜バインダー樹脂の製造＞
［製造例２６］
バインダー樹脂（Ｂ１）の製造
反応容器にプロピレングリコールモノメチルエーテルアセテート８００部を入れ、容器に窒素ガスを注入しながら１００℃に加熱して、同温度で下記モノマーおよび熱重合開始剤の混合物を１時間かけて滴下して反応を行った。
・スチレン：６０．０部
・メタクリル酸：６０．０部
・メチルメタクリレート：６５．０部
・ブチルメタクリレート：６５．０部
・アゾビスイソブチロニトリル：１０．０部
滴下後、更に１００℃で３時間反応させた後、アゾビスイソブチロニトリル２．０部をプロピレングリコールモノメチルエーテルアセテート５０部に溶解させたものを添加し、更に１００℃で１時間反応を続けた。室温まで冷却した後、樹脂溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した樹脂溶液に不揮発分が２０質量％になるようにプロピレングリコールモノメチルエーテルアセテートを添加して、バインダー樹脂（Ｂ１）を得た。

<Manufacture of binder resin>
[Production Example 26]
Production of Binder Resin (B1) 800 parts of propylene glycol monomethyl ether acetate is put into a reaction vessel, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is kept at the same temperature for 1 hour. The reaction was performed dropwise.
・ Styrene: 60.0 parts ・ Methacrylic acid: 60.0 parts ・ Methyl methacrylate: 65.0 parts ・ Butyl methacrylate: 65.0 parts ・ Azobisisobutyronitrile: 10.0 parts after dropping and further at 100 ° C. After reacting for 3 hours, 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain a binder resin (B1).

<Production of salt-forming compound (D)>
C. with reference to Production Example 50 of JP2013-33194A. I. A salt-forming compound (D) comprising Acid Red 52 and a resin having a cationic group in the side chain was produced.

<Preparation of salt-forming compound solution (D1)>
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a dye solution.
Salt-forming compound (D): 11.0 parts Binder resin (B1): 40.0 parts Propylene glycol monomethyl ether acetate: 49.0 parts

<Preparation of pigment composition>
(Average primary particle diameter of pigment composition)
The average primary particle diameter of the produced pigment composition was measured (calculated) by the following method. Propylene glycol monomethyl ether acetate was added to the powder of the pigment composition, a small amount of Disperbyk-161 was added as a resin-type dispersant, and the mixture was treated with ultrasonic waves for 1 minute to prepare a measurement sample. This sample was taken with a transmission electron microscope (TEM), and three photographs (for three fields of view) in which 100 or more primary particles of the pigment composition could be confirmed were taken, and the size of 100 primary particles in order from the upper left. Was measured. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment composition are measured in nm units, and the average is defined as the primary particle diameter of the pigment composition, with a total of 300 distributions in 5 nm increments. Create a number average particle size by approximating the median value in 5 nm increments (for example, 8 nm for 6 nm or more and 10 nm or less) as the particle size of those particles, and calculating based on each particle size and its number did.

[Example 1]

<Pigment>
Hereinafter, pigments used in Examples or Comparative Examples are listed.
・ PB15: 6: “LIONOL BLUE E” manufactured by Toyocolor Co., Ltd.
・ PR254: “Irgazin Red L 3660 HD” manufactured by BASF
PR269: “Permanent Carmine 3810” manufactured by Sanyo Dye
・ PG36: “LIONOL GREEN 6YK” manufactured by Toyocolor Co., Ltd.
・ PG58: “FASTOGEN Green A110” manufactured by DIC
・ PY138: “Paliotol Yellow K 0961 HD” manufactured by BASF
・ PY150: “Yellow Pigment E4GN” manufactured by LANXESS

<Pigment derivative>
Hereinafter, pigment derivatives used in Examples or Comparative Examples are listed in Tables 2 and 3.

[Example 1]
Phthalocyanine blue pigment C.I. I. 145 parts of Pigment Blue 15: 6 (Toyocolor "LIONOL BLUE E"), 5 parts of pigment derivative i, 7.5 parts of kneaded resin A1, 1500 parts of sodium chloride, and 330 parts of diethylene glycol, 3L gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 10 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 145 parts of pigment composition P1 were obtained.

[Examples 2-36, Comparative Examples 1-3]
Pigment compositions P2 to P39 were obtained in the same manner as in Example 1 except that the composition was changed to the kneading composition shown in Table 4.

[Comparative Example 4]
Phthalocyanine blue pigment C.I. I. 145 parts of Pigment Blue 15: 6 (“LIONOL BLUE E” manufactured by Toyocolor Co., Ltd.), 5 parts of pigment derivative i, 1500 parts of sodium chloride, and 330 parts of diethylene glycol are charged into a stainless steel 3L gallon kneader (manufactured by Inoue Seisakusho). And kneading at 70 ° C. for 10 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 140 parts of pigment composition P40 were obtained.

<Preparation of colored composition>
[Example 37]
(Preparation of colored composition PP1)
The compound shown below was mix | blended, 100 parts of zirconia beads with a diameter of 1.2 mm were added, and it disperse | distributed for 3 hours with the paint conditioner, and produced pigment composition PP1.
Pigment composition P1: 14.85 parts Resin B1: 7.15 parts Propylene glycol monomethyl ether acetate: 78.0 parts

[Examples 38 to 72, Comparative Examples 5 to 8]
(Preparation of colored composition PP2-39)
Colored compositions PP2-39 were prepared in the same manner as in Example 37 except that the blending composition shown in Table 5 was changed.

[Comparative Example 8]
(Preparation of colored composition PP40)
The compound shown below was mix | blended, 100 parts of zirconia beads with a diameter of 1.2 mm were added, and it disperse | distributed for 3 hours with the paint conditioner, and produced pigment composition PP1.
Pigment composition P40: 14.85 parts Kneaded resin A1: 0.75 parts Resin B1: 6.45 parts Propylene glycol monomethyl ether acetate: 78.0 parts

<Evaluation of coloring composition>
About the coloring composition manufactured by Examples 37-72 and Comparative Examples 5-8, viscosity evaluation, evaluation of contrast ratio, and foreign material generation | occurrence | production evaluation on a coating film were performed as follows.

(Viscosity evaluation)
The viscosity of the pigment composition was adjusted to the initial viscosity η ₁ and kept at a constant temperature of 40 ° C. for 1 week, and the viscosity after aging was set to η ₂ , and the E type viscometer “ELD type viscometer” ( Using Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and rotation speed 20 rpm. A lower initial viscosity means higher dispersion stability. Regarding the viscosity stability, the difference between the initial viscosity and the viscosity with time was within ± 10%, and the difference between ± 10% and over was ±.

(Evaluation of contrast ratio)
The film thickness after heat treatment at 230 ° C. was changed to about 1 by using the spin coater on the 100 mm × 100 mm, 1.1 mm thick glass substrate of the colored composition produced in the examples and comparative examples. It is applied to 3 substrates so that the thickness is about 5 μm, then dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light quantity of 150 mJ / cm 2 using an ultra-high pressure mercury lamp, and an alkaline developer at 23 ° C. Development was performed to obtain a coated substrate. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. The larger the value, the better, and C is a difficult level to use.
S: CR ≧ 10000 or more A: CR = 5000 or more and less than 10000 B: CR = 3000 or more and less than 5000 C: CR = less than 3000

(Evaluation of occurrence of foreign matter on coating film)
The evaluation of the generation of foreign matter was performed by applying a colored composition on a transparent substrate so that the dried coating film was about 2.0 μm, and performing a heat treatment at 230 ° C. for 1 hour in an oven. The number of foreign objects was counted. The evaluation was performed by observing the surface using a metal microscope “BX60” (manufactured by Olympus System). The magnification was 500 times, and the number of foreign matters observable in arbitrary 5 fields of view through transmission was measured. In the following evaluation results, S and A are good with a small number of foreign matters, B is a level having no problem in use although the number of foreign matters is large, and C is not practically usable because uneven coating (spots) due to foreign matters occurs. Corresponds to the state.
S: The number of foreign matters is less than 5 A: The number of foreign matters is 5 or more and less than 20 B: The number of foreign matters is 21 or more and less than 100 C: The number of foreign matters is 100 or more The smaller the occurrence of foreign matters, There are few remaining coarse particles after dispersion, indicating that the dispersibility is good.

  From the results of Table 5, it can be seen that all of the examples of the present invention exhibited excellent initial viscosity, viscosity stability, and contrast ratio as compared with the comparative example. This suggests that the solid component in the pigment composition does not aggregate and has good dispersibility. On the other hand, as shown in the comparative example, a kneading resin containing a monomer having an aromatic ring close to the main chain of the resin or a kneading resin not containing a monomer having an aromatic ring is thickened because the resin hardly adsorbs during kneading. I understand that. Further, the colored composition (PP40) to which the kneaded resin is added at the time of dispersion is worse in contrast ratio and viscosity than the colored composition (PP1 to PP26) added at the time of wet kneading, and the pigment is not sufficiently adsorbed and aggregated. It is thought that.

<Preparation of photosensitive coloring composition>
[Example 73]
(Preparation of photosensitive coloring composition R1)
The coloring composition PP1 and the salt-forming compound solution D1 were dried at a coating film having a chromaticity of x = 0.090 and y = 0.139 in a microspectrophotometer (“OSP-SP100” C light source manufactured by Olympus Optical Co., Ltd.). A colored composition RR-1 was prepared by stirring and mixing the mixture shown in Table 5 so as to have a uniform mixing ratio. Further, the following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (R1).
Coloring composition (RR-1): 60.0 parts Resin B1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts-Sensitizer (Hodogaya Chemical "EAB-F"): 0.4 parts-Cyclohexanone: 5.2 parts-Propylene glycol Monomethyl ether acetate: 18.0 parts

[Examples 74 to 102, Comparative Examples 9 to 12]
(Production of photosensitive coloring compositions R2 to R30, R36 to 39)
Photosensitive coloring compositions R2 to R30 and R36 to 39 were produced in the same manner as in Example 73 except that the blending composition shown in Table 6 was changed.

[Example 103]
Next, the red photosensitive coloring composition was changed in the same manner as in Example 73 except that the blending composition shown in Table 6 was changed and the chromaticity of the dried coating film was adjusted to x = 0.661 and y = 0.323. A product (R31) was obtained.

[Examples 104 to 107]
Next, the green colored composition photosensitive composition was changed in the same manner as in Example 73 except that the formulation shown in Table 6 was changed and the chromaticity of the dried coating film was adjusted to x = 0.290 and y = 0.600. Property coloring compositions (R32 to R35) were obtained.

<Evaluation of photosensitive coloring composition>
(Evaluation of contrast ratio)
Evaluation similar to the coloring composition manufactured in Examples 37-72 and Comparative Examples 5-8 was performed.
(Evaluation of voltage holding ratio)
The obtained resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the film thickness of the dry film was 2.0 μm. Next, the coating film is exposed at an exposure amount of 40 mJ / cm @ 2, spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 DEG C. for 40 seconds, and baked at 230 DEG C. in an oven. A coated substrate of the material was obtained. 0.05 g of the coated film was scraped off from the obtained coated substrate, immersed in 2.0 g of liquid crystal (MJ971189, manufactured by Merck & Co.), aged for 65 minutes in a 120 ° C. clean oven, and centrifuged at 5000 rpm for 20 minutes. After separation, the supernatant liquid was collected to prepare a contamination source boiled liquid into the liquid crystal.
After completion of contamination source boiling, the liquid crystal is taken out and sealed in a glass cell with an ITO electrode, and the voltage holding ratio (holding ratio after 16.7 milliseconds at an applied voltage of 5 V) using a liquid crystal property evaluation machine (6254, manufactured by Toyo Technica). Was measured and evaluated according to the following criteria. C is a difficult level to use.
S: 95% or more A: 90% or more and less than 95% B: 85% or more and less than 90% C: Less than 85%

(Evaluation of transferability)
The photosensitive composition is applied on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed using a spin coater, and then prebaked for 2 minutes on a hot plate at 90 ° C. A coating film having a thickness of 2.4 μm was formed. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film with the exposure amount of 400 J / m <2> using the high pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm 2 (nozzle diameter: 1 mm). . Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film (T-1) on the substrate. With respect to the obtained cured film (T-1), using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a chromaticity coordinate value (x, y) in the CIE color system with a C light source and a 2-degree field of view, and The stimulus value (Y) was measured. Next, another photosensitive pigment composition was applied on the cured film (T-1) using a spin coater, and then pre-baked on a 90 ° C. hot plate for 2 minutes to form a coating film having a thickness of 2.5 μm. Formed. Next, after cooling the substrate to room temperature, a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged to the substrate at a developing pressure of 1 kgf / cm 2 2 (nozzle diameter 1 mm). Thus, shower development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water and air-dried. A series of steps from application of the coloring composition (S-1) to air drying is referred to as “(step-1)”. For the cured film (T-1) after (Step-1), the chromaticity coordinate value (x, y) and the stimulus value (Y) are measured, and the stimulus value change before and after (Step-1), that is, ΔY is evaluated. did. As a result, if the value of ΔY is less than 0.2, “S”, 0.2 to less than 0.4 is “A”, 0.4 to less than 0.7 is “B”, 0. The case of 7 or more was evaluated as “C”. It can be said that the smaller the ΔY value, the more the dye transfer property is suppressed.

  From Table 6, since the contrast ratio of Examples 73-107 is superior to Comparative Examples 9-12, it has shown favorable dispersibility. Further, Examples 73 to 87, 94 to 97, and 99 to 107 were very excellent results in voltage holding ratio and dye transfer property. This is because the aromatic ring contained in the kneaded resin added during wet kneading is adsorbed to the pigment with an appropriate length from the resin main chain, so that the voltage holding ratio is excellent, and there is almost no contamination to other colors. Dispersion stability is shown. On the other hand, compared with Examples 73 to 107, Comparative Examples 9 to 12 have a poor voltage holding ratio, and it is clear from this result that contamination to other colors occurs.

  From Table 6, it can be seen that by using the pigment composition of the present invention, a photosensitive coloring composition having excellent dispersibility, voltage holding ratio, and dye transfer property can be obtained.

<Manufacture of color filters>
Using the red photosensitive coloring composition R31 of the present invention, the green photosensitive coloring composition R33, and the blue photosensitive coloring composition R1, the dry film thickness is 1.7 μm by spin coating on the substrate. And dried. And after performing ultraviolet exposure through a mask having a predetermined pattern provided in a non-contact state with the coating film, after spraying an alkali developer by spraying to remove the uncured portion and forming a desired pattern, Heated at 230 ° C. for 1 hour. The same operation was repeated for green and blue to produce a color filter and an RGB three-color filter. It was confirmed that the obtained color filter had high brightness and excellent heat resistance, and was not significantly lowered by migration.

Claims (9)

A method for producing a pigment composition in which a pigment, a kneaded resin (A), and a pigment derivative are wet-kneaded,
A color characterized in that the kneaded resin (A) is a kneaded resin (A) obtained by polymerizing a monomer containing the ethylenically unsaturated monomer (a) represented by the general formula (1). A method for producing a pigment composition for a filter.

[In general formula (1),
Y represents — (CH ₂ CH ₂ O) _n —, — (CH ₂ CH ₂ CH ₂ O) _m —, — (CH ₂ CH (CH ₃ ) CH ₂ O) ₁ —, —CH ₂ CH ₂ C ( = O) O-, or a direct bond,
n, m, and l are integers of 1 to 10,
R ₁ is a hydrogen atom or a methyl group,
R ₂ represents an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. ] In the general formula (1), The process according to claim 1, color filter pigment composition, wherein the Y is _-CH 2 _CH 2 O-. The method for producing a pigment composition for a color filter according to claim 1 or 2, wherein R ₂ in the general formula (1) is a phenyl group. The kneaded resin (A) comprises an ethylenically unsaturated monomer (a) represented by the general formula (1) and an ethylenically unsaturated monomer (b) having no aromatic ring or heterocyclic ring in the molecule. The method for producing a pigment composition for a color filter according to any one of claims 1 to 3, wherein the polymer is radical polymerized. The method for producing a color filter pigment composition according to any one of claims 1 to 4, wherein the kneaded resin (A) is radically polymerized in a water-soluble organic solvent. The method for producing a color filter pigment composition according to any one of claims 1 to 5, wherein the pigment is an ε-type phthalocyanine pigment. Furthermore, dispersion resin, binder resin, and an organic solvent are included, The manufacturing method of the coloring composition for color filters of any one of Claims 1-6 characterized by the above-mentioned. Furthermore, a photopolymerizable monomer and / or a photoinitiator are contained, The manufacturing method of the coloring composition for color filters of any one of Claims 1-7 characterized by the above-mentioned. The manufacturing method of the color filter formed using the coloring composition for color filters manufactured by the manufacturing method of Claim 7 or 8.