JP6455748B1 - Pigment composition for color filter and color filter - Google Patents

Abstract

（一般式（１）中、Ｚ^１〜Ｚ^１６は、それぞれ独立して、臭素原子、塩素原子、水素原子又はスルホ基を表し、少なくともスルホ基の平均置換基数が０．１〜４個であり、ＭはＡｌ、Ｓｉ、Ｓｃ、Ｔｉ、Ｖ、Ｍｇ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｇａ、Ｇｅ、Ｙ、Ｚｒ、Ｎｂ、Ｉｎ、Ｓｎ又はＰｂを表す。）で表される顔料誘導体と、を含有することを特徴とするカラーフィルタ用顔料組成物及びこれを画素部に有してなるカラーフィルタを提供することができる。The problem to be solved by the present invention is to provide a pigment composition for obtaining a color filter with improved brightness without increasing the film thickness. The present invention relates to a halogenated zinc phthalocyanine pigment, the following general formula (1):

(In General Formula (1), Z ^{1 to} Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and at least the average number of substituents of the sulfo group is 0.1 to 4 , M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb.) It is possible to provide a color filter pigment composition characterized by containing a color filter and a color filter comprising the same in a pixel portion.

Description

  The present invention relates to a color filter pigment composition and a color filter.

  A color filter used in a liquid crystal display arranges a plurality of colors regularly on a transparent glass substrate, and transmits only light in a necessary wavelength region from white light of a backlight that passes through the color filter. It is a member that realizes color display. The colors used there generally include the three primary colors of red, green, and blue, and improvements have been made to color materials, resins, additives, and the like used to adjust the transmission spectrum. Among them, green colorants for color filters are required to have high brightness and an expanded color reproduction range from the viewpoint of improving display image quality.

  In order to increase the brightness, it is important to select a pigment having a high transmittance with respect to backlight light, and the improvement is advanced by using Pigment Green 58 as a main pigment instead of the conventional Pigment Green 36. In addition, high brightness by improving the pigment enables efficient use of the white light of the backlight, which makes it possible to save energy and reduce manufacturing costs of the display.

  In order to increase the color reproduction range, it is necessary to increase the saturation of the color material included in the color filter. In order to produce a highly saturated coating film, there are methods such as increasing the pigment concentration in the coating film or increasing the coating film thickness at the same pigment concentration. However, in any case, it is difficult to ensure various resistances of the coating film. Therefore, after the toning with the yellow color material than the pigment green 36 and the pigment green 58 conventionally used for the color filter application. Pigment Green 7 capable of thinning at a specific chromaticity is selected as the main pigment. Although the color reproduction range can be expanded by increasing the thickness of Pigment Green 36 and Pigment Green 58, it is impossible to achieve an NTSC ratio of 90% or more with a practical film thickness of about 3.5 μm. That is why Green 7 is selected. For example, it has been proposed to form a green pixel using a green photosensitive resin composition containing Pigment Green 7 and Pigment Yellow 185, and achieve high color reproduction with a thin film of 2.2 μm or less. However, since the pigment green 7 has a lower transmittance than the pigment green 36 and the pigment green 58, there is a problem that the luminance of the obtained display is lowered. In addition, the luminance can be compensated for by increasing the amount of light from the backlight, but an improvement is required because a new problem of increased power consumption occurs. From the above, a color material for color filters that achieves both luminance and color reproducibility is desired.

In order to solve these problems, when the main pigment is aluminum phthalocyanine, a color filter containing a phthalocyanine sulfonic acid derivative, excellent in color density, color purity, transparency, heat resistance and light resistance Has been proposed (Patent Document 1). However, due to the low heat resistance and light resistance of the aluminum phthalocyanine pigment as the main pigment, the performance required in recent years may not be satisfied.
In addition, a green pigment composition containing a halogenated copper phthalocyanine pigment and a low halogenated copper phthalocyanine sulfonic acid derivative, having an average primary particle diameter of 0.01 to 0.1 μm and an aspect ratio of 1 to 3 is used. It has been proposed to produce a color filter with good contrast (Patent Document 2). However, due to the low brightness of the copper phthalocyanine pigment as the main pigment, there have been cases where the performance required in recent years cannot be satisfied.
Thus, in order to form a color filter for the purpose of increasing the brightness and expanding the color reproduction range, these prior arts are not sufficient to satisfy the rapidly increasing required performance in recent years. The reality is that it has not been achieved.

JP 2011-057910 A JP 2005-316244 A

  The problem to be solved by the present invention is to provide a pigment composition for obtaining a color filter with improved brightness without increasing the film thickness.

  As a result of intensive studies in view of such a situation, the present inventors have used a zinc halide phthalocyanine pigment as a main pigment, and by adding a specific pigment derivative thereto, the brightness can be improved without increasing the film thickness. It has been found that a color filter capable of being produced can be produced. That is, the present invention relates to a zinc halide phthalocyanine pigment and the following general formula (1):

(In General Formula (1), Z ^{1 to} Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and at least the average number of substituents of the sulfo group is 0.1 to 4 , M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb.) The present invention relates to a color filter pigment composition characterized by containing a color filter and a color filter comprising the same in a pixel portion.

  According to the present invention, it is possible to produce a color filter capable of improving luminance without increasing the film thickness.

In the halogenated zinc phthalocyanine pigment used in the present invention, at least one halogen atom selected from chlorine, bromine, fluorine and iodine is present in the phthalocyanine ring which has zinc metal at the center and may be substituted with a substituent other than halogen. These are substituted compounds, and the total number of each substituent is 16 at the maximum. The portion not substituted with halogen and a substituent other than halogen refers to a hydrogen atom.
Among these, the halogenated zinc phthalocyanine pigment used in the present invention has an average of 10 to 14 halogen atoms in one molecule from the viewpoint of designing a color filter having a wide color reproduction range, and among these, the average number of bromine atoms is 8 The number is 12 and the number of chlorine atoms is preferably 2 to 5 on average.

The pigment derivative used in the present invention can be represented by the general formula (1).
Among these, from the viewpoint of making the hue of the main pigment and pigment derivative of the green color filter similar, in the general formula (1), Z ^{1 to} Z ¹⁶ are bromine atom, chlorine atom, hydrogen atom or sulfo group. And at least any one selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ^{16 on} the average in one molecule contains a chlorine atom. It is preferable to use what has.

Further, from the viewpoint of making the hues of the main pigment and pigment derivative of the green color filter similar, the pigment derivative is represented by the formula (1) in which Z ^{1 to} Z ¹⁶ are bromine atoms, chlorine atoms, hydrogen atoms or sulfo groups And any one or more selected from Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ has a bromine atom on average in one molecule. It is also preferable to use one.
In addition, when a chlorine atom or a bromine atom enters a position of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , Z ¹⁶ , the hue becomes greenish. It is described in.

From the viewpoint of making the hue of the pigment derivative more similar to the hue of the main pigment, 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 2 chlorine atoms on average in one molecule to Z ^{1 to} Z ¹⁶ . It is more preferable that five are contained.

  The above-described pigment composition of the present invention is not based on a simple combination of a conventional pigment and a pigment derivative of the same skeleton, but the present invention has been completed based on the following idea.

(A) First, a general organic pigment has a highly conjugated system formed as a whole molecule, and it is energetically stable to have a planar structure. When these planar molecules are arranged so as to be stacked (in parallel), conjugated π electrons between the molecules overlap each other, so that a more stable state is obtained. Since the pigment derivative represented by the general formula (1) used in the present invention has a phthalocyanine ring, it has a planar structure, and interaction with the planar structure of the organic pigment tends to work. Furthermore, when the main pigment is a halogenated phthalocyanine pigment, it is considered that the halogen-π interaction is particularly easy to work with the π electron of the derivative. When such a specific pigment derivative is allowed to coexist in the dispersion step of the organic pigment, it is considered that the derivative is efficiently adsorbed on the active surface of the halogenated phthalocyanine pigment newly generated during dispersion. In addition, since the halogenated phthalocyanine pigment can be dispersed and stabilized in a fine state by the polar sulfo group, the luminance can be improved. Here, the sulfonated phthalocyanine derivative of the present invention may be added at the time of pigmentation or can exert a good effect even when added at the time of dispersion. Since the primary particles can be finely held in between, the sulfonated phthalocyanine derivative of the present invention can realize a much larger luminance improvement when it is coexisted at the time of pigmentation than when it is added at the time of dispersion.
(B) Furthermore, the present invention has been completed by paying attention to how the absorption spectra of the pigment and the derivative overlap. In order to obtain a bright and clear display in the color filter of the green pixel, it is particularly preferable to increase the transmittance from 510 nm to 560 nm. In order to design a color filter that transmits only this narrow wavelength band, a combination of a green pigment and a yellow pigment is used, so the pigment derivative treated with the green pigment is similar to the transmission wavelength of the green pigment at 510 to 560 nm. It is preferable to use a combination.
(C) In addition, if the transmittance from 430 nm to 460 nm is high, the chromaticity y value is greatly reduced and the sharpness of green is greatly impaired. Therefore, it is preferable that the transmittance in this wavelength range is low. It is described in Kaihei 8-240708. When the chromaticity y value is low, it is necessary to increase the chromaticity y value by increasing the film thickness, but when the film thickness is increased, the luminance decreases. Therefore, it is necessary to select a pigment derivative so that the transmittance from 430 nm to 460 nm is as low as possible. In particular, the green pixel of the color filter is a C.I. I. It is common to use Pigment Yellow 138 (Y138) in combination. Y138 is described in Japanese Patent Application Laid-Open No. 2015-26077 when shifting from the absorption band to the transmission band around 460 nm. Therefore, although Y138 can produce absorption at a shorter wavelength than 460 nm, it is not suitable for making absorption at the longer wavelength side. For this reason, it is preferable that the derivative treated with the green pigment has a low transmittance at 460 nm.

  From the viewpoints of the above (B) and (C), the central metal M in the formula (1) is preferably Al or Zn, and more preferably Zn. If the viewpoint of (C) is described in detail, the transmittance at 430 nm to 460 nm is higher when the central metal M in the above formula (1) is Zn than when Al is used as the pigment derivative. Since it is low, a pigment composition with high brightness can be produced.

  Such a pigment derivative can be obtained by, for example, a conventionally known method as follows. That is, it can be obtained by dissolving phthalocyanine or halogenated phthalocyanine in sulfuric acid and heating it to 100 ° C. or higher, or dissolving it in fuming sulfuric acid and treating it at a low temperature. When a sulfo group is introduced into the phthalocyanine ring under severe reaction conditions, the phthalocyanine ring is oxidatively decomposed by sulfuric acid or fuming sulfuric acid, and the purity of the pigment derivative is lowered. From the viewpoint of using a pigment derivative with higher purity, in the general formula (1), the average number of sulfo groups in the molecule is preferably 0.1 to 4, and preferably 0.5 to 2 More preferably.

  The sulfo group may be a sulfonic acid or a salt. Examples of counter ions that form salts include ammonium ions, 1 to 3 metal ions (specific examples include lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, strontium ions, aluminum ions, and the like. And organic cations (specific examples include monoalkyl ammonium ions such as ethyl ammonium ion and butyl ammonium ion, dialkyl ammonium ions such as dimethyl ammonium ion and diethyl ammonium ion, trialkyl ammonium ions such as trimethyl ammonium ion and triethyl ammonium ion) Alkanol ammonium such as ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion On, tetramethylammonium ion, tetramethylguanidium ion, tetramethyl phosphonium ion) are included. In particular, the sulfo group of the pigment derivative in the present invention is preferably a sulfonic acid or an organic cation salt, from the viewpoint that the elution amount of the pigment derivative in the development step in color filter production can be reduced.

  In the present invention, the average number of halogen atoms of the halogenated zinc phthalocyanine pigment can be determined by mass spectrometry. Mass spectrometry is performed using a matrix-assisted laser desorption ionization time-of-flight mass spectrometer (JEOL Ltd. JMS-S3000), and when mass analysis of a compound whose molecular weight is known to be Q is performed, m Each measurement parameter is set so that / z = Q is detected. In the present invention, the JMS-S3000 setting was adjusted so that m / z = 1840 was detected when mass spectrometry of a known compound having a molecular weight of 1840 was performed. Mass spectrometry was performed using 1 μL of a suspension in which 0.5 mg of zinc halide phthalocyanine pigment was dispersed in 1 mL of tetrahydrofuran.

  In this invention, the average sulfonation rate of a pigment derivative can be calculated | required with a high performance liquid chromatograph mass spectrometer (Shimadzu LC-MS-8040). A gradient elution profile was used using a fixed volume of the pigment derivative with dimethyl sulfoxide and a mixed solvent of 10 mmol / L aqueous ammonium hydrogen carbonate / methanol / tetrahydrofuran as a mobile phase. The obtained peaks were qualitatively determined by mass spectrometry (ionization mode: DUIS), and the sulfonation rate was calculated from the peak area ratio.

In the pigment derivative of the present invention, in the general formula (1), the number of halogen substituents m of Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ , and Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ , Z ¹⁵ , the number n of halogen substituents is determined by decomposing the pigment derivative with cerium sulfate into phthalimides, It is calculated | required by analyzing by chromatography. The total molar concentration of all phthalimides obtained as a result of liquid chromatography is a, and the total molar concentration of phthalimides having halogen at the 3rd or 6th position is b (in the case of phthalimides having halogen at both the 3rd and 6th positions) (The molar concentration of phthalimides is calculated as twice the actual measurement.) The total molar concentration of phthalimides having a halogen at the 4th or 5th position is c (in the case of phthalimides having a halogen at both the 4th and 5th positions) When the molar concentration of phthalimides is calculated as twice the actual measurement), it is calculated as m = 4 × b / a and n = 4 × c / a. In addition, although m and n are calculated | required also by a liquid chromatography analysis, m and n can be determined freely by controlling a raw material. For example, a pigment derivative obtained by sulfonating tetrachlorozinc phthalocyanine synthesized using 3-chlorophthalic anhydride as a raw material has m = 4 and n = 0. A pigment derivative obtained by sulfonating tetrachlorozinc phthalocyanine synthesized using 4-chlorophthalic anhydride as a raw material has m = 0 and n = 4.

  In the present invention, the average number of halogen atoms of the pigment derivative can be determined by mass spectrometry using the matrix-assisted laser desorption / ionization time-of-flight mass spectrometer.

  The pigment derivative of the present invention may be added at the time of synthesizing the crude pigment or after pigmentation, but can also be pigmented together with the crude pigment at the time of pigmentation. Further, since the dispersibility of the color filter dispersion and the color filter resist ink is increased and the luminance is improved, a pigment derivative can be added at the time of dispersion or resist preparation. Since the pigment derivative used in the present invention can enter between the molecules of the halogenated zinc phthalocyanine pigment and keep the primary particles finely, it is preferable to add the pigment derivative at the time of pigmentation and pigmentize with the crude pigment.

  The above-described pigment composition containing the halogenated zinc phthalocyanine pigment and the pigment derivative represented by the above formula (1) may be dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill, etc. Then, by pigmenting with a solvent salt milling method, a solvent boiling method, or the like, it is possible to obtain a pigment that is excellent in dispersibility and coloring power and has a high lightness and green color than before pigmentation.

  The ratio between the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) is not particularly limited, but the pigment derivative represented by the above formula (1) per 100 parts of the halogenated zinc phthalocyanine pigment in terms of mass is 0. 0.1 to 10 parts is preferable because the brightness can be improved without increasing the film thickness when the pigment composition is used as a color filter.

  There is no particular limitation on the pigmentation method of the green pigment composition comprising the halogenated zinc phthalocyanine pigment and the pigment derivative represented by the formula (1). For example, the zinc halide phthalocyanine pigment before pigmentation and the formula (1) The pigment composition containing the pigment derivative represented by formula (1) may be dispersed in a dispersion medium and pigmented at the same time, but the zinc halide phthalocyanine pigment and the formula (1) in a large amount of an organic solvent may be used. The solvent salt milling treatment is preferably employed in that pigment particles having a large specific surface area can be obtained more easily than the solvent treatment in which the pigment composition comprising the pigment derivative is heated and stirred.

  This solvent salt milling is a pigment composition comprising a halogenated zinc phthalocyanine pigment not subjected to pigmentation and a pigment derivative represented by the above formula (1), which is ground immediately after synthesis or thereafter, and an inorganic salt. It means kneading and grinding with an organic solvent. As a kneading machine at this time, for example, a kneader, a mix muller, a trimix, a twin screw extruder or the like can be used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  In the present invention, a pigment composition comprising a zinc halide phthalocyanine pigment having an average primary particle diameter of 0.01 to 0.10 μm and a pigment derivative represented by the above formula (1) is used for a color filter. Is preferred. In obtaining the above preferred particle diameter in the present invention, it is preferable to increase the amount of inorganic salt used relative to the amount of crude pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass with respect to 1 part by mass of the crude pigment.

  As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol. Although the usage-amount of the said water-soluble organic solvent is not specifically limited, 0.01-5 mass parts is preferable with respect to 1 mass part of crude pigments.

  When a pigment composition comprising a halogenated zinc phthalocyanine pigment and a pigment derivative represented by the above formula (1) is produced by solvent salt milling, the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) are prepared. Each may be subjected to solvent salt milling and may be combined later. Alternatively, the halogenated zinc phthalocyanine pigment and the phthalocyanine pigment derivative represented by the formula (1) may be mixed in the apparatus at the same time to perform solvent salt milling. In the optical characteristic evaluation by the color filter, there is no big difference in that the luminance can be improved by either method.

  As described above, in the pigment composition of the present invention, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum is 500 to 525 nm, like the conventional zinc halide phthalocyanine pigment. The half width of the curve is as sharp as 110 nm or less (this wavelength is not affected by the photosensitive resin as described later).

Spectral transmission spectrum in color filter evaluation is determined according to the first class spectrophotometer of Japanese Industrial Standard JIS Z 8722 (color measurement method-reflection and transmission object color). The resin film containing the pigment composition formed into a predetermined dry film thickness is obtained by plotting each transmittance value at each wavelength by scanning and irradiating light in a predetermined wavelength region.
Here, the integral value of the transmittance of 510 nm to 560 nm of the coating film formed using the halogenated zinc phthalocyanine pigment so that the spectral transmittance at the maximum transmission wavelength is 70% is defined as D1, and the general formula (1) The integral value of the transmittance of 510 nm to 560 nm of the coating film formed so that the spectral transmittance at the maximum transmission wavelength is 70% using the derivative carrier obtained by supporting the pigment derivative represented by aluminum oxide on D2 is D2. The color filter pigment composition having spectral characteristics with a ratio of D1 to D2 (D2 / D1) of 0.7 or more minimizes a decrease in luminance of the green color filter due to the pigment derivative. This is preferable because it can be maintained. Further, in order to design a green color filter with higher luminance, it is more preferable that the color filter pigment composition has a spectral characteristic in which the ratio of D1 to D2 (D2 / D1) is 1.0 or more. More preferably, the pigment composition for color filters has spectral characteristics such that the ratio of D2 to D2 (D2 / D1) is 1.2 or more.
And the coating film formed at 460 nm using a derivative carrier obtained by supporting the pigment derivative represented by the general formula (1) on aluminum oxide so that the spectral transmittance at the maximum transmission wavelength becomes 70%. A pigment composition for a color filter having spectral characteristics with a transmittance of 60% or less is preferable because a green color filter with high color reproducibility in which a decrease in chromaticity y is suppressed can be produced. In order to design a green color filter with higher color reproducibility, it is more preferably a color filter pigment composition having spectral characteristics such that the transmittance at 460 nm is 55% or less, and the transmittance at 460 nm is 50. It is more preferable that the color filter pigment composition has a spectral characteristic of not more than%.

  The pigment composition of the present invention can be used as it is for the production of the green pixel portion of the color filter, but may be used in combination with other green pigments as necessary.

  In addition to the green pigment, a yellow pigment may be used for toning to develop characteristics. Examples of yellow pigments that can be used here include C.I. I. And yellow organic pigments such as CI Pigment Yellow 83, 110, 129, 138, 139, 150, 180, 185, and 231. The combined ratio of the halogenated zinc phthalocyanine pigment composition of the present invention and the yellow pigment is 1 to 200 parts by mass of the yellow pigment per 100 parts by mass of the halogenated zinc phthalocyanine pigment composition.

(Color filter)
A color filter can be obtained by forming a green pixel using the pigment composition of the present invention.

(Color filter manufacturing method)
The pigment composition of the present invention can be used for forming a pattern of a green pixel portion of a color filter by a known method. Typically, a photosensitive composition for a color filter green pixel portion containing the present pigment composition and a photosensitive resin as essential components can be obtained.

  As a method for producing a color filter, for example, after the pigment composition for a color filter of the present invention is dispersed in a dispersion medium made of a photosensitive resin, glass is formed by a spin coating method, a roll coating method, a slit coating method, an ink jet method, or the like. This is called photolithography, which is applied on a transparent substrate, etc., and is then subjected to pattern exposure with ultraviolet rays through a photomask to obtain a green pattern by washing unexposed portions with a solvent or the like. Methods and the like.

  Examples of other manufacturing methods include a method of manufacturing a color filter by forming a pattern of a green pixel portion by a method such as an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method. . The red pixel portion pattern and the blue pixel portion pattern can also be formed by a similar method using a known pigment.

  In order to prepare the photosensitive composition for the color filter green pixel portion, for example, the pigment composition for the color filter of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are essential. Mix as an ingredient. More specifically, a method of preparing a dispersion by using a pigment composition of the present invention, an organic solvent, and a dispersant as required, and then adding a photosensitive resin or the like to the dispersion is common. .

  Examples of the dispersant include Disperbyk (DISPERBYK, registered trademark) 130, 161, 162, 163, 170, LPN-6919, LPN-21116, etc. manufactured by BYK Chemie. Further, a leveling agent, a coupling agent, a cationic surfactant and the like may be used together.

  Examples of the organic solvent include aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvents such as methanol, ethanol solvents such as methanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, etc. Aliphatic hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, Diphosphate, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate, there is water. As the organic solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, water and the like that are water-soluble are particularly suitable.

  A dispersion is obtained by stirring and dispersing 300 to 1000 parts by mass of an organic solvent and, if necessary, 0 to 100 parts by mass of a dispersant per 100 parts by mass of the pigment composition of the present invention so as to be uniform. Can do. Next, 3 to 20 parts by mass of the photosensitive resin per 100 parts by mass of the pigment composition of the present invention, 0.05 to 3 parts by mass of a photopolymerization initiator per 1 part by mass of the photosensitive resin, and Accordingly, an organic solvent is further added, and the mixture is stirred and dispersed so as to be uniform, whereby a photosensitive composition for a color filter green pixel portion can be obtained.

  Examples of the photosensitive resin include thermoplastic resins such as urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and 1,6-hexane, for example. Bifunctional monomers such as diol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, trimethylol propaton tri Multi-functional such as acrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate etc. Photopolymerizable monomer, such monomers.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 '-Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.

  The prepared photosensitive composition for the color filter green pixel portion is subjected to pattern exposure with ultraviolet rays through a photomask, and then the unexposed portion is washed with an organic solvent or alkaline water to obtain a color filter. Can do.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by this. In Examples and Comparative Examples, “part” and “%” are based on mass unless otherwise specified.
Moreover, the measuring method used in the Example mentioned later is as follows.

[Brightness evaluation]
The chromaticity x, y and luminance of the obtained color filter in the C light source were measured with a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.). The higher the brightness, the better.

Reference example 1
In a 300 ml flask, 90 g of sulfuryl chloride (Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (Kanto Chemical Reagent), 14 g of sodium chloride (Tokyo Chemical Industry), 27 g of zinc phthalocyanine from DIC Corporation, bromine (Wako Pure Chemical Industries) 55 g was charged. After heating up to 130 degreeC and taking out in water, the halogenated zinc phthalocyanine (R1) was obtained by filtering, washing with water, and drying. The halogenated zinc phthalocyanine (R1) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average chlorination rate was 2.9 and the average bromination rate was 9.3. In addition, the delay time at the time of mass spectrometry was 510 ns, the laser intensity was 40%, and the resolving power value of the peak at m / z = 1820 to 1860 was 65086.
40 g of the zinc halide phthalocyanine (R1) thus obtained, 400 g of crushed sodium chloride, and 63 g of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (RG1). 2.48 g of green pigment composition (RG1) is 0.3 to 0.00 together with 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Corporation, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using 4 mm zircon beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (RMG1). Coloring composition (RMG1) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added, and the composition for evaluation (RCG1) is mixed by a paint shaker. Obtained. This evaluation composition (RCG1) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 2511.6, and the transmittance at 460 nm was 8.79.

Reference example 2
In a 300 ml flask, 91 g of sulfuryl chloride (Wako Pure Chemical Industries reagent), 109 g of aluminum chloride (Kanto chemical reagent), 15 g of sodium chloride (Tokyo Chemical Industry reagent), 30 g of zinc phthalocyanine manufactured by DIC Corporation, bromine (Wako Pure Chemical Industries reagent) 230 g was charged. After heating up to 130 degreeC and taking out in water, the halogenated zinc phthalocyanine (R2) was obtained by filtering, washing with water, and drying. The halogenated zinc phthalocyanine (R2) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average chlorination rate was 1.8 and the average bromination rate was 13.2. The delay time at the time of mass spectrometry was 500 ns, the laser intensity was 44%, and the resolving power value of the peak at m / z = 1820 to 1860 was 31804.
40 g of the thus obtained zinc halide phthalocyanine (R2), 400 g of crushed sodium chloride, and 63 g of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (RG2). 2.48 g of the green pigment composition (RG2) is 0.3 to 0.00 with 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Corporation, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using 4 mm zircon beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (RMG2). Coloring composition (RMG2) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added, and the composition for evaluation (RCG2) is mixed by a paint shaker. Obtained. This evaluation composition (RCG2) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 2787.8, and the transmittance at 460 nm was 3.07.

Synthesis example 1
288 g of 98% sulfuric acid and 272 g of 30% fuming sulfuric acid were stirred while being cooled to 10 ° C., and 70 g of zinc phthalocyanine manufactured by DIC Corporation was added. Subsequently, it stirred at 60 degreeC for 3 hours. The reaction solution was taken out in 1750 g of water, stirred for 1 hour, filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanine derivative (S1). The sulfonated zinc phthalocyanine derivative (S1) was confirmed to have an average sulfonation rate of 1 by LC-MS measurement. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated zinc phthalocyanine derivative (S1) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A1). Derivative support (A1) 2.48 g is combined with BYK-LPN6919 1.24 g manufactured by BYK-Chemie Co., Ltd., Unidic ZL-295 1.86 g manufactured by DIC Corporation, and 0.32-0.4 together with 10.92 g propylene glycol monomethyl ether acetate. Using a zircon bead of mm, it was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (AMG1). Coloring composition (AMG1) 4.0g, DIC Corporation Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g is added, and the composition for evaluation (ACG1) is mixed by a paint shaker. Obtained. This composition for evaluation (ACG1) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Corporation. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 1988.8, and the transmittance at 460 nm was 55.27.

Synthesis example 2
A 1 L flask was charged with 55 g of 3-chlorophthalic anhydride, 45 g of phthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 250 g of sulfolane, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, the mixture was allowed to cool, filtered, and washed with 780 g of 2-propanol, 1000 g of 1% aqueous sodium hydroxide, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain blue solid dichlorozinc phthalocyanine. 20 g of 95% sulfuric acid and 180 g of 30% fuming sulfuric acid were stirred while cooling to 10 ° C., and 20 g of dichlorozinc phthalocyanine was added. Subsequently, it stirred at 80 degreeC for 5 hours. The reaction solution was taken out in 1000 g of water, stirred for 30 minutes, filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanine derivative (S2). The sulfonated zinc phthalocyanine derivative (S2) was confirmed to have an average sulfonation rate of 1 and an average chlorination rate of 2 by LC-MS measurement. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated zinc phthalocyanine derivative (S2) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A2). Derivative carrier (A2) 2.48 g, BYK-LPN6919 1.24 g manufactured by BYK-Chemie Co., Ltd. Unidic ZL-295 1.86 g manufactured by DIC Corporation 0.3.0.4 with propylene glycol monomethyl ether acetate 10.92 g Using a zircon bead of mm, the mixture was dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (AMG2). Coloring composition (AMG2) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added, and the composition for evaluation (ACG2) is mixed by a paint shaker. Obtained. This composition for evaluation (ACG2) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 3054.6, and the transmittance at 460 nm was 57.47.

Synthesis example 3
A 1 L flask was charged with 111 g of 3-chlorophthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 250 g of sulfolane, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, the mixture was allowed to cool, filtered, and washed with 780 g of 2-propanol, 1000 g of 1% aqueous sodium hydroxide, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain a blue solid tetrachlorozinc phthalocyanine. 131 g of 30% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 15 g of tetrachlorozinc phthalocyanine was added. Subsequently, it stirred at 90 degreeC for 3 hours. The reaction solution was taken out in 750 g of water, filtered, washed with water and dried after stirring for 15 minutes to obtain a sulfonated zinc phthalocyanine derivative (S3). The sulfonated zinc phthalocyanine derivative (S3) was confirmed to have an average sulfonation rate of 1.6 and an average chlorination rate of 4 by LC-MS measurement. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated zinc phthalocyanine derivative (S3) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A3). 2.48 g of the derivative carrier (A3) is 0.3 to 0.4 together with 1.24 g of BYK-LPN6919 manufactured by Big Chemie, 1.86 g of Unidic ZL-295 manufactured by DIC, and 10.92 g of propylene glycol monomethyl ether acetate. Using a zircon bead of mm, the mixture was dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (AMG3). Coloring composition (AMG3) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added, and the composition for evaluation (ACG3) is mixed by a paint shaker. Obtained. This composition for evaluation (ACG3) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 3065.8, and the transmittance at 460 nm was 53.41.

Synthesis example 4
In a 300 ml flask, 54 g of sulfuryl chloride (Wako Pure Chemical Industries), 63 g of aluminum chloride (Kanto Chemical), 8.6 g of sodium chloride (Tokyo Chemical Industry), 17 g of sulfonated zinc phthalocyanine derivative (A), bromine (Wako Pure) 87 g of a pharmaceutical industry reagent) was charged. After heating up to 130 degreeC and taking out to water, the sulfonated zinc phthalocyanine derivative (S4) was obtained by filtering, washing with water, and drying. The sulfonated zinc phthalocyanine derivative (S4) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and the average sulfonation rate was 1, the average chlorination rate was 2.2, and the average bromination rate was 10.8. It was confirmed that. The delay time at the time of mass spectrometry was 275 ns, the laser intensity was 42%, and the Resolving Power Value of the peak at m / z = 1820 to 1860 was 42559. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated zinc phthalocyanine derivative (S4) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A4). Derivative carrier (A4) 2.48 g was combined with BYK-LPN6919 1.24 g manufactured by BYK-Chemie Corporation, Unidic ZL-295 1.86 g manufactured by DIC Corporation, and 0.32-0.4 together with 10.92 g propylene glycol monomethyl ether acetate. Using a zircon bead of mm, it was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (AMG4). Coloring composition (AMG4) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added, and the composition for evaluation (ACG4) is mixed by a paint shaker. Obtained. This composition for evaluation (ACG4) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Corporation. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 3273.1, and the transmittance at 460 nm was 42.89.

Synthesis example 5
A 1 L flask was charged with 60 g of phthalonitrile, 300 g of 1-chloronaphthalene and 16 g of aluminum chloride and stirred for 6 hours under reflux. Thereafter, the heating was stopped, the mixture was allowed to cool to 200 ° C., filtered while hot, and washed with 600 g of hot toluene and 300 g of acetone. The obtained wet cake was dispersed in 250 g of toluene and stirred and refluxed for 3 hours. The mixture was again filtered while hot, washed with 600 g of hot toluene and 300 g of acetone, dispersed in 1500 g of ion-exchanged water, and heated and stirred at 60 ° C. for 60 minutes. Filtration, washing with water and vacuum drying at 50 ° C. gave blue solid aluminum phthalocyanine (AlPc—Cl). 30 g of aluminum phthalocyanine (AlPc—Cl) was gradually dissolved in 1200 g of concentrated sulfuric acid while keeping the temperature at 5 ° C., and stirred at this temperature for 1 hour. This was added to 6000 g of ice water with stirring so that the temperature did not exceed 5 ° C., and further stirred for 1 hour after the end of the addition. After filtration and washing with water, it was redispersed in 6500 g of ion-exchanged water and filtered again. After washing with water, the wet cake was redispersed in 2500 g of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum-dried at 50 ° C. to obtain blue solid aluminum phthalocyanine (AlPc—OH). 288 g of 98% sulfuric acid and 272 g of 30% fuming sulfuric acid were stirred while cooling to 10 ° C., and 70 g of aluminum phthalocyanine (AlPc—OH) was added. Subsequently, it stirred at 60 degreeC for 3 hours. The reaction solution was taken out in 1750 g of water, stirred for 1 hour, filtered, washed with water, and dried to obtain a sulfonated aluminum phthalocyanine derivative (S5). The sulfonated aluminum phthalocyanine derivative (S5) was confirmed to have an average sulfonation rate of 1 by LC-MS measurement. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated aluminum phthalocyanine derivative (S5) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A5). Derivative carrier (A5) 2.48 g, BYK-LPN6919 1.24 g manufactured by BYK Chemie Co., Ltd. Unidic ZL-295 1.86 g manufactured by DIC Corporation, propylene glycol monomethyl ether acetate 10.92 g and 0.3 to 0.4 Using a zircon bead of mm, it was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (AMG5). Coloring composition (AMG5) 4.0g, DIC Corporation Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g is added, and the composition for evaluation (ACG5) is mixed with a paint shaker. Obtained. This evaluation composition (ACG5) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 2757.5, and the transmittance at 460 nm was 64.24.

Synthesis Example 6
After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of Solsperse 12000 (sulfonated copper phthalocyanine derivative manufactured by Nippon Lubrizol Corporation) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A6). Derivative carrier (A6) 2.48 g was combined with BYK-LPN6919 1.24 g manufactured by BYK Chemie Co., Ltd. Unidic ZL-295 1.86 g manufactured by DIC Corporation, and 0.32-0.4 together with 10.92 g propylene glycol monomethyl ether acetate. Using a zircon bead of mm, the mixture was dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (AMG6). Coloring composition (AMG6) 4.0g, DIC Corporation Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g is added, and the composition for evaluation (ACG6) is mixed with a paint shaker. Obtained. This composition for evaluation (ACG6) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Co., Ltd. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 1303.8, and the transmittance at 460 nm was 64.19.

Synthesis example 7
A 1 L flask was charged with 15 g of sulfolane, 10 g of titanium tetrachloride, 200 g of dimethyl phthalate, 100 g of sodium 4-chlorophthalate and 31 g of 20% fuming sulfuric acid, heated at 170 ° C. for 30 minutes, 150 g of urea, and copper (I) 9 .5 g was added. Furthermore, it heated at 150 degreeC for 1 hour, 170 degreeC for 1 hour, and 190 degreeC for 8 hours. After cooling to 80 ° C., it was taken out in 700 g of water in which 60 g of sodium hydroxide was dissolved. After stirring at 85 ° C. for 1 hour, the mixture was poured into 2300 g of water with stirring, and further stirred at 80 ° C. for 2 hours. After filtration and hot water washing, the slurry was reslurried in 2300 g of water in which 140 g of 35% hydrochloric acid was dissolved, and heated at 70 ° C. for 1 hour with stirring. After filtration and hot water washing, a blue solid tetrachlorocopper phthalocyanine was obtained by drying at 80 ° C. for 17 hours. 131 g of 30% fuming sulfuric acid was stirred while being cooled to 10 ° C., and 15 g of tetrachlorocopper phthalocyanine was added. Subsequently, it stirred at 90 degreeC for 3 hours. The reaction solution was taken out in 750 g of water, stirred for 15 minutes, filtered, washed with water, and dried to obtain a sulfonated copper phthalocyanine derivative (S7). The sulfonated copper phthalocyanine derivative (S7) was confirmed to have an average sulfonation rate of 1 and an average chlorination rate of 4 by LC-MS measurement. After adding 100 g of ethanol to 30 g of aluminum oxide (AEROXIDE Alu C) manufactured by Nippon Aerosil Co., Ltd. and stirring well, 2000 g of water was added to prepare a white slurry. 1.5 g of a sulfonated copper phthalocyanine derivative (S7) was added, the pH was adjusted to 12 with an aqueous potassium hydroxide solution, and the mixture was stirred at room temperature for 2 hours. The pH was adjusted to 3 with 10% hydrochloric acid, and the mixture was further stirred at room temperature for 1 hour, and then filtered, washed with water, dried and pulverized to obtain a derivative carrier (A7). Derivative carrier (A7) 2.48 g, BYK-LPN6919 1.24 g manufactured by Big Chemie Co., Ltd. Unidic ZL-295 1.86 g manufactured by DIC Corporation, propylene glycol monomethyl ether acetate 10.92 g and 0.3 to 0.4 Using a zircon bead of mm, the mixture was dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (AMG7). Coloring composition (AMG7) 4.0g, DIC Corporation Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g is added, and the composition for evaluation (ACG7) is mixed by a paint shaker. Obtained. This composition for evaluation (ACG7) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes, and then the spectral transmission spectrum was measured with U-3900 manufactured by Hitachi High-Tech Science Corporation. In addition, the spectral transmission spectrum in which the maximum transmittance is 70% was measured by adjusting the spin rotation number when spin coating. For transmission spectrum measurement, soda glass was used to perform baseline correction. The integral value of the transmittance at 510 nm to 560 nm was 1401.9, and the transmittance at 460 nm was 64.60.

Production Example 1
36 g of halogenated zinc phthalocyanine (R1), 4 g of sulfonated zinc phthalocyanine derivative (S1), 400 g of crushed sodium chloride and 63 g of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G1).

Production Example 2
A green pigment composition (G2) was obtained in the same manner as in Production Example 1 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S2).

Production Example 3
A green pigment composition (G3) was obtained in the same manner as in Production Example 1 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S3).

Production Example 4
A green pigment composition (G4) was obtained in the same manner as in Production Example 1 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S4).

Production Example 5
A green pigment composition (G5) was obtained in the same manner as in Production Example 1 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated aluminum phthalocyanine derivative (S5).

Production Example 6
A green pigment composition (G6) was obtained in the same manner as in Production Example 1 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated copper phthalocyanine derivative (S7).

Production Example 7
38 g of halogenated zinc phthalocyanine (R1), 2 g of sulfonated zinc phthalocyanine derivative (S1), 400 g of crushed sodium chloride and 63 g of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G7).

Production Example 8
A green pigment composition (G8) was obtained in the same manner as in Production Example 7 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S2).

Production Example 9
A green pigment composition (G9) was obtained in the same manner as in Production Example 7 except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S3).

Production Example 10
36 g of halogenated zinc phthalocyanine (R2), 4 g of sulfonated zinc phthalocyanine derivative (S3), 400 g of crushed sodium chloride and 63 g of diethylene glycol were charged into a double-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G10).

Production Example 11
A green pigment composition (G11) was obtained in the same manner as in Production Example 10 except that the sulfonated zinc phthalocyanine derivative (S3) was replaced with the sulfonated zinc phthalocyanine derivative (S4).

Production Example 12
A green pigment composition (G12) was obtained in the same manner as in Production Example 10 except that the sulfonated zinc phthalocyanine derivative (S3) was replaced with Solsperse 12000 (sulfonated copper phthalocyanine derivative manufactured by Nippon Lubrizol Corporation).

Production Example 13
Pigment Yellow 138 (Chromofine Yellow 6206EC, manufactured by Dainichi Seika Co., Ltd.) 1.65 g, 3.85 g of DISPERBYK-161 (manufactured by Big Chemie), 0.3-0.4 mm zircon together with 11.00 g of propylene glycol monomethyl ether acetate Using beads, the mixture was dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (MY1). Coloring composition (MY1) 4.0g, Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g was added, and the composition for toning (TY1) was obtained by mixing with a paint shaker.

Example 1
2.48 g of green pigment composition (G1) is 0.3 to 0.00 together with 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Corporation, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using 4 mm zircon beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (MG1). Coloring composition (MG1) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added and mixed with a paint shaker to form a green pixel portion for a color filter. An evaluation composition (CG1) was obtained. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG1) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 2
An evaluation composition (CG2) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G2) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG2) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 3
An evaluation composition (CG3) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G3) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG3) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 4
An evaluation composition (CG4) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G4) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG4) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 5
An evaluation composition (CG5) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G5) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG5) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 6
An evaluation composition (CG7) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G7) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG7) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 7
An evaluation composition (CG8) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G8) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG8) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 8
An evaluation composition (CG9) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G9) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG9) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 9
Green pigment composition (RG1) 2.23 g, sulfonated zinc phthalocyanine derivative (S1) 0.25 g, BYK-LPN6919 1.24 g manufactured by BYK Chemie Co., Ltd. UNIDIC ZL-295 1.86 g manufactured by DIC Corporation, propylene glycol monomethyl Using 0.32-0.4 mm zircon beads together with 10.92 g of ether acetate, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (MG10). Coloring composition (MG10) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added and mixed with a paint shaker to form a green pixel portion for a color filter. To obtain a composition for evaluation (CG10). A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG10) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 10
An evaluation composition (CG11) was obtained in the same manner except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S2) in Example 9. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG11) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 11
An evaluation composition (CG12) was obtained in the same manner except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S3) in Example 9. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG12) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 12
An evaluation composition (CG13) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G10) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG13) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.275, 0.570) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Example 13
An evaluation composition (CG14) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G11) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG14) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes. A coating film showing chromaticity (x, y) = (0.275, 0.570) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Comparative Example 1
An evaluation composition (CG6) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G6) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG6) was spin-coated on soda glass, dried at 90 ° C. for 3 minutes, and then used in a C light source. A coating film showing chromaticity (x, y) = (0.250, 0.615) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

Comparative Example 2
An evaluation composition (CG12) was obtained in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G12) in Example 1. A coating liquid obtained by mixing the toning composition (TY1) prepared in Production Example 13 and the evaluation composition (CG12) was spin-coated on soda glass and dried at 90 ° C. for 3 minutes. A coating film showing chromaticity (x, y) = (0.275, 0.570) was produced. The brightness was measured with U-3900 manufactured by Hitachi High-Tech Science, and the film thickness was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science.

  As shown in Tables 1 and 2, it was confirmed that those using the sulfonated zinc phthalocyanine derivative and the sulfonated aluminum phthalocyanine derivative had higher brightness than those using the sulfonated copper phthalocyanine derivative. In addition, when the film thickness was less than 3.4 μm, ◎, 3.4 μm or more and 3.6 μm or less were evaluated as ◯, and those thicker than 3.6 μm were evaluated as ×, sulfonated zinc phthalocyanine derivative, sulfonated Those using an aluminum phthalocyanine derivative were marked with ◎ or ○.

  In the present invention, since a pigment derivative having a D2 / D1 higher than that of a conventionally used sulfonated copper phthalocyanine (SOLSPERSE 12000, sulfonated copper phthalocyanine derivative (S7)) is selected and used, the luminance is high. Furthermore, in the present invention, since a pigment derivative having a transmittance of 460 nm lower than that of a conventionally used sulfonated copper phthalocyanine (SOLSPERSE 12000, sulfonated copper phthalocyanine derivative (S7)) is selected and used, Is thin.

Claims (11)

A zinc halide phthalocyanine pigment;
The following general formula (1):

(In General Formula (1), Z ^{1 to} Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and at least the average number of substituents of the sulfo group is 0.1 to 4 , M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb.) A color filter pigment composition characterized by comprising:
In addition, the integral value of the transmittance of 510 nm to 560 nm of the coating film formed using the halogenated zinc phthalocyanine pigment so that the spectral transmittance at the maximum transmission wavelength becomes 70% is set to D1, and the pigment derivative is changed to aluminum oxide. When the integral value of the transmittance of 510 nm to 560 nm of the coating film formed so as to have a spectral transmittance of 70% at the maximum transmission wavelength using the derivative carrier obtained by carrying is D2,
A pigment composition for a color filter having a spectral characteristic in which a ratio (D2 / D1) of D1 and D2 is 0.7 or more. In the pigment derivative, in the formula (1), Z ^{1 to} Z ¹⁶ are any one of a bromine atom, a chlorine atom, a hydrogen atom, and a sulfo group, and an average in one molecule is at least Z ¹ , Z ⁴ , ^{Z 5, Z 8, Z 9} , Z 12, Z 13, a color filter pigment composition according to claim 1, wherein the one or two or more selected from ^{Z 16} is a pigment derivative having a chlorine atom . In the pigment derivative, in the formula (1), Z ^{1 to} Z ¹⁶ have any one of a bromine atom, a chlorine atom, a hydrogen atom, and a sulfo group, and at least Z ¹ and Z ^{4 on} average in one molecule. 2. A pigment composition for a color filter according to claim 1, wherein any two or more selected from Z ⁵ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ is a pigment derivative having a bromine atom. object. In the pigment derivative, Z ^{1 to} Z ¹⁶ in the formula (1) contain 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms on average in one molecule. The color filter pigment composition according to any one of claims 1 to 3, wherein the pigment composition is a pigment derivative. Furthermore, a yellow pigment is contained, The pigment composition for color filters as described in any one of Claims 1-4 characterized by the above-mentioned. A color filter comprising the color filter pigment composition according to any one of claims 1 to 5 in a pixel portion. A zinc halide phthalocyanine pigment;
The following general formula (1):

(In General Formula (1), Z ^{1 to} Z ¹⁶ each independently represent a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and at least the average number of substituents of the sulfo group is 0.1 to 4 , M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb.) It is a color filter characterized by containing,
In addition, the integral value of the transmittance of 510 nm to 560 nm of the coating film formed using the halogenated zinc phthalocyanine pigment so that the spectral transmittance at the maximum transmission wavelength becomes 70% is set to D1, and the pigment derivative is changed to aluminum oxide. When the integral value of the transmittance of 510 nm to 560 nm of the coating film formed so as to have a spectral transmittance of 70% at the maximum transmission wavelength using the derivative carrier obtained by carrying is D2,
A color filter having a spectral characteristic in which a ratio (D2 / D1) of D1 and D2 is 0.7 or more. In the pigment derivative, in the formula (1), Z ^{1 to} Z ¹⁶ are any one of a bromine atom, a chlorine atom, a hydrogen atom, and a sulfo group, and an average in one molecule is at least Z ¹ , Z ⁴ , The color filter according to claim 7, wherein any two or more selected from Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ is a pigment derivative having a chlorine atom. In the pigment derivative, in the formula (1), Z ^{1 to} Z ¹⁶ have any one of a bromine atom, a chlorine atom, a hydrogen atom, and a sulfo group, and at least Z ¹ and Z ^{4 on} average in one molecule. The color filter according to claim 7, wherein any two or more selected from Z ⁵ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ , and Z ¹⁶ is a pigment derivative having a bromine atom. In the pigment derivative, Z ^{1 to} Z ¹⁶ in the formula (1) contain 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms on average in one molecule. The color filter according to claim 7, wherein the color filter is a pigment derivative. The color filter according to any one of claims 7 to 10, further comprising a yellow pigment.