CN110402404B

CN110402404B - Pigment composition for color filter and color filter

Info

Publication number: CN110402404B
Application number: CN201880017245.1A
Authority: CN
Inventors: 坂本圭亮; 千叶祐奈; 清水郁马; 木村亮
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2017-04-03
Filing date: 2018-03-22
Publication date: 2021-09-07
Anticipated expiration: 2038-03-22
Also published as: KR102531076B1; TWI745571B; TW201843247A; JP6455748B1; WO2018186182A1; KR20190137072A; CN110402404A; JPWO2018186182A1

Abstract

The present invention addresses the problem of providing a pigment composition for obtaining a color filter having improved brightness without increasing the thickness of the film. The present invention can provide a pigment composition for a color filter, which is characterized by containing a zinc halide phthalocyanine pigment and a pigment derivative represented by the following general formula (1), and a color filter having the pigment composition for a color filter in a pixel portion.

(in the general formula (1), Z¹～Z¹⁶Each independently represents a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, the average number of substituents of at least the sulfo group is 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb).

Description

Pigment composition for color filter and color filter

Technical Field

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

Background

The color filter for a liquid crystal display is a member of: by regularly arranging a plurality of colors on a transparent glass substrate, only light in a desired wavelength region is transmitted from white light of a backlight passing through the glass substrate, and color display of a display is realized. The colors used therein generally include three primary colors of red, green and blue, and the color materials, resins, additives and the like used are repeatedly improved in order to adjust the transmission spectra, respectively. Among them, a green colorant for color filters is required to have higher luminance and an expanded color reproduction range from the viewpoint of improving the image quality of displays.

For the improvement of brightness, it is important to select a pigment having high transmittance to backlight light, and the pigment green 58 is used as a main pigment instead of the conventional pigment green 36. Further, the white light of the backlight can be efficiently used by increasing the luminance by the pigment improvement, and therefore, energy saving and manufacturing cost reduction of the display can be achieved.

In order to expand the color reproduction range, it is necessary to increase the chroma of the coloring material contained in the color filter. In order to produce a coating film having high chroma, there are methods of increasing the pigment concentration in the coating film or increasing the thickness of the coating film at the same pigment concentration. However, in any case, it is difficult to ensure various resistances of the coating film, and therefore, pigment green 7, which can be made thinner at a specific chroma after color-mixing with a yellow coloring material than pigment green 36 and pigment green 58 conventionally used for color filter applications, is selected as the main pigment. Although the color reproduction range can be widened by thickening pigment green 36 and pigment green 58, the reason why pigment green 7 was selected is that the NTSC ratio of 90% or more cannot be achieved with a practical film thickness of about 3.5 μm. 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 to realize high color reproduction with a thin film of 2.2 μm or less. However, since pigment green 7 has a lower transmittance than pigment green 36 and pigment green 58, the luminance of the resultant display is reduced. Further, the luminance can be compensated for by increasing the amount of backlight light, but a new problem of increased power consumption occurs, and thus improvement is required. From the above, a color material for color filters is desired which is compatible with both brightness and color reproducibility.

In order to solve these problems, proposed are: when aluminum phthalocyanine is used as a main pigment, a phthalocyanine sulfonic acid derivative is added to produce a color filter having excellent color density, color purity, and transparency, and also having excellent heat resistance and light resistance (patent document 1). However, aluminum phthalocyanine pigments, which are main pigments, have low heat resistance and light resistance, and thus cannot satisfy the performance required in recent years.

Further, it has been proposed to produce a color filter having a good contrast by using a green pigment composition containing a copper halide phthalocyanine pigment and a low-halide copper phthalocyanine sulfonic acid derivative, wherein the green pigment composition has an average particle diameter of primary particles of 0.01 to 0.1 μm and an aspect ratio of 1 to 3 (patent document 2). However, the copper phthalocyanine pigment as a main pigment has low brightness, and thus the performance required in recent years may not be satisfied.

Thus, the actual situation is: these prior arts are insufficient for satisfying the rapidly increasing performance requirements in recent years in order to form a color filter aiming at higher brightness and an expanded color reproduction range, and the object has not yet been achieved.

Patent document 1: japanese patent laid-open publication No. 2011-057910

Patent document 2: japanese patent laid-open publication No. 2005-316244

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a pigment composition for obtaining a color filter having improved brightness without increasing the thickness of the film.

Means for solving the problems

The present inventors have conducted intensive studies in view of such circumstances, and as a result, have found that: by using a zinc halide phthalocyanine pigment as a main pigment and incorporating a specific pigment derivative, a color filter which can improve luminance without increasing the thickness of the film can be produced. That is, the present invention relates to a pigment composition for a color filter, which is characterized by containing a zinc halide phthalocyanine pigment and a pigment derivative represented by the following general formula (1), and a color filter having the pigment composition for a color filter in a pixel portion.

[ solution 1]

(in the general formula (1), Z¹～Z¹⁶Each independently represents a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, at least one of the sulfo groupsThe number of the substituents is 0.1 to 4, and M represents Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb. )

Effects of the invention

According to the present invention, a color filter capable of improving luminance without increasing the thickness of the film can be manufactured.

Detailed Description

The zinc halide phthalocyanine pigment used in the present invention is a compound in which zinc metal is arranged at the center, and at least 1 or more halogen atoms selected from chlorine, bromine, fluorine and iodine are substituted on a phthalocyanine ring which may be substituted with a substituent other than halogen, and the total number of the substituents is at most 16. The moiety not substituted by halogen and a substituent other than halogen means a moiety which is a hydrogen atom.

Among them, from the viewpoint of designing a color filter having a wide color reproduction range, the zinc halide phthalocyanine pigment used in the present invention is preferably a pigment having 10 to 14 halogen atoms on average in 1 molecule, wherein the number of bromine atoms is 8 to 12 on average, and the number of chlorine atoms is 2 to 5 on average.

The pigment derivative used in the present invention may be represented by the above general formula (1).

Among them, from the viewpoint of making the hues of the main pigment of the green color filter and the pigment derivative similar, the following pigment derivatives are preferably used as the pigment derivative: in the above general formula (1), Z¹～Z¹⁶Has any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and is at least from Z on average in one molecule¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (1) have a chlorine atom.

In addition, from the viewpoint of making the hues of the main pigment and the pigment derivative of the green color filter similar, the following pigment derivatives are also preferably used as the pigment derivative: in the above general formula (1), Z¹～Z¹⁶Has any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and is at least from Z on average in one molecule¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (a) have a bromine atom.

Japanese patent application laid-open No. 2010-189528 describes: if a chlorine or bromine atom enters Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶The color of the green pigment is relatively green.

From the viewpoint of making the hue of the pigment derivative more similar to that of the main pigment, it is more preferable that Z is represented by the average in one molecule¹～Z¹⁶Contains 10-14 halogen atoms, 8-12 bromine atoms, and 2-5 chlorine atoms.

The pigment composition of the present invention as described above is not a pigment composition in which a conventional pigment and a pigment derivative having a skeleton of the same system are simply combined, but the present invention has been completed based on the following idea.

(A) First, a general organic pigment forms a highly conjugated system as a whole molecule and has a planar structure, which is stable in energy. When the planar molecules are arranged in a stacked manner (in parallel), pi electrons of conjugated systems between the molecules overlap with each other, and thus a more stable state is obtained. The pigment derivative represented by the general formula (1) used in the present invention has a planar structure because it has a phthalocyanine ring, and thus easily interacts with the planar structure of an organic pigment. Further, it is considered that: in the case where the main pigment is a halogenated phthalocyanine pigment, it is particularly easy to generate a halogen-pi interaction between the derivative and pi electrons. Consider that: if such a specific pigment derivative is allowed to coexist in the organic pigment dispersion step, the derivative is efficiently adsorbed on the active surface of the halogenated phthalocyanine pigment newly generated at the time of dispersion. Further, the halogenated phthalocyanine pigment can be dispersed and stabilized in a fine state by the sulfonic group as a polar group, and thus the luminance can be improved. Here, although the sulfonated phthalocyanine derivative of the present invention can be added at the time of pigmenting and can exert a good effect even when added at the time of dispersing, if it is allowed to coexist in the pigmenting step, it can enter between the molecules of the halogenated phthalocyanine pigment to keep the primary particles fine, and therefore, the sulfonated phthalocyanine derivative of the present invention can achieve a much greater improvement in luminance when coexisted at the time of pigmenting than when added at the time of dispersing.

(B) Further, the present invention has been completed with a view to overlapping absorption spectra of a pigment and a derivative. In order to obtain a bright and vivid display in the color filter of the green pixel, it is particularly preferable to increase the transmittance of 510nm to 560 nm. In order to design a color filter which transmits only the narrow wavelength region, a combination of a green pigment and a yellow pigment is used, and therefore, it is preferable to form a combination in which a pigment derivative treated in the green pigment has a similar transmission wavelength to that of the green pigment at 510 to 560 nm.

(C) Further, Japanese patent application laid-open No. 8-240708 discloses: if the transmittance of 430nm to 460nm is high, the chromaticity y value is greatly reduced, the vividness of green is greatly impaired, and therefore the transmittance in this wavelength range is preferably low. When the chromaticity y value is low, the chromaticity y value must be increased by increasing the film thickness, but if the film thickness is increased, the luminance is lowered. Therefore, it is necessary to select a pigment derivative having as low a transmittance as possible from 430nm to 460 nm. In particular, the green pixel of the color filter is generally used in combination with a green pigment, c.i. pigment yellow 138(Y138) which is a quinophthalone-based yellow pigment. Japanese laid-open patent publication No. 2015-26077 describes: since Y138 shifts from the absorption band to the transmission band around 460nm, Y138 can absorb light having a wavelength shorter than 460nm but is not suitable for absorption on the long-wavelength side, and thus the derivative treated with a green pigment preferably has a low transmittance at 460 nm.

From the viewpoint of the above (B) and (C), the central metal M in the above formula (1) is preferably Al or Zn, and particularly preferably Zn. When the point of (C) is described in detail, the transmittance at 430nm to 460nm is lower when the pigment derivative of the formula (1) is a substance in which the metal M is Zn than when the pigment derivative of the formula (1) is a substance in which the metal M is Al, and therefore a pigment composition having high brightness can be produced.

Such a pigment derivative can be obtained by, for example, the following conventionally known method. That is, it can be obtained by dissolving phthalocyanine or halogenated phthalocyanine in sulfuric acid and heating to 100 ℃ or higher, or dissolving in fuming sulfuric acid and treating at low temperature. If a sulfo group is introduced into a 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. In the general formula (1), the average number of substituents of the sulfo group is preferably 0.1 to 4, more preferably 0.5 to 2 on average in one molecule, from the viewpoint of using a pigment derivative having a higher purity.

The sulfo group may be a sulfonic acid or may be in the form of a salt. As examples of the counter ion forming the salt, there may be included: ammonium ions, metal ions having a valence of 1 to 3 (specific examples thereof include lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, strontium ions, aluminum ions, etc.), and organic cations (specific examples thereof include monoalkylammonium ions such as ethylammonium ions and butylammonium ions, dialkylammonium ions such as dimethylammonium ions and diethylammonium ions, trialkylammonium ions such as trimethylammonium ions and triethylammonium ions, alkanolammonium ions such as monoethanolammonium ions, diethanolaminium ions and triethanolammonium ions, tetramethylammonium ions, tetramethylguanidine ions, tetramethylphosphonium ions, etc.). In particular, the sulfo group of the pigment derivative in the present invention is preferably a sulfonic acid or an organic cation salt, in terms of reducing the elution amount of the pigment derivative in the development step for producing a color filter.

In the present invention, the average number of halogen atoms of the halogenated zinc phthalocyanine pigment can be determined by mass analysis. Mass analysis was performed using a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (JMS-S3000, manufactured by japan electronics), and when mass analysis of a known compound having a molecular weight of Q was performed, each measurement parameter was set so that m/z ═ Q was detected. In the present invention, when mass analysis of a known compound having a molecular weight of 1840 is performed, the setting of JMS-S3000 is adjusted so that m/z ═ l840 is detected. The mass analysis was performed using 1. mu.L of a suspension obtained by dispersing 0.5mg of a zinc halide phthalocyanine pigment in 1mL of tetrahydrofuran.

In the present invention, the average sulfonation ratio of the pigment derivative can be determined by a high performance liquid chromatography mass spectrometer (LC-MS-8040 manufactured by Shimadzu corporation). The pigment derivative was subjected to constant volume with dimethyl sulfoxide, and a gradient elution curve was used in which a mixed solvent of 10mmol/L aqueous ammonium bicarbonate solution/methanol/tetrahydrofuran was used as a mobile phase. The obtained peaks were respectively characterized by mass analysis (ionization mode: DUIS), and the sulfonation ratio was calculated from the peak area ratio.

In the pigment derivative of the present invention, Z in the general formula (1)¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Number of halogen substituents m and Z²、Z³、Z⁶、Z⁷、Z¹⁰、Z¹¹、Z¹⁴、Z¹⁵The number n of halogen substituents of (b) is determined by decomposing a pigment derivative with cerium sulfate to produce phthalimides, and then analyzing the obtained phthalimides by liquid chromatography. The total molar concentration of all phthalimides obtained as a result of liquid chromatography is represented by a, the total molar concentration of phthalimides having a halogen at the 3-position or 6-position is represented by b (in the case of phthalimides having a halogen at both the 3-and 6-positions, the molar concentration of the phthalimides is calculated as 2 times the actual concentration), and the total molar concentration of phthalimides having a halogen at the 4-position or 5-position is represented by c (in the case of phthalimides having a halogen at both the 4-and 5-positions, the molar concentration of the phthalimides is calculated as 2 times the actual concentration), the molar concentrations are calculated as m 4 × b/a and n 4 × c/a. Although m and n can be obtained by liquid chromatography, m and n can be freely determined by controlling the amount of raw materials to be charged. For example, in a pigment derivative obtained by sulfonating tetrachlorozinc phthalocyanine synthesized from 3-chlorophthalic anhydride as a raw material, m is 4 and n is 0. In addition, in the pigment derivatives obtained by sulfonating tetrachlorozinc phthalocyanine synthesized by using 4-chlorophthalic anhydride as a raw material, m is 0 and n is 4.

In the present invention, the average number of halogen atoms of the pigment derivative can be determined by mass analysis 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 the formation of the pigment, or may be formed into the pigment together with the crude pigment at the time of formation of the pigment. Further, since the dispersibility of the dispersion liquid for color filters and the resist ink for color filters is increased to improve the brightness, the pigment derivative may be added at the time of dispersion or at the time of resist production. The pigment derivative used in the present invention is preferably incorporated into the zinc halide phthalocyanine pigment so as to be able to enter between the molecules thereof and keep the primary particles fine, and is thus preferably formed into a pigment together with a crude pigment.

The pigment composition containing the zinc halide phthalocyanine pigment and the pigment derivative represented by the formula (1) is subjected to dry milling in a mill such as an attritor, a ball mill, a vibration mill or a vibration ball mill, if necessary, and then is subjected to pigmenting by a solvent salt milling method, a solvent boiling method or the like, whereby a pigment which is excellent in dispersibility and tinting strength compared with those before pigmenting and emits a green color with high brightness can be obtained.

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

The method of pigmenting the green pigment composition comprising the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) is not particularly limited, and for example, the pigment composition comprising the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) before pigmenting may be simultaneously pigmentized while being dispersed in a dispersion medium, but the solvent salt milling treatment is preferably employed in that the crystal growth can be easily suppressed and pigment particles having a large specific surface area can be obtained, as compared with the solvent treatment in which the pigment composition comprising the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) is heated and stirred in a large amount of organic solvent.

The solvent salt milling is a process in which a pigment composition comprising a zinc halide phthalocyanine pigment and a pigment derivative represented by the above formula (1), which has been milled immediately after or after the synthesis and is not subjected to pigmentation, an inorganic salt, and an organic solvent are kneaded and milled. Examples of the kneading machine in this case include a kneader, a mixing roll (Mix Muller), a triple mixer (Trimix), and a twin-screw extruder.

As the inorganic salt, a water-soluble inorganic salt can be suitably used, and for example, inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate are preferably used. Further, it is more preferable to use an inorganic salt having an average particle diameter of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing a general inorganic salt.

In the present invention, it is preferable that a pigment composition containing a zinc halide phthalocyanine pigment and a pigment derivative represented by the above formula (1) and having an average primary particle diameter of 0.01 to 0.10 μm is used for color filters. In order to obtain the preferred particle size in the present invention, it is preferable to increase the amount of the inorganic salt used relative to the amount of the crude pigment used in the solvent salt mill. 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, based on 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, and 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 monobutyl ether, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol, and the like can be used. The amount of the water-soluble organic solvent used is not particularly limited, but is preferably 0.01 to 5 parts by mass relative to 1 part by mass of the crude pigment.

In the case of producing a pigment composition containing a zinc halide phthalocyanine pigment and a pigment derivative represented by the above formula (1) by solvent salt milling, the zinc halide phthalocyanine pigment and the pigment derivative represented by the above formula (1) may be separately subjected to solvent salt milling and then brought together, or the zinc halide phthalocyanine pigment and the phthalocyanine pigment derivative represented by the above formula (1) may be simultaneously mixed in an apparatus and subjected to solvent salt milling. In the evaluation of optical characteristics by color filters, there is not much difference in the way that luminance can be improved in any of the methods.

As described above, the pigment composition of the present invention has a wavelength (Tmax) of 500 to 525nm at which the transmittance of a spectral transmission spectrum at 380 to 780nm becomes maximum, and a half-value width of a transmission curve thereof is 110nm or less, and is extremely sharp (the wavelength is not affected by a photosensitive resin as described later), similarly to a conventional zinc halide phthalocyanine pigment.

The spectral transmission spectrum in the evaluation of color filters is obtained by scanning a resin film containing a pigment composition formed in the above-mentioned predetermined dry film thickness on a glass substrate or the like and irradiating the resin film with light in a predetermined wavelength range, and plotting each transmittance value at each wavelength, according to a first spectral photometer of JIS Z8722 (color measurement method — reflection and transmission object color).

Here, it is preferable that the pigment composition for color filters having a spectral characteristic in which the ratio of D1 to D2 (D2/D1) is 0.7 or more, when the integrated value of the transmittance at 510nm to 560nm of a coating film formed using a zinc halide phthalocyanine pigment so that the spectral transmittance at the maximum transmission wavelength becomes 70% is D1, and the integrated value of the transmittance at 510nm to 560nm of a coating film formed using a derivative carrier obtained by supporting a pigment derivative represented by the above general formula (1) on alumina so that the spectral transmittance at the maximum transmission wavelength becomes 70% is D2, since the decrease in the luminance of a green color filter due to the pigment derivative can be minimized. In order to design a green color filter having higher brightness, a pigment composition for color filters having spectral characteristics in which the ratio of D1 to D2 (D2/D1) is 1.0 or more is more preferable, and a pigment composition for color filters having spectral characteristics in which the ratio of D1 to D2 (D2/D1) is 1.2 or more is even more preferable.

Further, a pigment composition for color filters having spectral characteristics in which the 460nm transmittance of a coating film formed using a derivative support obtained by supporting a pigment derivative represented by the above general formula (1) on alumina so that the spectral transmittance at the maximum transmission wavelength is 70% is 60% or less is preferable because a green color filter having high color reproducibility in which a decrease in chromaticity y is suppressed can be produced. In order to design a green color filter having higher color reproducibility, a pigment composition for a color filter having a spectral characteristic that the transmittance at 460nm is 55% or less is more preferable, and a pigment composition for a color filter having a spectral characteristic that the transmittance at 460nm is 50% or less is even more preferable.

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

Further, in addition to the green pigment, a yellow pigment is sometimes used for toning in order to express characteristics. Examples of the yellow pigment usable in combination include yellow organic pigments such as c.i. pigment yellow 83, c.i. pigment yellow 110, pigment yellow 129, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 180, c.i. pigment yellow 185, and c.i. pigment yellow 231. The present invention relates to a combination of a zinc halide phthalocyanine pigment composition and a yellow pigment, wherein the yellow pigment is used in an amount of 1 to 200 parts by mass per 100 parts by mass of the zinc halide phthalocyanine pigment composition.

(color Filter)

The pigment composition of the present invention is used to form a green pixel, thereby obtaining a color filter.

(method for manufacturing color Filter)

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 green pixel portion of a color filter containing the present pigment composition and a photosensitive resin as essential components can be obtained.

Examples of a method for manufacturing a color filter include a method called photolithography: the pigment composition for a color filter of the present invention is dispersed in a dispersion medium containing a photosensitive resin, and then applied onto a transparent substrate such as glass by a spin coating method, a roll coating method, a slit coating method, an ink jet method, or the like, and then the applied film is subjected to pattern exposure with ultraviolet rays through a photomask, and then an unexposed portion is washed with a solvent or the like to obtain a green pattern.

Other production methods include, for example: a method of forming a pattern of a green pixel portion by a method such as an Electrodeposition method, a transfer method, a micelle electrolysis method, or a PVED (photo electro deposition) method, and a method of manufacturing a color filter. The pattern of the red pixel portion and the pattern of the blue pixel portion may be formed by the same method using a known pigment.

For preparing the photosensitive composition for a green pixel portion of a color filter, for example, the pigment composition for a color filter of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent for dissolving the above resin are mixed as essential components. More specifically, the following method is generally used: the pigment composition of the present invention, an organic solvent and, if necessary, a dispersant are used to prepare a dispersion, and then a photosensitive resin or the like is added thereto to prepare the pigment composition.

Examples of the dispersant include: DISPERBYK (DISPERBYK, registered trademark) 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, DISPERBYK LPN-6919, DISPERBYK LPN-21116, etc., of Bikk chemical company. Further, a leveling agent, a coupling agent, a cationic surfactant, and the like may be used in combination.

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

The dispersion liquid can be obtained by stirring and dispersing 300 to 1000 parts by mass of the organic solvent and, if necessary, 0 to 100 parts by mass of the dispersant with respect to 100 parts by mass of the pigment composition of the present invention so as to be uniform. Then, a photosensitive resin in an amount of 3 to 20 parts by mass per 100 parts by mass of the pigment composition of the present invention and a photopolymerization initiator in an amount of 0.05 to 3 parts by mass per 1 part by mass of the photosensitive resin are added to the dispersion, and an organic solvent is further added as needed, and the mixture is stirred and dispersed so as to be uniform, thereby obtaining a photosensitive composition for a green pixel portion of a color filter.

Examples of the photosensitive resin include: thermoplastic resins such as polyurethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins; 2-functional monomers such as 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloyloxyethoxy) bisphenol A, and 3-methylpentanediol diacrylate; and photopolymerizable monomers such as polyfunctional monomers including trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

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

The photosensitive composition for a green pixel portion of a color filter can be obtained by pattern exposure using ultraviolet rays through a photomask and then cleaning the unexposed portion with an organic solvent, alkaline water, or the like.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, "part(s)" and "%" are based on mass unless otherwise specified.

The measurement method used in the examples described below is as follows.

[ evaluation of Brightness ]

The chromaticity x, y and luminance of the obtained color filter under the C light source were measured by a spectral luminance meter U-3900 (manufactured by Hitachi Kagaku K.K.). The higher the luminance, the more excellent.

Reference example 1

90g of sulfuryl chloride (Wako Junyaku chemical industries, Ltd.), 105g of aluminum chloride (Kanto chemical industries, Ltd.), 14g of sodium chloride (Tokyo Kasei Chemicals, Ltd.), 27g of zinc phthalocyanine (manufactured by DIC Co., Ltd.), and 55g of bromine (Wako Junyaku chemical industries, Ltd.) were put into a 300ml flask. The temperature was raised to 130 ℃, and the mixture was taken out into water, and then filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R1). When the zinc halide phthalocyanine (R1) was subjected to mass analysis using JMS-S3000, manufactured by Nippon electronic Co., Ltd., it was confirmed that the average chlorination rate was 2.9 and the average bromination rate was 9.3. In mass analysis, Delay Time was 510ns, Laser Intensity was 40%, and resolution Power Value of a peak having an m/z Value of 1820 to 1860 was 65086.

40g of the zinc phthalocyanine halide (R1) thus obtained, 400g of pulverized sodium chloride and 63g of diethylene glycol were put into a double arm type kneader and kneaded at 80 ℃ for 8 hours. After kneading, the mixture was taken out to 2kg of water at 80 ℃ and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization to obtain a green pigment composition (RG 1). 2.48g of a green pigment composition (RG1) was dispersed for 2 hours using 0.3 to 0.4mm zirconium beads, together with BYK-LPN69191.24g, manufactured by Bikken chemical Co., Ltd., UNIDIC ZL-2951.86 g, and 10.92g of propylene glycol monomethyl ether acetate by using a paint shaker, manufactured by Toyo Seiki Seiko K.K., to obtain a colored composition (RMG 1). 4.0g of the coloring composition (RMG1), UNIDIC ZL-2950.98g of DIC, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (RCG 1). The composition for evaluation (RCG1) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then measured for spectral transmission spectrum using U-3900 manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 2511.6, and the transmittance at 460nm was 8.79.

Reference example 2

Into a 300ml flask, 91g of sulfuryl chloride (Wako pure chemical industries, Ltd.), 109g of aluminum chloride (Kanto chemical industries, Ltd.), 15g of sodium chloride (Tokyo chemical industries, Ltd.), 30g of zinc phthalocyanine (manufactured by DIC Co., Ltd.), and 230g of bromine (Wako pure chemical industries, Ltd.). The temperature was raised to 130 ℃, and the mixture was taken out into water, and then filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R2). When the zinc halide phthalocyanine (R2) was subjected to mass analysis using JMS-S3000, manufactured by Nippon electronic Co., Ltd., it was confirmed that the average chlorination rate was 1.8 and the average bromination rate was 13.2. In mass analysis, Delay Time was 500ns, Laser Intensity was 44%, and resolution Power Value of a peak having an m/z Value of 1820 to 1860 was 31804.

40g of the zinc phthalocyanine halide (R2) thus obtained, 400g of pulverized sodium chloride and 63g of diethylene glycol were put into a double arm type kneader and kneaded at 80 ℃ for 8 hours. After kneading, the mixture was taken out to 2kg of water at 80 ℃ and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization to obtain a green pigment composition (RG 2). 2.48g of a green pigment composition (RG2) was dispersed for 2 hours using 0.3 to 0.4mm zirconium beads, together with BYK-LPN69191.24g, manufactured by Bikken chemical Co., Ltd., UNIDIC ZL-2951.86 g, and 10.92g of propylene glycol monomethyl ether acetate by using a paint shaker, manufactured by Toyo Seiki Seiko K.K., to obtain a colored composition (RMG 2). 4.0g of the coloring composition (RMG2), UNIDIC ZL-2950.98g of DIC, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (RCG 2). The composition for evaluation (RCG2) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then measured for spectral transmission spectrum using U-3900 manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 2787.8, and the transmittance at 460nm was 3.07.

Synthesis example 1

288g of 98% sulfuric acid and 272g of 30% fuming sulfuric acid were stirred while cooling to 10 ℃ and 70g of zinc phthalocyanine manufactured by DIC was added thereto. Subsequently, the mixture was stirred at 60 ℃ for 3 hours. The reaction solution was taken out to 1750g 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 found to have an average sulfonation ratio of 1 by LC-MS measurement. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of sulfonated zinc phthalocyanine derivative (S1) was added thereto, and the mixture was adjusted to pH12 with an aqueous solution of potassium hydroxide and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A1). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A1) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 1). 4.0g of the coloring composition (AMG1), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 1). The composition for evaluation (ACG1) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 1988.8, and the transmittance at 460nm was 55.27.

Synthesis example 2

55g of 3-chlorophthalic anhydride, 45g of phthalic anhydride, 20g of zinc chloride, 116g of urea, 600mg of hexaammonium heptamolybdate tetrahydrate, and 250g of sulfolane were put into a 1L flask, and stirred at 190 ℃ for 5 hours. After that, the heating was stopped, the mixture was left to cool, and then filtered, and washed with 780g of 2-propanol, 1000g of 1% aqueous sodium hydroxide solution, and 1000g of 1% hydrochloric acid. After washing with water, the obtained wet cake (wetcake) was dried at 90 ℃ for 12 hours to obtain dichlorozinc phthalocyanine as a blue solid. While cooling 95% sulfuric acid 20g and 30% fuming sulfuric acid 180g to 10 ℃ and stirring, dichlorozinc phthalocyanine 20g was added. Subsequently, the mixture was stirred at 80 ℃ for 5 hours. The reaction solution was taken out to 1000g 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 found to have an average sulfonation ratio of 1 and an average chlorination ratio of 2 by LC-MS measurement. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of sulfonated zinc phthalocyanine derivative (S2) was added thereto, and the mixture was adjusted to pH12 with an aqueous solution of potassium hydroxide and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A2). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A2) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 2). 4.0g of the coloring composition (AMG2), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 2). The composition for evaluation (ACG2) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 3054.6, and the transmittance at 460nm was 57.47.

Synthesis example 3

111g of 3-chlorophthalic anhydride, 20g of zinc chloride, 116g of urea, 600mg of hexaammonium heptamolybdate tetrahydrate, and 250g of sulfolane were placed in a 1L flask, and stirred at 190 ℃ for 5 hours. After that, the heating was stopped, the mixture was left to cool, and then filtered, followed by washing with 780g of 2-propanol, 1000g of an aqueous solution of sodium hydroxide (l%), and 1000g of hydrochloric acid (1%). After washing with water, the obtained wet cake was dried at 90 ℃ for 12 hours to obtain tetrachlorozinc phthalocyanine as a blue solid. While cooling 131g of 30% fuming sulfuric acid to 10 ℃ and stirring, 15g of tetrachlorozinc phthalocyanine was added. Subsequently, the mixture was stirred at 90 ℃ for 3 hours. The reaction solution was taken out into 750g of water, stirred for 15 minutes, filtered, washed with water, and dried to obtain a sulfonated zinc phthalocyanine derivative (S3). The sulfonated zinc phthalocyanine derivative (S3) was found to have an average sulfonation ratio of 1.6 and an average chlorination ratio of 4 by LC-MS measurement. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of sulfonated zinc phthalocyanine derivative (S3) was added thereto, and the mixture was adjusted to pH12 with an aqueous solution of potassium hydroxide and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A3). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A3) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 3). 4.0g of the coloring composition (AMG3), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 3). The composition for evaluation (ACG3) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 3065.8, and the transmittance at 460nm was 53.41.

Synthesis example 4

Into a 300ml flask were charged 54g of sulfuryl chloride (Wako pure chemical industries, Ltd.), 63g of aluminum chloride (Kanto chemical industries, Ltd.), 8.6g of sodium chloride (Tokyo chemical industries, Ltd.), 17g of sulfonated zinc phthalocyanine derivative (A), and 87g of bromine (Wako pure chemical industries, Ltd.). The temperature is raised to 130 ℃, and the sulfonated zinc phthalocyanine derivative is obtained by taking out the sulfonated zinc phthalocyanine derivative into water, filtering, washing and drying (S4). The sulfonated zinc phthalocyanine derivative (S4) was subjected to mass analysis using JMS-S3000 manufactured by japan electronics corporation, and it was confirmed that the average sulfonation ratio was 1, the average chlorination ratio was 2.2, and the average bromination ratio was 10.8. In mass analysis, Delay Time was 275ns, Laser Intensity was 42%, and resolution Power Value of a peak having an m/z Value of 1820 to 1860 was 42559. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of sulfonated zinc phthalocyanine derivative (S4) was added thereto, and the mixture was adjusted to pH12 with an aqueous solution of potassium hydroxide and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A4). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A4) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 4). 4.0g of the coloring composition (AMG4), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 4). The composition for evaluation (ACG4) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 3273.1, and the transmittance at 460nm was 42.89.

Synthesis example 5

A1L flask was charged with 60g of phthalonitrile, 300g of 1-chloronaphthalene and 16g of aluminum chloride, and the mixture was stirred under reflux for 6 hours. Thereafter, the heating was stopped, and the mixture was left to cool to 200 ℃ and then subjected to hot filtration, followed by washing with 600g of hot toluene and 300g of acetone. The resulting wet cake was dispersed in 250g of toluene and stirred under reflux for 3 hours. The mixture was again subjected to thermal filtration, washed with 600g of hot toluene and 300g of acetone, dispersed in 1500g of ion-exchanged water, and stirred at 60 ℃ for 60 minutes. After filtration and washing with water, vacuum drying was carried out at 50 ℃ to obtain aluminum phthalocyanine (AlPc-Cl) as a blue solid. 30g of aluminum phthalocyanine (AlPc-Cl) was gradually dissolved in 1200g of concentrated sulfuric acid while keeping the temperature at 5 ℃ and stirred at that temperature for 1 hour. The mixture was poured into 6000g of ice water at a temperature not exceeding 5 ℃ while stirring, and after the pouring was completed, the mixture was further stirred for 1 hour. After filtration and washing with water, the mixture was redispersed in 6500g of ion-exchanged water and filtered again. After washing with water, the wet cake was redispersed in 2500g of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the filter cake was washed with ion-exchanged water and then vacuum-dried at 50 ℃ to obtain aluminum phthalocyanine (AlPc-OH) as a blue solid. While stirring while cooling 288g of 98% sulfuric acid and 272g of 30% fuming sulfuric acid to 10 ℃, 70g of aluminum phthalocyanine (AlPc-OH) was added. Subsequently, the mixture was stirred at 60 ℃ for 3 hours. The reaction solution was taken out to 1750g of water, stirred for 1 hour, filtered, washed with water, and dried to obtain a sulfonated aluminum phthalocyanine derivative (S5). As to the sulfonated aluminum phthalocyanine derivative (S5), the average sulfonation ratio was 1 as determined by LC-MS. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of a sulfonated aluminum phthalocyanine derivative (S5) was added thereto, and the mixture was adjusted to pH12 with an aqueous potassium hydroxide solution and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A5). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A5) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 5). 4.0g of the coloring composition (AMG5), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 5). The composition for evaluation (ACG5) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 2757.5, and the transmittance at 460nm was 64.24.

Synthesis example 6

100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of Solsperse 12000 (sulfonated copper phthalocyanine derivative available from Lubrizol corporation, Japan) was added thereto, the pH was adjusted to 12 with an aqueous solution of potassium hydroxide, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A6). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A6) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 6). 4.0g of the coloring composition (AMG6), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 6). The composition for evaluation (ACG6) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 1303.8, and the transmittance at 460nm was 64.19.

Synthesis example 7

A1L flask was charged with 15g of sulfolane, 10g of titanium tetrachloride, 200g of dimethyl phthalate, 100g of sodium 4-chlorophthalate and 31g of 20% oleum, heated at 170 ℃ for 30 minutes, and then charged with 150g of urea and 9.5g of copper (I) chloride. Further, the mixture was heated at 150 ℃ for 1 hour, at 170 ℃ for 1 hour, and at 190 ℃ for 8 hours. After cooling to 80 ℃, the mixture was taken out into 700g of water in which 60g of sodium hydroxide was dissolved. After stirring at 85 ℃ for 1 hour, the mixture was poured into 2300g of water while stirring, and further stirred at 80 ℃ for 2 hours. After filtration and hot water washing, the resulting mixture was reslurried in 2300g of water in which 140g of 35% hydrochloric acid was dissolved, and heated at 70 ℃ for 1 hour while stirring. After filtration and hot water washing, the mixture was dried at 80 ℃ for 17 hours to obtain tetrachlorocopper phthalocyanine as a blue solid. While cooling 131g of 30% fuming sulfuric acid to 10 ℃ and stirring, 15g of tetrachlorocopper phthalocyanine was added. Subsequently, the mixture was stirred at 90 ℃ for 3 hours. The reaction solution was taken out to 750g 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 found to have an average sulfonation ratio of 1 and an average chlorination ratio of 4 by LC-MS measurement. 100g of ethanol was added to 30g of alumina (AEROXIDE Alu C) manufactured by AEROSIL, Japan, followed by stirring thoroughly, and 2000g of water was added thereto to prepare a white slurry. 1.5g of a sulfonated copper phthalocyanine derivative (S7) was added thereto, and the mixture was adjusted to pH12 with an aqueous potassium hydroxide solution and stirred at room temperature for 2 hours. The reaction mixture was adjusted to pH3 with 10% hydrochloric acid, and stirred at room temperature for 1 hour, followed by filtration, washing with water, drying, and pulverization to obtain a derivative carrier (A7). Using 0.3 to 0.4mm zirconium beads, 2.48g of the derivative support (A7) was dispersed in BYK-LPN69191.24g, Unidic ZL-2951.86 g, produced by Pico chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate for 2 hours by a paint shaker, produced by Toyo Seiki Seiko K.K., to obtain a colored composition (AMG 7). 4.0g of the coloring composition (AMG7), UNIDIC ZL-2950.98g of DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added thereto and mixed by a paint shaker to obtain a composition for evaluation (ACG 7). The composition for evaluation (ACG7) was spin-coated on sodium glass, dried at 90 ℃ for 3 minutes, and then the spectral transmission spectrum was measured by U-3900, manufactured by Hitachi high tech. The spectral transmittance spectrum having a maximum transmittance of 70% was measured by adjusting the number of revolutions of the spin at the time of spin coating. In the measurement of the transmission spectrum, a base line correction was performed using soda glass. The integrated value of the transmittance at 510nm to 560nm was 1401.9, and the transmittance at 460nm was 64.60.

Production example 1

36g of zinc phthalocyanine halide (R1), 4g of sulfonated zinc phthalocyanine derivative (S1), 400g of pulverized sodium chloride, and 63g of diethylene glycol were put into a double arm type kneader and kneaded at 80 ℃ for 8 hours. After kneading, the mixture was taken out to 2kg of water at 80 ℃ and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization 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

38g of zinc phthalocyanine halide (R1), 2g of sulfonated zinc phthalocyanine derivative (S1), 400g of pulverized sodium chloride, and 63g of diethylene glycol were put into a double arm type kneader and kneaded at 80 ℃ for 8 hours. After kneading, the mixture was taken out to 2kg of water at 80 ℃ and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization 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

36g of zinc phthalocyanine halide (R2), 4g of sulfonated zinc phthalocyanine derivative (S3), 400g of pulverized sodium chloride, and 63g of diethylene glycol were put into a double arm type kneader and kneaded at 80 ℃ for 8 hours. After kneading, the mixture was taken out to 2kg of water at 80 ℃ and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization 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 (a sulfonated copper phthalocyanine derivative available from Lubrizol corporation, Japan).

Production example 13

A coloring composition (MY1) was obtained by dispersing 1.65g of pigment yellow 138 (CHROMOFINE yellow 6206EC, manufactured by Daiyi Seisaku-Sho Ltd.) together with 3.85g of DISPERBYK-161 (manufactured by Bikk chemical Co., Ltd.) and 11.00g of propylene glycol monomethyl ether acetate for 2 hours using 0.3 to 0.4mm zirconium beads with a paint shaker manufactured by Toyo Seiki Seisaku-Sho K. 4.0g of the coloring composition (MY1), 4.0g of UNIDIC ZL-2950.98g, and 0.22g of propylene glycol monomethyl ether acetate were added thereto, and the mixture was mixed by a paint shaker to obtain a composition for color adjustment (TY 1).

Example 1

2.48G of a green pigment composition (G1) was dispersed for 2 hours using 0.3 to 0.4mm zirconium beads, together with BYK-LPN69191.24g, manufactured by Bikken chemical Co., Ltd., UNIDIC ZL-2951.86G, and 10.92G of propylene glycol monomethyl ether acetate by using a paint shaker, manufactured by Toyo Seiki Seisaku-Sho K.K., to obtain a coloring composition (MG 1). 4.0g of the coloring composition (MG1), UNIDIC ZL-2950.98g manufactured by DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added and mixed by a paint shaker to obtain an evaluation composition (CG1) for forming a green pixel portion for a color filter. A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG1) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 2

A composition for evaluation (CG2) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G2). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG2) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 3

A composition for evaluation (CG3) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G3). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG3) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 4

A composition for evaluation (CG4) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G4). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG4) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 5

A composition for evaluation (CG5) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G5). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG5) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 6

A composition for evaluation (CG7) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G7). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG7) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 7

A composition for evaluation (CG8) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G8). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG8) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 8

A composition for evaluation (CG9) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G9). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG9) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. Brightness was measured with a Hitachi high-tech technology U-3900, and film thickness was measured with a Hitachi high-tech technology white interference microscope VS 1330.

Example 9

2.23g of a green pigment composition (RG1) and 0.25g of a sulfonated zinc phthalocyanine derivative (S1) were dispersed for 2 hours together with BYK-LPN69191.24g, UniDIC ZL-2951.86 g, manufactured by Nikko chemical Co., Ltd., and 10.92g of propylene glycol monomethyl ether acetate using 0.3 to 0.4mm zirconium beads by a paint shaker, manufactured by Toyo Seiki K.K., to obtain a colored composition (MG 10). 4.0g of the coloring composition (MG10), UNIDIC ZL-2950.98g manufactured by DIC corporation, and 0.22g of propylene glycol monomethyl ether acetate were added and mixed by a paint shaker to obtain an evaluation composition (CG10) for forming a green pixel portion for a color filter. A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG10) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 10

A composition for evaluation (CG11) was obtained in the same manner as in example 9, except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S2). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG11) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 11

A composition for evaluation (CG12) was obtained in the same manner as in example 9, except that the sulfonated zinc phthalocyanine derivative (S1) was replaced with the sulfonated zinc phthalocyanine derivative (S3). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG12) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 12

A composition for evaluation (CG13) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G10). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG13) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.275, 0.570) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Example 13

A composition for evaluation (CG14) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G11). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG14) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.275, 0.570) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

Comparative example 1

A composition for evaluation (CG6) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G6). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG6) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.250, 0.615) under a C light source was prepared. Brightness was measured with a Hitachi high-tech technology U-3900, and film thickness was measured with a Hitachi high-tech technology white interference microscope VS 1330.

Comparative example 2

A composition for evaluation (CG12) was obtained in the same manner as in example 1, except that the green pigment composition (G1) was replaced with the green pigment composition (G12). A coating liquid obtained by mixing the toning composition (TY1) prepared in preparation example 13 and the evaluation composition (CG12) was spin-coated on soda glass, and after drying at 90 ℃ for 3 minutes, a coating film having a chromaticity (x, y) of (0.275, 0.570) under a C light source was prepared. The brightness was measured by U-3900, manufactured by Hitachi high-tech, and the film thickness was measured by white interference microscope VS1330, manufactured by Hitachi high-tech.

TABLE 1

TABLE 2

As shown in tables 1 and 2, it was confirmed that the brightness was higher when the sulfonated zinc phthalocyanine derivative or the sulfonated aluminum phthalocyanine derivative was used than when the sulfonated copper phthalocyanine derivative was used. Further, the film thickness was judged to be excellent when the film thickness was thinner than 3.4 μm, good when the film thickness was not less than 3.4 μm and not more than 3.6 μm, and good when the film thickness was not less than 3.6 μm.

In the present invention, a pigment derivative having a D2/D1 ratio higher than that of a conventionally used sulfonated copper phthalocyanine (SOLSPERSE 12000, sulfonated copper phthalocyanine derivative (S7)) is selected and used, and thus the brightness is high. Further, in the present invention, a pigment derivative having a lower transmittance at 460nm than that of a conventionally used sulfonated copper phthalocyanine (solpperse 12000, sulfonated copper phthalocyanine derivative (S7)) is selected and used, and therefore the film thickness is thin.

Claims

1. A pigment composition for color filters, which comprises a zinc halide phthalocyanine pigment and a pigment derivative represented by the following general formula (1),

[ solution 1]

In the general formula (1), Z¹～Z¹⁶Each independently represents a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, the average number of substituents of at least 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,

when the integral value of the transmittance at 510nm to 560nm of a coating film formed using the zinc halide phthalocyanine pigment so that the spectral transmittance at the maximum transmission wavelength becomes 70% is D1, and the integral value of the transmittance at 510nm to 560nm of a coating film formed using a derivative carrier in which the pigment derivative is supported on alumina so that the spectral transmittance at the maximum transmission wavelength becomes 70% is D2,

has a spectral characteristic that the ratio of D1 to D2, namely D2/D1, is 0.7 or more,

has a spectral characteristic that the 460nm transmittance of a coating film formed by using a derivative carrier obtained by supporting the pigment derivative on alumina is 60% or less so that the spectral transmittance at the maximum transmission wavelength is 70%.

2. A pigment composition for color filters according to claim 1, wherein the pigment derivative is a pigment derivative of: in the formula (1), Z¹～Z¹⁶Is any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and on average in one molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (1) have a chlorine atom.

3. A pigment composition for color filters according to claim 1, wherein the pigment derivative is a pigment derivative of: in the formula (1), Z¹～Z¹⁶Has any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and is at least from Z on average in one molecule¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (a) have a bromine atom.

4. A pigment composition for color filters according to claim 1 or 2, wherein the pigment derivative is a pigment derivative of: z in the formula (1) on average in one molecule¹～Z¹⁶Contains 10 to 14 halogen atoms, 8 to 12 bromine atoms and 2 to 5 chlorine atoms.

5. A pigment composition for color filters according to claim 1 or 2, further comprising a yellow pigment.

6. A color filter comprising the pigment composition for a color filter according to any one of claims 1 to 5 in a pixel portion.

7. A color filter comprising a zinc halide phthalocyanine pigment and a pigment derivative represented by the following general formula (1),

[ solution 2]

8. A color filter as defined in claim 7, characterzed in that the pigment derivative is a pigment derivative as follows: in the formula (1), Z¹～Z¹⁶Is any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and on average in one molecule, at least from Z¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (1) have a chlorine atom.

9. A color filter as defined in claim 7, characterzed in that the pigment derivative is a pigment derivative as follows: in the formula (1), Z¹～Z¹⁶Has any one of a bromine atom, a chlorine atom, a hydrogen atom or a sulfo group, and is at least from Z on average in one molecule¹、Z⁴、Z⁵、Z⁸、Z⁹、Z¹²、Z¹³、Z¹⁶Any 2 or more selected from (a) have a bromine atom.

10. A color filter as defined in claim 7 or 8, CHARACTERZED in that the pigment derivative is a pigment derivative represented by the following formula: z in the formula (1) on average in one molecule¹～Z¹⁶Contains 10 to 14 halogen atoms, 8 to 12 bromine atoms and 2 to 5 chlorine atoms.

11. A color filter as defined in claim 7 or 8, CHARACTERZED in that it further contains a yellow pigment.