WO2018159372A1 - キノフタロン化合物 - Google Patents
キノフタロン化合物 Download PDFInfo
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- WO2018159372A1 WO2018159372A1 PCT/JP2018/005875 JP2018005875W WO2018159372A1 WO 2018159372 A1 WO2018159372 A1 WO 2018159372A1 JP 2018005875 W JP2018005875 W JP 2018005875W WO 2018159372 A1 WO2018159372 A1 WO 2018159372A1
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- 0 Cc(cc1)nc2c1cc(*c1cc(*)c3nc(C)ccc3c1)cc2* Chemical compound Cc(cc1)nc2c1cc(*c1cc(*)c3nc(C)ccc3c1)cc2* 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Definitions
- the present invention relates to a novel quinophthalone compound.
- Patent Documents 1 and 2 disclose bisquinophthalone compounds having a certain structure.
- Patent Document 3 discloses a quinophthalone compound having a certain structure.
- Patent Documents 1, 2, and 3 do not disclose the compound of the present invention represented by the following formula (1).
- colored compositions are used in various fields. Specific applications include printing inks, paints, resin colorants, fiber colorants, information recording colorants (for color filters, toners, ink jets, etc.). Colorant to be used). Colors used in coloring compositions are mainly divided into pigments and dyes. The required properties include color characteristics (coloring power, sharpness) and resistance (weather resistance, light resistance, heat resistance, solvent resistance). )and so on. Usually, unlike a dye that develops color in a molecular state, a pigment develops from a particle state (aggregates of primary particles). For this reason, pigments are generally superior in resistance compared to dyes, but are often inferior in coloring power and sharpness. From such a background, pigments with high coloring power and high saturation are demanded. Of these, organic pigments, which have been dominant in terms of coloring power, are particularly attracting attention.
- yellow organic pigments many new pigments have been actively developed so far, with yellow pigments having the second largest number of registered color indexes after red pigments.
- yellow organic pigments that are actually used include C.I. I. Pigment Yellow 3, 12, and 74, etc. are used for paint, and 74, 83, 109, and 110 are used for paint, and 129, 138, 150, and 185 are used for color filter. Yes.
- their basic structures are mainly azo, azomethine, isoindoline, isoindolinone and the like. Therefore, the structural variation in the yellow organic pigment is not yet sufficient to meet various required uses.
- color filters for liquid crystal displays or pigments used in these color filters are required to have characteristics different from conventional general-purpose applications.
- high luminance that can reduce the power consumption of the backlight
- high coloring power that enables color filter thinning and high color reproduction.
- the current yellow pigment for color filters has no pigment that meets all these requirements.
- the color filter includes a red pixel portion (R), a green pixel portion (G), and a blue pixel portion (B), and the yellow pigment is often used for toning of the green pixel portion.
- the most used amount is C.I. I. Pigment Yellow 138, which has poor coloring power and is not practical in color standards that require high color reproducibility.
- C.I. I. Pigment Yellow 150 is used as the current yellow pigment, but it cannot be said that 150 also has sufficient luminance and coloring power. Thus, there is a demand for the creation of a new yellow pigment having both excellent brightness and coloring power.
- the present inventors have found that dimerization of the quinophthalone skeleton exhibits more selective absorption and transmission. Furthermore, the dimerization technique was also studied, and it was found that excessive redness can be suppressed by using a lower alkylene chain as a spacer and cleaving the conjugate, rather than simply adopting a direct bond. In addition, dispersibility was improved by introducing polyhalogenated and imide structures. The present inventors have found that a compound represented by the following formula (1) can solve the above problems based on such examination results, and have completed the present invention. That is, the present invention provides the following formula (1):
- X 1 to X 16 are each independently a hydrogen atom or a halogen atom, Y is a hydrogen atom or a halogen atom, and Z is a lower alkylene group) , Sometimes referred to as “the compound of the present invention”).
- the compound of the present invention has excellent luminance and coloring power.
- the compound of the present invention has a brightness superior to that of the current yellow pigment (CI Pigment Yellow 150) and an excellent coloring power exceeding this. Have.
- halogen atom in the above formula (1) examples include fluorine, chlorine, bromine or iodine atoms, among which a fluorine atom, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable.
- Examples of the lower alkylene group in the above formula (1) include C1-3 groups such as methylene, ethylene, propylene, etc. Among them, the case of methylene is more preferable.
- the quinophthalone compound represented by the above formula (1) has tautomers having structures such as the following general formula (1-i) and general formula (1-ii), and these are also included in the present invention. It is included.
- Such a production method of the compound of the present invention is not particularly limited, and can be produced by appropriately using a conventionally known method.
- a conventionally known method for example, one embodiment of the production method of the compound of the present invention will be described.
- the present invention is not limited to these.
- the compound of the present invention can be obtained, for example, by a method including the following step I, step II, step III and step IV.
- bishaloaniline is added in an amount of 2 to 3 equivalents to 1 equivalent of bishaloaniline, and reacted in a strong acid in the presence of an oxidizing agent.
- the compound of 2) is synthesized.
- the strong acid examples include hydrochloric acid, sulfuric acid, nitric acid and the like.
- the oxidizing agent include sodium iodide, p-chloranil, nitrobenzene and the like.
- the reaction temperature can be 80 ° C. to 100 ° C., preferably 90 ° C. to 100 ° C.
- the reaction time can be 1 hour to 6 hours, preferably 3 hours to 6 hours.
- the compound of formula (3) can be obtained by reacting the obtained compound of formula (2) with fuming nitric acid in the presence of concentrated sulfuric acid.
- the reaction temperature can be 40 ° C to 70 ° C, preferably 40 ° C to 50 ° C, and the reaction time can be 1 hour to 3 hours, preferably 1 hour to 2 hours.
- the reaction temperature can be 60 to 80 ° C., preferably 70 to 80 ° C.
- the reaction time can be 1 to 3 hours, preferably 2 to 3 hours.
- Step IV Furthermore, 4 to 6 equivalents of phthalic anhydride or tetrahalophthalic anhydride are added to 1 equivalent of the compound of the formula (4) obtained by the method described in JP2013-61622A in the presence of an acid catalyst.
- the acid catalyst include benzoic acid and zinc chloride.
- the reaction temperature can be 180 ° C. to 250 ° C., preferably 210 ° C. to 250 ° C.
- the reaction time can be 1 hour to 8 hours, preferably 3 hours to 8 hours.
- the compound of the present invention may be used alone, or two or more compounds may be appropriately selected and used in combination.
- the compound of the present invention is considered applicable to various uses.
- it can be used as a colorant for a wide range of uses such as printing ink, paint, colored plastic, toner, inkjet ink, light-shielding member for display, and seed coloring.
- the compound of the present invention exhibits properties as an organic pigment and may be used more suitably by subjecting the pigment particles to a finer size, such as by salt milling. Such processing may be performed by a known and conventional method.
- the present compound may be used in combination with a coloring material such as an organic pigment, an organic dye, or an organic pigment derivative other than the present compound for the purpose of toning.
- a coloring material such as an organic pigment, an organic dye, or an organic pigment derivative other than the present compound for the purpose of toning.
- any of known pigments, dyes and the like may be used.
- C.I. I. Pigment Yellow 3, 12, 12, etc. are for paint applications, 74, 83, 109, 110, etc., and for color filters are 83, 129, 138, 139, 150, 150, etc. 185, 231 and the like.
- the compound of the present invention when used for forming a green pixel portion in a color filter application, for example, C.I. I. Pigment Green 1, 2, 4, 4, 7, 10, 13, 14, 14, 17, 17, 18, 19, 26, 36, 45, 48, It can be used in combination with green pigments such as 50, 51, 54, 55, 58, 59, 62, and 63, but is not limited thereto.
- the combination ratio of the green pigment and the yellow pigment of the present invention is, for example, 10 to 150 parts by mass of the yellow pigment per 100 parts by mass of the green pigment. It is.
- this invention compound when using this invention compound for green pixel part formation, this invention compound and a blue pigment can also be used together.
- the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, aluminum phthalocyanine derivatives, and the like.
- the aluminum phthalocyanine derivative include compounds represented by the following general formula (5-1).
- R is a halogen atom, a hydroxy group, or a group represented by the following general formula (5-2).
- X is a direct bond or an oxygen atom.
- Ar is a phenyl group or a naphthyl group. In the formula, an asterisk represents a binding site.
- halogen atom in R in the above formula (5-1) examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the halogen atom in R is preferably a chlorine atom or a bromine atom.
- R is preferably a chlorine atom, a bromine atom, a hydroxy group, or a group represented by the general formula (5-2).
- X is preferably an oxygen atom.
- Preferred examples of the formula (5-1) include hydroxyaluminum phthalocyanine, chloroaluminum phthalocyanine, bromoaluminum phthalocyanine, a compound represented by the following formula (5-1-1), and a compound represented by the following formula (5-1-2). ), A compound represented by the following formula (5-1-3), and the like.
- the compound of the present invention can be used in combination with a red pigment for forming a red pixel portion in color filter applications.
- red pigments include C.I. I. Pigment red 177, 254, and the like.
- a known method can be employed.
- a photosensitive composition for a color filter containing the compound of the present invention and a photosensitive resin as essential components can be obtained.
- the compound of the present invention is dispersed in a dispersion medium made of a photosensitive resin, and then applied onto a transparent substrate such as glass by a spin coating method, a roll coating method, an ink jet method, etc.
- a method called photolithography in which the coating 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.
- photolithography in which the coating 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.
- the present invention is used for forming the pattern of the red pixel portion of the color filter.
- a color filter may be manufactured by forming a pattern of the pixel portion by an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method.
- a photosensitive composition for a color filter for example, a pigment, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are mixed as essential components.
- a method is generally used in which a dispersion is prepared using a pigment, an organic solvent, and a dispersant as required, and then a photosensitive resin or the like is added thereto.
- a pigment when obtaining a green pixel portion, a pigment obtained by compounding the compound of the present invention and the above-described green pigment or blue pigment can be used.
- a red pixel portion when obtaining a red pixel portion, a pigment obtained by compounding the compound of the present invention and the red pigment described above can be used.
- Dispersants used as necessary include, for example, DISPERBYK (registered trade name) 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BIF Chem. Examples include Fuka 47 and Fuka 4300.
- a doctorBYK registered trade name 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BIF Chem. Examples include Fuka 47 and Fuka 4300.
- a doctorBYK registered trade name 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BIF Chem.
- Examples include Fuka 47 and Fuka 4300.
- a cyst rigging agent, a coupling agent, a cationic surfactant, and the like can be used together.
- organic solvent examples include aromatic solvents such as toluene, xylene, and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethoxyethyl propionate.
- Propionate solvents such as 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, and fats such as hexane Group hydrocarbon solvents, N, N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, a Phosphorus, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as ⁇ - butyrolactone, there are carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate.
- ether solvents such as butyl cellosolve
- propylene glycol monomethyl ether diethylene glycol ethyl ether
- the organic solvent in an amount of 300 to 1000 parts by mass per 100 parts by mass of the pigment composition for a color filter of the present invention, and optionally 100 parts by mass or less of a dispersant and / or 20 parts by mass or less of a quinophthalone derivative
- the dispersion can be obtained by stirring and dispersing as described above.
- a photosensitive composition for a color filter pixel portion can be obtained by adding a solvent and stirring and dispersing so as to be uniform.
- the above-mentioned color filter pigment composition is used for a green pixel, per 10 parts by mass of the quinophthalone pigment composition of the present invention, and for a green pixel, 200 parts by mass or less of a green pigment and / or 200 parts by mass or less of a blue pigment.
- a green pixel 200 parts by mass or less of a green pigment and / or 200 parts by mass or less of a blue pigment.
- 200 parts by mass or less of a red pigment is mixed.
- photosensitive resins examples include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like, Bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, Trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. It includes photopolymerizable monomers such as polyfunctional monomers, such as.
- photopolymerization initiator examples 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 thus prepared photosensitive composition for a color filter pixel portion is subjected to pattern exposure with ultraviolet rays through a photomask, and then a color filter is prepared by washing an unexposed portion with an organic solvent or alkaline water. Can do.
- Synthesis example 2 4.15 g (11.3 mmol) of the intermediate (A) obtained in Synthesis Example 1 and 7.55 mL of concentrated sulfuric acid were added to the flask and stirred at 45 ° C. for 20 minutes. Thereafter, 1.62 mL of fuming nitric acid was added dropwise, and the temperature was maintained and stirring was continued for 1 hour. After standing to cool, 250 mL of ice water was slowly poured into the system. Further, the pH was adjusted to 8-9 using a 10 wt% aqueous sodium hydroxide solution.
- Synthesis example 3 In the flask, 5.00 g (10.9 mmol) of the intermediate (B) obtained in Synthesis Example 2 and 23.3 mL of ethanol were added and stirred at room temperature for 10 minutes. Thereafter, 4.88 g (87.4 mmol) of iron was added to the system, and the mixture was further stirred at room temperature for 10 minutes. Subsequently, 6.33 mL of concentrated hydrochloric acid was added dropwise, the temperature was raised to 80 ° C., and stirring was continued for 6 hours. After cooling, the mixture was poured into 150 mL of distilled water, and the pH was adjusted to 9 using a 10% aqueous sodium hydroxide solution. The precipitated powder was collected by vacuum filtration.
- Pigmentation 0.500 parts by mass of the quinophthalone compound (compound of formula (D)) obtained in the above synthesis example was ground together with 1.50 parts by mass of sodium chloride and 0.750 parts by mass of diethylene glycol. Thereafter, this mixture was poured into 600 parts by mass of warm water and stirred for 1 hour. The water-insoluble matter was separated by filtration and washed well with warm water, and then air-dried at 90 ° C. for pigmentation. The pigment particle system was 100 nm or less and the average particle length / width ratio was less than 3.00. The following dispersion test and color filter evaluation test were conducted using the yellow pigment of the obtained quinophthalone compound.
- Production Example 1 0.700 parts by mass of a quinophthalone compound (D) is placed in a glass bottle, 12.8 parts by mass of propylene glycol monomethyl ether acetate, 0.47 parts by mass of DISPERBYK (registered trademark) LPN-6919 (manufactured by BYK Chemie), DIC Corporation Acrylic resin solution Unidic (registered trademark) ZL-295 0.700 parts by mass, 0.3-0.4 mm ⁇ Sepul beads 22.0 parts by mass were added and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion was obtained.
- DISPERBYK registered trademark
- LPN-6919 manufactured by BYK Chemie
- DIC Corporation Acrylic resin solution Unidic (registered trademark) ZL-295 0.700 parts by mass, 0.3-0.4 mm ⁇ Sepul beads 22.0 parts by mass were added and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co.
- Example 1 The composition for yellow toning obtained in Production Example 1 and the composition for green toning obtained in Production Example 2 were mixed, applied onto a glass substrate with a spin coater, and then dried. After heating the obtained glass substrate for evaluation at 230 degreeC for 1 hour, the green color filter which shows each green chromaticity at the time of using C light source in the color specification for high color reproduction was produced.
- the green chromaticity the values used in Japanese Patent Laid-Open No. 2013-205581 (0.210, 0.710) and the color used in Japanese Patent Laid-Open No. 2011-242425 (0.230, 0.670) are used. It was.
- Production Example 3 In Production Example 1, C.I. was used instead of the quinophthalone compound (D).
- a yellow toning composition was prepared in the same manner except that CI Pigment Yellow 138 (manufactured by BASF) and 6.42 parts by weight of propylene glycol monomethyl ether acetate added before dispersion were used.
- Comparative Example 1 A green color filter was produced in the same manner as in Example 1 except that the composition obtained in Production Example 3 was used instead of the composition obtained in Production Example 1 as a yellow toning composition.
- Pigment Yellow 150 (manufactured by Sanyo Dye) 1.14 parts by mass in a plastic bottle, 12.0 parts by mass of propylene glycol monomethyl ether acetate, DISPERBYK (registered trademark) LPN-21116 (manufactured by Big Chemie Co., Ltd.) 2.84 Part by mass, 38.0 parts by mass of 0.3-0.4 mm ⁇ Sepul beads were added, and the mixture was dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion.
- DISPERBYK registered trademark
- LPN-21116 manufactured by Big Chemie Co., Ltd.
- Comparative Example 2 A green color filter was produced in the same manner as in Example 1 except that the composition obtained in Production Example 4 was used instead of the composition obtained in Production Example 1 as a yellow toning composition.
- Production Example 5 In Production Example 3, C.I. I. A yellow toning composition was prepared in the same manner except that quinophthalone monomer (6) synthesized by the method described in JP-A-53-228 was used instead of CI Pigment Yellow 138 (manufactured by BASF). did.
- Comparative Example 3 A green color filter was produced in the same manner as in Example 1 except that the composition obtained in Production Example 5 was used instead of the composition obtained in Production Example 1 as the yellow toning composition.
- Example 1 compared with Comparative Example 2 using the current yellow pigment (CI Pigment Yellow 150), the brightness was excellent and the film thickness was significantly reduced. This indicates that the yellow pigment of the present invention has high luminance and high coloring power in the high color reproducibility standard, and is suitable as a yellow pigment for a color filter. Similarly, in comparison with Comparative Example 3 (quinophthalone monomer (6)), Example 1 shows higher luminance and thinner film thickness, so that the color filter characteristics due to dimerization are remarkable. Improvement was confirmed.
- the quinophthalone monomer (6) is a compound described as Example 2 of JP-A-53-228. Note that Comparative Example 1 (CI Pigment Yellow 138) is not at a practical level because of its low luminance and extremely thick film thickness. As described above, the compound of the present invention has a remarkable effect over current representative yellow pigments.
- Production Example 6 A yellow toning composition was prepared in the same manner as in Production Example 1 except that the quinophthalone compound (E) obtained in Synthesis Example 5 was used instead of the quinophthalone compound (D).
- Example 2 In Example 1, the same method as in Example 1 except that the yellow toning composition obtained in Production Example 6 was used instead of the yellow toning composition obtained in Production Example 1. A green color filter was obtained.
- Example 2 of color filter test the chromaticity and transmission spectrum were measured by a spectrophotometer (U3900 / 3900H type manufactured by HITACHI), and the film thickness meter (VS1000 scanning white interference microscope manufactured by HITACHI). ) To measure the film thickness (the thinner the film, the higher the coloring power). The results are shown in Table 3 below.
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Abstract
Description
ここで、カラーフィルタは、赤色画素部(R)、緑色画素部(G)及び青色画素部(B)からなり、黄色顔料は、緑色画素部の調色用として用いられる場合が多い。黄色顔料の中で、最も使用量が多いのはC.I.ピグメント イエロー138であるが、この同138は着色力に乏しく、高色再現性が求められる色規格では実用性がない。よって、高色再現性の色規格においては、C.I.ピグメント イエロー150が現行の黄色顔料として用いられているが、同150も輝度・着色力ともに十分であるとはいえない。そこで、優れた輝度と着色力を兼備する新規黄色顔料の創出が希求されている。
本発明者らは、このような検討結果に基づき下記式(1)で表される化合物が上記課題を解決できることを見出し、本発明を完成させた。即ち本発明は、下記式(1):
<工程I>
まず、J.Heterocyclic,Chem,30,17(1993)に記載の方法などにより、ビスハロアニリンを1当量に対し、クロトンアルデヒドを2~3当量加え、酸化剤存在下、強酸中において反応させ、後記する式(2)の化合物を合成する。
酸化剤としては、ヨウ化ナトリウム、p-クロラニル、ニトロベンゼンなどが挙げられる。
工程Iに関し、反応温度は、80℃~100℃、好ましくは90℃~100℃で行うことができ、反応時間は、1時間~6時間、好ましくは3時間~6時間で行うことができる。
さらに、得られた式(2)の化合物と発煙硝酸を濃硫酸存在下において反応させることで、式(3)の化合物を得ることができる。
さらに、得られた式(3)の化合物を1当量に対し、還元鉄を6~8当量加え、反応させることで、式(4)の化合物を得ることができる。
さらに、特開2013-61622号公報に記載の方法などにより、得られた式(4)の化合物1当量に対し、無水フタル酸あるいはテトラハロフタル酸無水物4~6当量を酸触媒存在下において反応させることで、式(1)の化合物を得ることができる。
ここで、酸触媒としては、安息香酸、塩化亜鉛などが挙げられる。
工程IVに関し、反応温度は、180℃~250℃、好ましくは210℃~250℃で行うことができ、反応時間は、1時間~8時間、好ましくは3時間~8時間で行うことができる。
用途によって、アゾ系、ジスアゾ系、アゾメチン系、アントラキノン系、キノフタロン系、キナクリドン系、ジケトピロロピロール系、ジオキサジン系、ベンズイミダゾロン系、フタロシアニン系、イソインドリン系、イソインドリノン系、ペリレン系顔料、及びキサンテン系、アゾ系、ジスアゾ、アンラキノン系、キノフタロン系、トリアリールメタン系、メチン系、フタロシアニン系、ローダミン系染料などが挙げられる。
ここで、上記のアルミニウムフタロシアニン誘導体とは、例えば、下記一般式(5-1)で表される化合物等が挙げられる。
合成例1
フラスコ中に4,4’-メチレンビス(2-クロロアニリン)30.4g(114mmol)、p-クロラニル56.1g(228mmol)、濃塩酸29.5mL、n-ブタノール147mLを添加して95℃で30分間攪拌した。この混合物に、クロトンアルデヒド19.2g(274mmol)を滴下して、さらに1時間攪拌した。温度を80℃に下げ、塩化亜鉛15.5g(114mmol)を少量ずつ加えた後、THF100mLを添加して80℃を保ったまま1時間攪拌した。室温まで放冷した後、氷浴につけ、減圧ろ過にて黒色粉末を回収した。得られた黒色粉末をエタノール500mLで洗浄し、再び減圧ろ過にて黒色粉末を回収した。さらに、得られた黒色粉末をフラスコに移し、エタノール200mLと10%水酸化ナトリウム水溶液400mLを加え、80℃で1時間攪拌した。減圧ろ過にて粉末を回収し、中間体(A)35.6g(96.9mmol)を得た。(収率:85%)
13C-NMR (CDCl3) δppm: 25.8, 41.1, 123.2, 126.2, 127.8, 130.9, 133.1, 136.3, 137.6, 143.1, 160.0
FT-IR cm-1: 3435, 3054, 3030, 2915, 1603, 1487, 1206
FD-MS: 366 M+
フラスコ中に合成例1で得た中間体(A)4.15g(11.3mmol)と濃硫酸7.55mLを加え、45℃で20分間攪拌した。その後、発煙硝酸1.62mLを滴下し、温度を保持し1時間攪拌を続けた。放冷後、氷水250mLを系中にゆっくりと注いだ。さらに、10wt%水酸化ナトリウム水溶液を用いて、pHを8-9に調整した。析出した粉末を減圧ろ過で回収し、蒸留水200mL、エタノール100mLで洗浄することで、黄橙色粉末である中間体(B)5.13g(11.2mmol)を得た。(収率:99%)
13C-NMR (CDCl3) δppm: 25.7, 32.4, 119.9, 125.6, 127.5, 130.1, 131.1, 137.3, 143.1, 145.9, 162.2
FT-IR cm-1: 3465, 1604, 1530, 1487, 1362
フラスコ中に合成例2で得た中間体(B)5.00g(10.9mmol)とエタノール23.3mLを加え、室温で10分間攪拌した。その後、鉄4.88g(87.4mmol)を系中に加え、室温でさらに10分間攪拌した。続いて、濃塩酸6.33mLを滴下し、温度を80℃に昇温し、6時間攪拌を続けた。放冷後、蒸留水150mLに注ぎ、10%水酸化ナトリウム水溶液を用いて、pHを9に調整した。析出した粉末を減圧ろ過で回収した。さらに、回収した粉末を酢酸エチル700mL中で十分攪拌させ、減圧ろ過を行った。そこで得られたろ液の溶媒を減圧留去することで、黄土色粉末である中間体(C)1.47g(3.69mmol)を得た。(収率:34%)
13C-NMR (CDCl3) δppm: 25.4, 31.9, 116.8, 117.7, 117.9, 121.0, 131.8, 132.2, 142.0, 143.1, 158.9
FT-IR cm-1: 3476, 3373, 1627, 1605, 1409, 1359, 1250
窒素雰囲気下、フラスコ中に安息香酸14.1g(116mmol)を量りとり、140℃にて溶融させた。そこに、合成例3で得た中間体(C)1.44g(3.62mmol)とテトラクロロフタル酸無水物5.53g(19.3mmol)を加え、220℃にて4時間攪拌した。放冷後、反応溶液にアセトン300mLを加え、1時間攪拌した後、減圧ろ過にて黄色粉末である目的物(D)を4.41g(3.00mmol)得た。(収率:83%)
FD-MS: 1467 M+
前記合成例で得たキノフタロン化合物(式(D)の化合物) 0.500質量部を塩化ナトリウム1.50質量部、ジエチレングリコール0.750質量部とともに磨砕した。その後、この混合物を600質量部の温水に投じ、1時間攪拌した。水不溶分をろ過分離して温水でよく洗浄した後、90℃で送風乾燥して顔料化を行った。顔料の粒子系は、100nm以下、粒子の平均長さ/幅比は3.00未満であった。得られたキノフタロン化合物の黄色顔料を用いて以下の分散試験及びカラーフィルタ評価試験を行った。
キノフタロン化合物(D)0.700質量部をガラス瓶に入れ、プロピレングリコールモノメチルエーテルアセテート12.8質量部、DISPERBYK(登録商標名)LPN-6919(ビックケミー株式会社製)0.467質量部、DIC株式会社製アクリル樹脂溶液ユニディック(登録商標名)ZL-295 0.700質量部、0.3-0.4mmφセプルビーズ22.0質量部を加え、ペイントコンディショナー(東洋精機株式会社製)で4時間分散し、顔料分散体を得た。さらに、得られた顔料分散体2.00質量部、DIC株式会社製アクリル樹脂溶液ユニディック(登録商標名)ZL-295 0.490質量部、プロピレングリコールモノメチルエーテルアセテート0.110質量部をガラス瓶に入れ、振とうさせることで黄色調色用組成物を作製した。
C.I.ピグメント グリーン59(DIC株式会社製)2.48質量部をガラス瓶に入れ、プロピレングリコールモノメチルエーテルアセテート10.9量部、DISPERBYK(登録商標名)LPN-6919(ビックケミー株式会社製)1.24質量部、DIC株式会社製アクリル樹脂溶液ユニディック(登録商標名)ZL-295 1.86質量部、0.3-0.4mmφセプルビーズを加え、ペイントコンディショナー(東洋精機株式会社製)で2時間分散し、顔料分散体を得た。さらに、得られた顔料分散体4.00質量部、DIC株式会社製アクリル樹脂溶液ユニディック(登録商標名)ZL-295 0.980質量部、プロピレングリコールモノメチルエーテルアセテート0.220質量部をガラス瓶に入れ、振とうさせることで緑色調色用組成物を作製した。
製造例1で得られた黄色調色用組成物と製造例2で得られた緑色調色用組成物を混合し、スピンコーターによりガラス基板上に塗布後、乾燥させた。得られた評価用ガラス基板を230℃で1時間加熱した後に、高色再現用色規格におけるC光源を用いた場合の各緑色色度を示す緑色カラーフィルタを作製した。なお、緑色色度としては、特開2013-205581で使用されている(0.210,0.710)、及び特開2011-242425で使用されている(0.230,0.670)を用いた。
製造例1において、キノフタロン化合物(D)に代えてC.I.ピグメント イエロー138(BASF社製)を、また、分散前に加えるプロピレングリコールモノメチルエーテルアセテートを6.42重量部用いた以外は同様の方法で黄色調色用組成物を作製した。
実施例1において、黄色調色用組成物として製造例1で得られた組成物に代えて、製造例3で得られた組成物を用いた以外は同様の方法で緑色カラーフィルタを作製した。
C.I.ピグメント イエロー150(山陽色素社製)1.14質量部をポリ瓶に入れ、プロピレングリコールモノメチルエーテルアセテート12.0質量部、DISPERBYK(登録商標名)LPN-21116(ビックケミー株式会社社製)2.84質量部、0.3-0.4mmφセプルビーズ38.0質量部を加え、ペイントコンディショナー(東洋精機株式会社製)で4時間分散し、顔料分散体を得た。さらに、得られた顔料分散体2.00質量部、DIC株式会社製アクリル樹脂溶液ユニディック(登録商標名)ZL-295 0.490質量部、プロピレングリコールモノメチルエーテルアセテート0.110質量部をガラス瓶に入れ、振とうさせることで黄色調色用組成物を作製した。
実施例1において、黄色調色用組成物として製造例1で得られた組成物に代えて、製造例4で得られた組成物を用いた以外は同様の方法で緑色カラーフィルタを作製した。
製造例3において、C.I.ピグメント イエロー138(BASF社製)に代えて、特開昭53-228に記載の方法で合成したキノフタロン単量体(6)を用いた以外は、同様の方法で黄色調色用組成物を作製した。
実施例1において、黄色調色用組成物として製造例1で得られた組成物に代えて、製造例5で得られた組成物を用いた以外は同様の方法で緑色カラーフィルタを作製した。
・カラーフィルタ特性試験
それぞれ作製したカラーフィルタを用いて、分光光度計(HITACHI社製U3900/3900H形)によって色度ならびに透過スペクトルを、膜厚計(HITACHI社製 VS1000 走査型白色干渉顕微鏡)によって膜厚を(膜厚は薄いほど高着色力)、それぞれ測定した。結果を以下の表1および表2に示す。
また、比較例3(キノフタロン単量体(6))との比較検討でも同様に、実施例1の方がより高い輝度を示し、膜厚がより薄いことから、二量化によるカラーフィルタ特性の顕著な向上が確認された。キノフタロン単量体(6)は、特開昭53-228の実施例2として記載されている化合物である。
なお、比較例1(C.I.ピグメント イエロー138)は、輝度が低く、膜厚が非常に厚いため、実用レベルにない。このように、本発明化合物は、現行の代表的な黄色顔料を超える顕著な効果を有するものである。
窒素雰囲気下、フラスコ中に安息香酸70.0g(573mmol)を量りとり、140℃にて溶融させた。そこに、合成例3で得た中間体(C) 2.50g(6.29mmol)と4,5-ジクロロフタル酸無水物7.24g(33.3mmol)を加え、220℃にて6時間攪拌した。放冷後、反応溶液にアセトン500mLを加え、1時間攪拌した後、減圧ろ過にて黄色粉末である目的物(E)を5.92g(4.96mmol)得た。(収率:79%)
FD-MS: 1192 M+
前記合成例5で得たキノフタロン化合物(式(E)の化合物) 0.500質量部を塩化ナトリウム1.50質量部、ジエチレングリコール0.750質量部とともに磨砕した。その後、この混合物を600質量部の温水に投じ、1時間攪拌した。水不溶分をろ過分離して温水でよく洗浄した後、90℃で送風乾燥して顔料化を行った。得られた顔料の粒子系は、100nm以下、粒子の平均長さ/幅比は3.00未満であった。得られたキノフタロン化合物の黄色顔料を用いて以下の分散試験及びカラーフィルタ評価試験を行った。
キノフタロン化合物(D)の代わりに合成例5で得たキノフタロン化合物(E)を用いた以外は前記製造例1と同様の方法で黄色調色用組成物を作製した。
前記実施例1において、製造例1で得られた黄色調色用組成物の代わりに、製造例6で得られた黄色調色用組成物を用いた以外は、前記実施例1と同様の方法で緑色カラーフィルタを得た。
実施例2で得られた緑色カラーフィルタを用いて、分光光度計(HITACHI社製U3900/3900H形)によって色度ならびに透過スペクトルを、膜厚計(HITACHI社製 VS1000 走査型白色干渉顕微鏡)によって膜厚を(膜厚は薄いほど高着色力)測定した。結果を以下の表3に示す。
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WO2020045197A1 (ja) * | 2018-08-31 | 2020-03-05 | Dic株式会社 | 顔料組成物、着色組成物及びカラーフィルタ |
WO2021117410A1 (ja) * | 2019-12-13 | 2021-06-17 | Dic株式会社 | キノフタロン化合物、顔料組成物及びカラーフィルタ |
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