TWI696667B - Blue coloring composition containing dibenzopiperan dye, coloring agent for color filter and color filter - Google Patents

Abstract

The present invention relates to a blue coloring composition containing a dibenzopyran dye represented by the following general formula (1). In the formula, R ² and R ³ can be bonded to each other to form a ring, R ⁶ and R ⁷ can be bonded to each other to form a ring, R ⁹ ~ R ¹² can be adjacent groups bonded to each other to form a ring, R ¹³ ~ adjacent groups of R ¹⁶ may bond to each other to form a ring, R ⁹ ~ R to form a ring, R ¹⁷ ~ R ²¹ may be bonded to each other adjacent to each other of the group of at least one set ²¹ -SO ₃ ^-, M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, x represents an integer of 0~3, y represents an integer of 1 or 2,

Description

Blue coloring composition containing dibenzopiperan dye, coloring agent for color filter and color filter

The present invention relates to a blue coloring composition containing a dibenzopyran dye, a colorant for a color filter containing the composition, and a color filter using the colorant.

Color filters are used in liquid crystal or electroluminescence (EL) display devices. The color filter is manufactured by laminating colored layers on a light-transmitting substrate such as glass by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. The coloring agents used in the colored layer are roughly classified into pigments and dyes, but generally, pigments considered to be excellent in heat resistance and light resistance are widely used (for example, refer to Patent Documents 1 and 2). However, regarding the use of a color filter with pigments, it is known that the display contrast of a color liquid crystal display device is deteriorated due to the depolarization caused by the reflected light reflected on the surface of the pigment particles in the filter. In addition, since pigments are generally insoluble in solvents, they must be dispersed in a dispersion of resin or the like in the form of fine particles. However, the fine particles cause light scattering, and there is a problem in improving transparency or color purity.

In order to improve these problems, a method using only a dye as a coloring agent or a method using a dye and a pigment in combination is proposed. Since the dye is soluble in the solvent, the use of a color filter with a dye is suppressed in depolarization compared with the case of using a coloring agent with a pigment, and the spectral characteristics are excellent. As dyes used for color filters, triarylmethane-based dyes are known for their excellent color rendering properties (for example, refer to Patent Documents 3 and 4). However, although triarylmethane-based pigments have good color rendering, heat resistance is not It is sufficient, and the heat resistance is expected to be further improved.

On the other hand, dyes having a dibenzopyran skeleton such as C.I. Acid Red 289 are excellent in heat resistance, and are expected as coloring agents for color filters (for example, refer to Patent Document 5). Furthermore, the so-called C.I. means color index.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Special Publication No. 2007-533802

Patent Document 2: Japanese Patent Laid-Open No. 2011-252044

Patent Document 3: Japanese Patent Laid-Open No. 2008-304766

Patent Document 4: Japanese Patent Laid-Open No. 2003-246935

Patent Literature 5: Japanese Patent Laid-Open No. 2013-205833

Patent Document 6: Japanese Patent Laid-Open No. 2011-148973

However, when these dyes are used as colorants for blue color filters, they are usually used in combination with blue pigments and are used for the purpose of improving color rendering, thereby achieving both color rendering and heat resistance The development of the blue-based dibenzopyran-based dyes of both natures is left as a problem.

The present invention has been completed to solve the above-mentioned problems, and its object is to provide a coloring composition containing a dibenzopyran dye that exhibits blue color and excellent heat resistance, and a colorant for color filters containing the coloring composition . In addition, an object of the present invention is to provide a color filter using the colorant for the color filter.

The present invention has been intensively researched to achieve the above-mentioned object, and as a result, the subject is obtained as follows.

1. A blue coloring composition containing a dibenzopyran dye represented by the following general formula (1),

In the formula, R ¹ to R ⁸ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a nitroso group, a thiol group, and a carbon atom which may have a substituent. 20 straight-chain or branched-chain alkyl groups, optionally substituted cycloalkyl groups having 3 to 20 carbon atoms, and optionally substituted 1 to 20 carbon atoms linear or branched-chain alkyl groups Oxygen, or a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, R ⁹ to R ¹⁶ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a nitroso group, a thiol group, -SO ₃ ^-, may have an alkyl substituent having a carbon number of 1 to 20 atoms of straight-chain or branched-chain, the substituent may have carbon atoms of the cycloalkyl group having 3 to 20 of the Group, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, R ¹⁷ to R ²¹ may be The same or different, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, -SO ₃ ^- , a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent which may have a substituent Cycloalkyl having 3 to 20 carbon atoms, linear or branched alkoxy having 1 to 20 carbon atoms which may have substituents, and cycloalkoxy having 3 to 20 carbon atoms which may have substituents Group, or a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, R ² and R ³ may be bonded to each other to form a ring, and R ⁶ and R ⁷ may be bonded to each other to form Rings, R ⁹ ~R ¹² may be adjacent to each other to form a ring, R ¹³ ~R ¹⁶ may be adjacent to each other to form a ring, R ¹⁷ ~R ²¹ may be adjacent to each other to form a ring bonded to form a ring, where, R ⁹ ~ R ²¹ to at least one of -SO ₃ ^-, M represents a hydrogen atom, an alkali metal atom or alkaline earth metal atom, x represents an integer of 0 to 3, y is 1 Or an integer of 2, wherein the compound represented by general formula (1) is neutral in overall charge.

2. The blue coloring composition according to the above 1, wherein in the above general formula (1), R ¹⁷ ~ R ²¹ in any of 1 or 2 is -SO ₃ ^-.

3. The blue-based coloring composition according to the above 1 or 2, wherein in the above general formula (1), R ¹⁷ is -SO _^3.

4. The blue-based coloring composition according to the above 1 or 2, wherein in the above general formula (1), R ¹⁹ is -SO ₃ ^-.

5. The blue coloring composition according to the above 1 or 2, wherein in the above general formula (1), R ¹⁷ and R ¹⁹ are -SO ₃ ^-.

6. The blue coloring composition as described in 1 or 2 above, wherein in the above general formula (1), R ² and R ³ are bonded to each other to form a ring, and R ⁶ and R ⁷ are bonded to each other to form a ring .

7. The blue coloring composition as described in 6 above, wherein the ring is a saturated ring.

8. A colorant for a color filter, which contains the blue coloring composition as described in any one of 1 to 7 above.

9. A color filter using the colorant for color filters as described in 8 above.

The dibenzopyran dye of the present invention is blue and has high heat resistance and excellent solubility in organic solvents, so it is used as a blue coloring composition, especially a blue color filter The coloring agent of light film is useful.

Hereinafter, the embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof. First, the dibenzopyran dye represented by the general formula (1) will be described.

In the general formula (1), examples of the "halogen atom" represented by R ¹ to R ²¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

In the general formula (1), as R ¹ to R ¹⁶ "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" or "a carbon atom which may have a substituent" Cycloalkyl group having 3 to 20 carbon atoms, "Straight or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" or "3 to 20 carbon ring which may have a substituent""Alkoxy""straight chain or branched chain alkyl group with 1 to 20 carbon atoms", "cycloalkyl group with 3 to 20 carbon atoms", "straight chain with 1 to 20 carbon atoms" Or branched-chain alkoxy" or "cycloalkoxy having 3 to 20 carbon atoms", specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl , Octyl, nonyl, decyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third butyl, isooctyl and other branched chain alkyl groups; cyclopropyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and other cycloalkyl groups; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy , Heptoxy, octoxy, nonoxy, decoxy and other linear alkoxy groups; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctoxy Branched-chain alkoxy groups; cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and other cycloalkoxy groups.

In the general formula (1), as the "straight or branched alkyl group having 1 to 20 carbon atoms with substituents" represented by R ¹ to R ¹⁶ , and "the carbon number with substituents 3""~20cycloalkyl","a linear or branched alkoxy group having 1 to 20 carbon atoms with a substituent" or "a cycloalkoxy group having 3 to 20 carbon atoms with a substituent" In the "substituent group", specifically, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; a carbon atom such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group have 3 to 10 carbon atoms Cycloalkyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy and other carbon atoms 1~ 10 linear alkoxy groups; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy and other branched chain alkoxy groups with 1 to 10 carbon atoms Group; cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and other cycloalkoxy groups with 3 to 10 carbon atoms; phenyl, naphthyl, biphenyl, anthracenyl and other carbon atoms 6 to 18 aromatic hydrocarbon groups or 6 to 18 carbon atoms condensed polycyclic aromatic groups, etc. These "substituents" may contain only one or plural ones, and when plural plural ones are included, they may be the same or different from each other. Furthermore, these "substituents" may further have the substituents exemplified above.

In the general formula (1), as R ¹⁷ to R ²¹ , "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" or "a carbon atom which may have a substituent""Cycloalkyl group having 3-20", "Straight-chain or branched alkoxy group having 1-20 carbon atoms which may have a substituent", "Ring having 3-20 carbon atoms which may have a substituent""Alkoxygroup" or "straight-chain or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent""straight-chain or branched alkyl group having 1 to 20 carbon atoms" , "Cycloalkyl having 3 to 20 carbon atoms", "Straight-chain or branched alkoxy having 1 to 20 carbon atoms", "Cycloalkoxy having 3 to 20 carbon atoms" or " Straight-chain or branched alkenyl group having 2 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl Straight-chain alkyl groups such as phenyl and decyl; branched-chain alkyl groups such as isopropyl, isobutyl, second butyl, third butyl, and isooctyl; cyclopropyl, cyclopentyl, cyclic Cycloalkyl groups such as hexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, Linear alkoxy groups such as octoxy, nonoxy, decoxy, etc.; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctoxy, etc. Alkoxy; cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and other cycloalkoxy; vinyl, 1-propenyl, allyl, 1-butenyl, 2- Linear alkenyl such as butenyl, 1-pentenyl, 1-hexenyl; branched alkenyl such as isopropenyl, isobutenyl, etc.

In the general formula (1), as the "straight-chain or branched alkyl group having 1 to 20 carbon atoms with substituents" represented by R ¹⁷ to R ²¹ , and "the number of carbon atoms with substituent groups 3""~20 cycloalkyl group", "straight chain or branched chain alkoxy group having 1 to 20 carbon atoms with substituents", "cycloalkoxy group having 3 to 20 carbon atoms with substituents" Or "substituent" in "straight-chain or branched alkenyl group having 2 to 20 carbon atoms with substituents", specifically, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Halogen atoms; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and other cycloalkyl groups with 3 to 10 carbon atoms; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl Straight chain alkoxy groups with 1 to 10 carbon atoms, such as oxy, heptoxy, octoxy, nonoxy, decoxy, etc.; isopropoxy, isobutoxy, second butoxy, Branched-chain alkoxy groups with 1 to 10 carbon atoms, such as third butoxy, isooctoxy, etc.; 3 carbon atoms with cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, etc. ~10 cycloalkoxy groups; phenyl, naphthyl, biphenyl, anthracenyl and other aromatic hydrocarbon groups with 6 to 18 carbon atoms or condensed polycyclic aromatic groups with 6 to 18 carbon atoms, etc. These "substituents" may contain only one or plural ones, and when plural plural ones are included, they may be the same or different from each other. Furthermore, these "substituents" may further have the substituents exemplified above.

In the general formula (1), R ² and R ³ or R ⁶ and R ⁷ may be bonded to each other via a single bond or a methylene group which may have a substituent to form a ring. In R ⁹ to R ¹² or R ¹³ to R ¹⁶ , adjacent groups may be bonded to each other via a single bond or a methylene group which may have a substituent to form a ring. In addition, in R ¹⁷ to R ²¹ , adjacent groups may be bonded to each other via a single bond or a methylene group which may have a substituent to form a ring. In addition, as the "substituent" in these "methylene groups which may have a substituent", there may be exemplified a linear or 1 to 20 carbon atom having a substituent, which is represented by R ¹ to R ¹⁶ "Branched alkyl group", "cycloalkyl group having 3 to 20 carbon atoms with substituents", "linear or branched alkoxy group having 1 to 20 carbon atoms with substituents" or The "substituent" in the "cycloalkoxy group having 3 to 20 carbon atoms having a substituent" is the same, and the same can be cited as the adopted form.

In the general formula (1), R ¹ to R ^{8 are} preferably a hydrogen atom, a halogen atom, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, Or a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, more preferably a hydrogen atom or a linear or branched chain having 1 to 20 carbon atoms which may have a substituent The alkyl group is further preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, more preferably a hydrogen atom or 1 to 10 carbon atoms which may have a substituent 5 linear or branched alkyl group.

In the general formula (1), R ² and R ³ or R ⁶ and R ⁷ may be bonded to each other to form a ring, and the ring formed in this case is preferably a 5-membered ring or a 6-membered ring , More preferably a 6-member ring. Also, the rings are preferably saturated rings. R ² and R ³ may form a ring with each other, and R ⁶ and R ⁷ may form a ring with each other.

In the general formula (1), as R ⁹ ~ R ^16, is preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ ^-, may have a substituent group of carbon atoms of 1 to 20 linear Or a branched alkyl group, or a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, and further preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group,- SO ₃ ^-, a substituent may have carbon atoms of straight-chain or branched alkyl group of 1 to 10 of, or an alkoxy substituent having a carbon number of 1 to 10 atoms of straight-chain or branched-chain of Group, particularly preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ ^- , a linear or branched alkyl group having 1 to 5 carbon atoms which may have a substituent, or may have a substituent The linear or branched alkoxy group having 1 to 5 carbon atoms.

In the general formula (1), in R ⁹ to R ¹² or R ¹³ to R ¹⁶ , adjacent groups may be bonded to each other to form a ring, and the ring formed in this case is preferably 5 Member ring or 6 member ring, more preferably 6 member ring. Rings may be formed in R ⁹ to R ¹² and R ¹³ to R ¹⁶ or only in any group.

In the general formula (1), as R ¹⁷ ~ R ^21, is preferably a hydrogen atom, a halogen atom, -SO ₃ ^-, can be substituted by an alkoxy group having a carbon number of 1 to 20 atoms of the straight-chain or branched group, or a substituent having a carbon number of 1 to 20 atoms of the straight-chain or branched alkoxy group, more preferably a hydrogen atom or -SO ₃ ^-.

In the general formula (1), in R ¹⁷ to R ²¹ , adjacent groups may be bonded to each other to form a ring. The ring formed in this case is preferably a 5-membered ring or a 6-membered ring. The best is a 6-member ring.

In the general formula (1), R ⁹ ~ R ²¹ in at least one set of -SO ₃ ^-, -SO ₃ ^- of the maximum number is preferably 5, -SO ₃ ^- Number of preferably 1 ~ Three, more preferably one or two, especially one.

In the general formula (1), preferred is any of the ¹⁷ ~ R ²¹ R is at least one of -SO ₃ ^-, more preferably R ¹⁷ or R ¹⁹ is -SO ₃ ^-, particularly preferably R ¹⁷ is -SO ₃ ^- . Both R ¹⁷ and also R ¹⁹ is -SO ₃ ^-.

In the general formula (1), "M" represents a hydrogen atom; alkali metal atoms such as lithium atoms, sodium atoms, potassium atoms; alkaline earth metal atoms such as beryllium atoms, magnesium atoms, calcium atoms, and barium atoms, preferably hydrogen atoms or Alkali metal atom.

In the general formula (1), x represents the number of "M", which is an integer of 0~3, x is preferably 0~2, more preferably 0 or 1, particularly preferably 0.

In the general formula (1), y represents an integer of 1 or 2, preferably 1.

The compound represented by the general formula (1) is neutral in overall charge. For example, in the general formula (1), when only one of R ⁹ to R ²¹ is -SO ₃ ^- , x=0 (M does not exist) and y=1. In addition, when any two of R ⁹ to R ²¹ are -SO ₃ ^- , when M is a hydrogen atom or an alkali metal, x=1 and y=1, and when M is an alkaline earth metal, x=1, y=2. Furthermore, depending on the valence of each M (hydrogen atom, alkali metal, or alkaline earth metal), x takes any value from 1 to 3, and y becomes 1 or 2.

The dibenzopyran dye represented by the general formula (1) preferably has a maximum absorption wavelength in the range of 500 to 700 nm in the absorption spectrum measurement of the visible light region. For better color development of blue, the maximum absorption wavelength is preferably in the range of 530~700nm It is preferably in the range of 560 to 700 nm, further preferably in the range of 600 to 700 nm, and particularly preferably in the range of 610 to 680 nm.

]1',1'-二氧化物(3,6-Dichlorospiro[9H-xanthene-9,3'-[3H][2,1]benzoxathiole]1',1'-dioxide)(二氯磺基熒烷)衍生物、與具有合適之取代基之吲哚啉衍生物於N-甲基吡咯啶酮(NMP)等使原料溶解之任意溶劑中且於適當之溫度條件下進行反應而合成。 The dibenzopyran dye represented by the general formula (1) can be synthesized using a known method (for example, refer to Patent Document 6). For example, by using 3,6-dichlorospiro[9H-dibenzopyran-9,3'-[3H][2,1] represented by the following general formula (2) as a starting material Benzo

]1',1'-dioxide (3,6-Dichlorospiro[9H-xanthene-9,3'-[3H][2,1]benzoxathiole]1',1'-dioxide) (dichlorosulfofluorene Alkane) derivatives, and indoline derivatives with suitable substituents are synthesized in N-methylpyrrolidone (NMP) in any solvent in which the raw materials are dissolved and under suitable temperature conditions.

In the above general formula (2), R ¹⁸ to R ²¹ have the same definitions as in the general formula (1).

In the synthesis of dibenzopyran dyes represented by the general formula (1), the molar ratio of the added dichlorosulfofluoran derivatives and indoline derivatives used as starting materials is The sulfofluoran derivative is 1 mole, and the indoline derivative is preferably 2 to 20 times the molar equivalent, and more preferably 3 to 10 times the molar equivalent.

The target dibenzopyran dyes can be purified by column chromatography as needed; adsorption purification by silica gel, activated carbon, activated clay, etc.; dispersion washing by solvent; or by recrystallization, crystallization, etc. It is refined by a known method. The solvent used for purification is not particularly limited, and alcohols such as methanol and ethanol; halogenated methanes such as methylene chloride and chloroform; toluene and the like can be used alone or in combination.

Specific examples of preferred compounds of the dibenzopyran dye of the present invention represented by the general formula (1) are shown below, but the present invention is not limited to those compounds. In the following structural formula, a part of hydrogen atoms is omitted and described. In addition, even in the case where stereoisomers exist, the planar structural formula is also described.

[化7]

[化22]

The dibenzopyran dye of the present invention is preferably a decomposition starting temperature in thermogravimetry-differential thermal analysis (TG-DTA, Thermogravimetry-Differential Thermal Analysis) of 200°C or higher, more preferably 250°C or higher, especially It is preferably above 300°C. When considering the application to the color filter, the higher the decomposition start temperature, the better.

The colorant for a color filter of the present invention includes a blue coloring composition containing a dibenzopyran dye represented by the general formula (1), and a composition generally used in the manufacture of color filters Minute. Common color filters, for example, in the case of applying the photolithography step method, are pigments such as dyes or pigments and resin components (including monomers and oligomers) or solvents are applied by coating on a substrate such as glass or resin The liquid prepared by mixing is photopolymerized using a photomask to produce a coloring pattern of a pigment-resin composite film that is soluble/insoluble in solvent, washed and heated to obtain. In addition, in the electrodeposition method or the printing method, a coloring pattern is produced by mixing a pigment with a resin or other components. Therefore, as specific components of the colorant for color filters of the present invention, there may be mentioned dibenzopyran dyes represented by the general formula (1), other dyes or pigments such as pigments, resin components, organic solvents, And other additives such as photopolymerization initiator. Also, you can choose from these components, or add other components as needed.

The coloring composition contained in the colorant for a color filter must be dissolved or well dispersed in an organic solvent containing a resin or the like in the manufacturing process of the colorant for a color filter and the color filter, so it is preferably It has high solubility in organic solvents. The organic solvent is not particularly limited, and specific examples include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); and propylene glycol monomethyl ether acetate ( PGMEA) and other ether esters; ketones such as acetone and cyclohexanone; alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene, toluene and xylene; N,N-dimethylformamide (DMF), N -Acetamides such as methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO), etc. These solvents can be used alone or in combination of two or more.

As an organic solvent generally used in the manufacture of color filters, there is propylene glycol monomethyl ether (PGME), but the solubility of the dibenzopyran dye of the present invention in PGME is preferably 0.5% by weight or more, more preferably 1% by weight or more, more preferably 1.2% by weight or more, and particularly preferably 1.4% by weight or more.

系、二

系、偶氮系、不屬於本發明之二苯并吡喃系等藍色系之染料或顏料等，為了較高之溶解性，較佳為藍色系染料。其他色素相對於二苯并吡喃系染料之混合比較佳為5~2000重量%，更佳為設為10~1000重量%。關於液狀之彩色濾光片用著色劑中之染料等色素成分之混合比，相對於著色劑中整體，較佳為0.5~70重量%，更佳為1~50重量%。 The colorant for a color filter of the present invention may use the dibenzopyran dye represented by the general formula (1) alone, and may be used by mixing two or more kinds in order to adjust the color tone. In addition, other well-known pigments may be used in combination. Other dyes are not particularly limited, but in order to show blue, basic dyes such as CI Basic Blue 3, 7, 9, 54, 54, 65, 75, 77, 99, 129; CI acid Acid dyes such as Acid Blue 9, 74; Disperse dyes such as Disperse Blue 3, 7, 377; HC dyes such as HC Blue 2, 7, 11, 12, 14, 15, 16, 17; Spilon dye ; Cyanine series, indigo series, phthalocyanine series, anthraquinone series, methine series, triarylmethane series, indanthrene series,

Department, Second

Blue dyes and pigments, such as a series, azo series, and dibenzopyran series, which are not part of the present invention, are preferably blue series dyes for higher solubility. The mixing ratio of other pigments to the dibenzopyran dye is preferably 5 to 2000% by weight, and more preferably 10 to 1000% by weight. The mixing ratio of dye components such as dyes in the colorant for liquid color filters is preferably 0.5 to 70% by weight, and more preferably 1 to 50% by weight relative to the entire colorant.

As the resin component, if the color filter resin film formed by using such a material has a manufacturing method or properties necessary for use, a known one can be used. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (phenolic novolac) resins, other transparent The resin, photocurable resin or thermosetting resin can be used in appropriate combination of these monomer or oligomer components. Moreover, the copolymer of these resins can also be used in combination. Regarding the content of the resin in the colorants for color filters, in the case of a liquid coloring agent, it is preferably 5 to 95% by weight, and more preferably 10 to 50% by weight.

Examples of other additives include components necessary for the polymerization or hardening of resins such as photopolymerization initiators and crosslinking agents, and for stabilization of the properties of the components in the colorants for liquid color filters Surfactants or dispersants. These can be known in the manufacture of color filters, and are not particularly limited. The mixing of the total amount of these additives in the entire solid content of the colorant for color filters is preferably 5-60% by weight, more preferably 10-40% by weight.

[Example]

Hereinafter, the embodiment of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. In addition, the identification of the compound obtained in the synthesis example was performed by ¹ H-NMR analysis (a nuclear magnetic resonance apparatus manufactured by JEOL Ltd., JNM-ECA-600).

[Synthesis Example 1] (Synthesis of Compound A-1)

In a reaction vessel, 5.00 g of dichlorosulfofluorane, 5.88 g of indoline, and 50 mL of NMP were added, and the mixture was stirred at 110°C for 7 hours. After leaving to cool, the reaction solution was poured into 600 mL of water, 1 M hydrochloric acid was added until the pH value became 4, and the precipitated solid was filtered off. The obtained crude product was washed with ethanol to thereby obtain the target product (0.79 g, yield 11%) as a purple-red powder.

NMR (nuclear magnetic resonance) measurement was performed on compound A-1, and the following 26 hydrogen signals were detected. ¹ H-NMR (600 MHz, DMSO-d ₆ ): δ (ppm) = 8.22 (1H), 8.07 (1H), 7.66-7.68 (3H), 7.56-7.60 (3H), 7.50 (2H), 7.40 (3H ), 7.28-7.33 (3H), 7.11 (2H), 4.30 (4H), 3.22 (4H).

[Synthesis Example 2] (Synthesis of Compound A-2)

In a reaction vessel, 2.54 g of dichlorosulfofluorane, 4.05 g of 2,3,3-trimethylindoline and 25 mL of NMP were added, and the mixture was stirred at 120° C. for 10 hours. After leaving to cool, the reaction solution was poured into 350 mL of water, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform/methanol=10/1 (volume ratio)), thereby obtaining the target product (1.82g, produced as a purple powder) Rate 44%).

NMR measurement of compound A-2 detected the following 38 hydrogen signals. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.47-7.63 (6H), 7.25-7.36 (8H), 7.08-7.24 (3H), 4.17 (2H), 1.38 (6H ), 1.27 (6H), 1.25 (6H).

[Synthesis Example 3] (Synthesis of Compound A-3)

Add 2.03g of dichlorosulfofluorane, 1,2,3,3a,4,8b-hexahydrocyclopentane to the reaction vessel [b] Indole 3.18g, NMP 40mL, and stirred at 80°C for 8 hours. After leaving to cool, the reaction solution was poured into 400 mL of water, 1M hydrochloric acid was added until the pH value became 2, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform/methanol=10/1 (volume ratio)), thereby obtaining the target product (0.63g, produced as purple powder) Rate 19%).

The compound A-3 was subjected to NMR measurement, and the following 34 hydrogen signals were detected. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.06-7.65 (17H), 4.68-4.76 (2H), 3.92-3.97 (2H), 1.91-2.18 (8H), 1.71 (2H), 1.36 (2H).

[Synthesis Example 4] (Synthesis of Compound A-7)

In the reaction vessel, 1.93 g of dichlorosulfofluorane, 1.30,1,2,3,4,4a,9a-hexahydro-9H-carbazole 3.30 g, and 40 mL of NMP were added, and the mixture was stirred at 80° C. for 8 hours. After leaving to cool, the reaction solution was poured into 400 mL of water, 1M hydrochloric acid was added until the pH value became 2, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform/methanol = 8/1 (volume ratio)), thereby obtaining the target product (0.901g, produced as a purple powder) Rate 28%).

NMR measurement of compound A-7 detected the following 38 hydrogen signals. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.64 (1H), 7.47-7.54 (5H), 7.25-7.30 (8H), 7.16 (2H), 7.09 (1H), 4.48(2H), 3.62(2H), 2.36(2H), 2.19(2H), 1.86-1.91(4H), 1.61-1.68(4H), 1.19-1.29(4H).

[Synthesis Example 5] (Synthesis of Compound A-8)

Add 0.530g of dichlorosulfofluorane, 6-tert-butyl-1,2,3,4,4a,9a-hexahydro-9H-carbazole 1.20g, NMP 10mL to the reaction vessel, and at 80 ℃ Stir for 8 hours. After leaving to cool, the reaction solution was poured into 100 mL of water, 1M hydrochloric acid was added until the pH value became 2, and the precipitated solid was filtered off. The crude product obtained was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform/methanol=9/1 (volume ratio)), thereby obtaining the target product (0.328g, produced as a purple powder) Rate 32%).

NMR measurement of compound A-8 detected the following 54 hydrogen signals. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.64 (1H), 7.40-7.50 (5H), 7.09-7.28 (8H), 7.09 (1H), 4.47 (2H), 3.60 (2H), 2.39 (2H), 2.16 (2H), 1.88-1.92 (4H), 1.62-1.68 (4H), 1.21-1.38 (22H).

[Synthesis Example 6] (Synthesis of Compound A-9)

Add 0.530g of dichlorosulfofluorane, 3-tert-butyl-1,2,3,4,4a,9a-hexahydro-9H-carbazole 1.20g, NMP 10mL to the reaction vessel, and at 80 ℃ Stir for 8 hours. After leaving to cool, the reaction solution was poured into 100 mL of water, 1M hydrochloric acid was added until the pH value reached 1.5, 10 g of sodium chloride was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, dissolution solution: toluene/ethanol = 10/1 (volume ratio)), thereby obtaining the target product (0.510 g, produced as a purple powder) Rate 49%).

The compound A-9 was subjected to NMR measurement, and the following 54 hydrogen signals were detected. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.65 (1H), 7.47-7.54 (5H), 7.25-7.30 (8H), 7.16 (2H), 7.09 (1H), 4.40 (2H), 3.64 (2H), 2.20 (2H), 1.98 (4H), 1.68 (4H), 1.43 (2H), 1.26 (2H), 0.89 (18H).

[Synthesis Example 7] (Synthesis of Compound A-10)

Add 0.302g of dichlorosulfofluorane, 6-trifluoromethyl-1,2,3,4,4a,9a-hexahydro-9H-carbazole 0.720g, NMP 5mL to the reaction vessel, and at 100 ℃ Stir for 5.5 hours. After leaving to cool, the reaction solution was poured into 50 mL of water, 1 M hydrochloric acid was added until the pH value became 2, and 5 g of sodium chloride was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, dissolution solution: toluene/ethanol=10/1 (volume ratio)), thereby obtaining the target product (0.161 g, produced as a purple powder) Rate 26%).

The compound A-10 was subjected to NMR measurement, and the following 36 hydrogen signals were detected. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.46 (1H), 7.67 (1H), 7.58-7.61 (3H), 7.51-7.54 (6H), 7.33-7.37 (4H), 7.27 (1H ), 4.54 (2H), 3.65 (2H), 2.38 (2H), 2.24 (2H), 1.93 (2H), 1.69 (4H), 1.22-1.31 (6H).

[Synthesis Example 8] (Synthesis of Compound A-11)

Add 1.00g of dichlorosulfofluorane, 6-methoxy-1,2,3,4,4a,9a-hexahydro-9H-carbazole 2.00g, NMP 15mL to the reaction vessel at 70℃ Stir for 8 hours. After leaving to cool, the reaction solution was poured into 150 mL of water, 1 M hydrochloric acid was added until the pH value became 2, and 15 g of sodium chloride was added, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, dissolution solution: toluene/ethanol=10/1 (volume ratio)), thereby obtaining the target product (1.32 g, produced as a purple powder) Rate 73%).

NMR measurement was performed on compound A-11, and the following 42 hydrogen signals were detected. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.45 (1H), 7.62 (1H), 7.49 (1H), 7.38-7.45 (4H), 7.17 (4H), 7.08 (1H), 6.84 ( 2H), 6.75(2H), 4.45(2H), 3.86(6H), 3.57(2H), 2.31(2H), 2.16(2H), 1.99(2H), 1.85(2H), 1.62(2H), 1.20- 1.29(6H).

[Synthesis Example 9] (Synthesis of Compound A-12)

Add 1.51g of dichlorosulfofluoran, 6-chloro-1,2,3,4,4a,9a-hexahydro-9H-carbazole 3.10g, NMP 20mL to the reaction vessel, and stir at 80 ℃ 8 hour. After leaving to cool, the reaction solution was poured into 200 mL of water, 1 M hydrochloric acid was added until the pH value became 2, and 20 g of sodium chloride was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel column chromatography (carrier: silica gel, dissolution solution: toluene/ethanol=10/1 (volume ratio)), thereby obtaining the target product (1.62g, produced as a purple powder) 58%).

NMR measurement was performed on compound A-12, and the following 36 hydrogen signals were detected. ¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 8.44 (1H), 7.65 (1H), 7.50-7.53 (3H), 7.45 (1H), 7.40 (1H), 7.22-7.27 (8H), 7.09 (1H), 4.48 (2H), 3.60 (2H), 2.31 (2H), 2.20 (2H), 1.89 (2H), 1.66 (4H), 1.22-1.29 (6H).

[Example 1]

The dibenzopyran dye A-2 obtained in Synthesis Example 2 was subjected to ultraviolet-visible absorption spectroscopy using a spectrophotometer (manufactured by Hitachi, Ltd., U-3000). Determination. The measurement was performed at room temperature, and PGME was used as a solvent. From the obtained ultraviolet-visible absorption spectrum, the maximum absorption wavelength in the visible region is obtained.

In addition, using a thermogravimetric-differential thermal analysis device (manufactured by MAC Science Co., Ltd., TG-DTA 2000S), TG-DTA measurement was carried out under a nitrogen stream (sample weight: 4±1 mg, heating rate: 20° C./min) , Find the decomposition starting temperature. Furthermore, the solubility of PGME at room temperature was measured. Table 1 shows the measurement results.

[Example 2 to Example 7]

For the dibenzopyran dyes A-7 to A-12 obtained in Synthesis Examples 4 to 9, ultraviolet-visible absorption spectroscopy, TG-DTA and solubility in PGME were measured in the same manner as in Example 1. . The results are shown in Table 1.

[Comparative Example 1 and Comparative Example 2]

For comparison, for CI Acid Red 289 (manufactured by Chugai Chemicals Co., Ltd.) represented by the following structural formula (B-1) and CI Basic Blue 1 (Tokyo Chemical Industry) represented by the following structural formula (B-2) Co., Ltd.), in the same manner as in Example 1, ultraviolet-visible absorption spectroscopy measurement, TG-DTA measurement, and PGME solubility measurement. The results are shown in Table 1.

[Table 1]

As shown in Table 1, the dibenzopyran dyes of Examples 1 to 7 of the present invention have a maximum absorption wavelength in the range of 600 to 700 nm and appear blue. In addition, since the decomposition start temperature is 300° C. or higher and has sufficient heat resistance, it is useful as a colorant for color filters. In addition, the dibenzopyran dyes of Examples 1 to 7 of the present invention have no problem in terms of solubility in PGME as a colorant for color filters.

On the other hand, it can be seen that the dye B-1 of Comparative Example 1 has a dibenzopyran skeleton like the dye used in the examples, and the decomposition starting temperature is 300° C. or more, but the maximum absorption wavelength is 600 to 700 nm Outside the range, it is dark red instead of blue. Furthermore, although the dye B-2 of Comparative Example 2 has a maximum absorption wavelength in the range of 600 to 700 nm, it is blue, but the decomposition initiation temperature is lower than 200° C., and the heat resistance is insufficient.

Based on the above results, the dibenzopyran-based dye of the present invention is blue and has high heat resistance, and is useful as a blue-based coloring composition, especially a colorant for color filters.

The present invention has been described in detail and with reference to specific embodiments, and it is known to the practitioner that various modifications or changes can be made without departing from the spirit and scope of the present invention.

This application is based on the Japanese Patent Application 2015-061028 filed on March 24, 2015, and the contents thereof are incorporated herein by reference.

[Industry availability]

The dibenzopyran dye of the present invention is blue in itself, and is excellent in heat resistance and solubility in organic solvents, and is a blue coloring composition that replaces the previous pigment, especially blue for color filters It is useful as a colorant.

Claims (8)

A blue coloring composition containing a dibenzopyran dye represented by the following general formula (1),

[In the formula, R ¹ to R ⁸ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a nitroso group, a thiol group, and a carbon atom which may have a substituent 1 ~20 straight-chain or branched-chain alkyl, optionally substituted C3-C20 cycloalkyl, and optionally substituted C1-C20 straight-chain or branched-chain Alkoxy, or a cycloalkoxy having 3 to 20 carbon atoms which may have a substituent, R ⁹ to R ¹⁶ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , Nitroso, thiol group, -SO ₃ ^- , linear or branched alkyl group with 1 to 20 carbon atoms which may have substituents, ring with 3 to 20 carbon atoms which may have substituents Alkyl group, linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, or cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, R ¹⁷ to R ²¹ May be the same or different, and independently represent a hydrogen atom, a halogen atom, a hydroxyl group, -SO ₃ ^- , a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent Cycloalkyl group having 3 to 20 carbon atoms, linear or branched alkoxy group having 1 to 20 carbon atoms which may have substituents, and cycloalkane having 3 to 20 carbon atoms which may have substituents Oxygen, or a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, R ² and R ³ are bonded to each other to form a ring, and R ⁶ and R ⁷ are bonded to each other to form Rings, R ⁹ ~ R ¹² may be adjacent to each other to form a ring, R ¹³ ~ R ¹⁶ may be adjacent to each other to form a ring, R ¹⁷ ~ R ²¹ may be adjacent to each other to form a ring bonded to form a ring, where, R ⁹ ~ R ²¹ to at least one of -SO ₃ ^-, M represents a hydrogen atom, an alkali metal atom or alkaline earth metal atom, x represents an integer of 0 to 3, y is 1 Or an integer of 2, wherein the compound represented by the general formula (1) is neutral in overall charge]. The requested item blue coloring composition of 1, wherein (1) In the above formula, any of the ¹⁷ ~ R ²¹ R & lt 1 or 2 is -SO ₃ ^-. The requested item blue coloring composition 1 or 2, wherein in the above general formula (1), R ¹⁷ is -SO ₃ ^-. The requested item blue coloring composition 1 or 2, wherein in the above general formula (1), R ¹⁹ is -SO ₃ ^-. The requested item blue coloring composition 1 or 2, wherein in the above general formula (1), R ¹⁷ and R ¹⁹ are -SO ₃ ^-. The blue coloring composition according to claim 1, wherein at least one of a ring formed by mutually bonding R ² and R ³ and a ring formed by mutually bonding R ⁶ and R ⁷ is a saturated ring. A colorant for color filters, which contains the blue coloring composition according to any one of claims 1 to 6. A color filter using the colorant for a color filter as in claim 7.