KR20190026573A - Coloring agent compound and coloring composition comprising the same - Google Patents

Abstract

The present invention relates to a colorant compound of a novel structure, which exhibits excellent color properties, heat resistance, and solubility, and can be used for manufacturing a color filter, and to a coloring composition including the colorant compound. The colorant compound is represented by chemical formula 1. In chemical formula 1, R_1 to R_5 are each independently hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, an N-alkylene-piperidine dione having at least one aromatic ring of 6 to 20 carbon atoms combined therewith, or an N-alkylene-pyrrolidine dione.

Description

COLORING AGENTS AND COLORING COMPOSITIONS CONTAINING THE SAME [Technical Field]

The present invention relates to colorant compounds and to coloring compositions comprising them. More particularly, the present invention relates to a colorant compound having a novel structure showing excellent color characteristics, heat resistance and solubility, and a coloring composition comprising the same.

A color filter used for a liquid crystal display (LCD) and an organic light emitting diode (OLED) is used for realizing a color image in a display device. The color filter is coated on a basic substrate using various methods, And the like.

The color filter is formed by a red, green, and blue pixel portions on a transparent substrate such as a glass. Color filters used in an image display apparatus and a solid-state image pickup device are typically red (R), green And a blue (B) coloring pattern, and serves to color the passing light or to divide the light into three primary colors.

The dyes displaying red, green and blue are composed of fine particles, that is, dyes or pigments. These dyes are used for obtaining color display characteristics of a desired area, Are mixed to display red, green, and blue.

Materials commonly used as coloring matters are required to have preferable absorption characteristics on the color reproducibility, good resistance to oxidative gases such as light resistance, heat resistance and ozone under the conditions to be used, and the like.

BACKGROUND ART [0002] In recent years, a technology for developing a large-screen and high-definition liquid crystal display has been developed. In such a situation, a color filter used for a liquid crystal display or the like is required to have a high color purity. A variety of pigments or colorants that can be used in the production of color filters are known, but methods of improving color purity, brightness, and contrast ratio using only known color materials are gradually reaching their limit.

In particular, it is difficult to increase the pigment content in the photosensitive resin composition due to the pigment derivative and the dispersant added in accordance with the pigment dispersion method in the production of a color filter using the pigment dispersion method, and thus it is difficult to manufacture a thin film color filter. Therefore, development of a novel pigment for solving such a problem is required.

Korean Patent Publication No. 10-2014-01252183

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a colorant compound having a novel structure which is excellent in color reproducibility, color characteristics, heat resistance and solubility and can be used as a colorant for a color filter and a colorant composition containing the same do.

In order to solve the above problems, an embodiment of the present invention provides a colorant compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, an N-alkylene-piperidine dione in which at least one aromatic ring having 6 to 20 carbon atoms is bonded, - pyrrolidine dione;

R < ₆ >

Each of R ₇ to R ₁₀ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group or an alkoxy group having 1 to 30 carbon atoms;

(2)

(3)

In the above Formulas 2 and 3,

R ₁₁ to R ₂₀ each independently represent hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group or an alkoxy group having 1 to 30 carbon atoms,

At least one of R ₇ to R ₂₀ is a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms to be.

In another embodiment of the present invention, there is provided a coloring composition comprising the colorant compound.

In another embodiment of the present invention, there is provided a color filter comprising the coloring composition.

In another embodiment of the present invention, a display device including the color filter is provided.

The colorant compound of the present invention is a compound of a novel structure which is not known in the prior art and contains a specific group and can exhibit stable color reproducibility and excellent heat resistance and solubility. In addition, since the solubility of the pigment derivative and the dispersant in the solvent is excellent compared to the conventional art, the amount of the pigment derivative and the dispersant can be reduced when the pigment dispersion method is used.

Therefore, the color filter according to the present invention can provide a high-resolution color filter having high color reproduction rate and high brightness and contrast ratio due to excellent color reproducibility and heat resistance. In addition, it is possible to increase the pigment content in the coloring composition due to the excellent solubility of the novel colorant compound, thereby making it possible to manufacture a thin film color filter.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the colorant compound of the present invention and the coloring composition containing the colorant compound will be described in more detail.

Colorant compound

The colorant compound according to one embodiment of the present invention is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, an N-alkylene-piperidine dione in which at least one aromatic ring having 6 to 20 carbon atoms is bonded, - pyrrolidine dione;

R < ₆ >

Each of R ₇ to R ₁₀ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group) or an alkoxy group having 1 to 30 carbon atoms;

(2)

(3)

In the above Formulas 2 and 3,

R ₁₁ to R ₂₀ each independently represent hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group or an alkoxy group having 1 to 30 carbon atoms,

At least one of R ₇ to R ₂₀ is a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms to be.

는 다른 치환기에 연결되는 결합을 의미한다.In the present specification,

Quot; means a bond connected to another substituent.

A colorant compound according to another embodiment of the present invention is a colorant compound of Formula 1, wherein R ₁ , R ₂ , R ₄ and R ₅ are each hydrogen or halogen; The R ₃ may be a functional group of the following formula (4) or a functional group of the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 4 and 5, R < _{21 &} gt ; _, R < ₂₂ & R ₂₃ is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C1-C20 alkoxy group; A substituted or unsubstituted hydroxyalkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; A substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; A substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms; Wherein n, n ₁ and n ₂ may be an _{integer, 0≤n≤4, 0≤n 1 ≤3, 0≤n} 2 ≤3. In the present specification, n, n1 and n2 are to be construed to mean the number of functional groups substituted for the corresponding benzene rings.

The term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

The alkyl group may be a straight chain or branched chain alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

The alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-propyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, n-octyloxy, n-nonyloxy, n-mesyloxy, benzyloxy, p-methylbenzyloxy and the like. It does not.

The aryl group may be a monocyclic aryl group or a polycyclic aryl group having 6 to 30 carbon atoms, or 6 to 20 carbon atoms, or 6 to 12 carbon atoms. Examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and the like. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

The aryl group in the arylalkyl group and the alkylaryl group is the same as the aforementioned aryl group. The alkyl group in the arylalkyl group and the alkylaryl group is the same as the alkyl group described above.

The colorant compound according to another embodiment of the present invention is a colorant compound of Formula 1 wherein at least one of R ₇ to R ₁₀ is a cyclic or straight chain alkyl thio group having 1 to 30 carbon atoms, An aryl thio group having 1 to 30 carbon atoms, and each of R ₁₁ to R ₂₀ is hydrogen, halogen, or an aliphatic group having 1 to 10 carbon atoms.

The colorant compound according to another embodiment of the present invention is the colorant compound of Formula 1, wherein R ₇ to R ₁₀ are each hydrogen, halogen, or an aliphatic group having 1 to 10 carbon atoms, and one of R ₁₁ to R ₁₄ Or at least one of R ₁₅ to R ₂₀ is a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms or an aryl thio group having 1 to 30 carbon atoms.

In Formula 1, at least one of R ₇ to R ₂₀ is preferably a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms Or an alkoxy group having 1 to 30 carbon atoms, and more specifically, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms.

According to an embodiment of the present invention, at least one of R ₇ to R ₂₀ may be a cyclic or straight-chain alkyl thio group having 3 to 6 carbon atoms, for example, butyl It can be a thio group.

As described above, the colorant compound of formula (1) is a compound having at least one cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms at a specific position of a quinaphthalone derivative, An aryl thio group or an alkoxy group having 1 to 30 carbon atoms, and more specifically a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, or And an aryl thio group having 1 to 30 carbon atoms may be substituted.

Specifically, by introducing one or more alkylthio groups into the colorant compound of formula (1) as described above, it is possible to reduce the planarity of the molecule and reduce the? -Π interaction between the molecules. Whereby the solubility of the colorant compound in the organic solvent may be increased as the molecule is easily solvated in the organic solvent.

Accordingly, the solubility of the colorant compound in an organic solvent (for example, DMF) is remarkably improved. Therefore, when the coloring composition containing the colorant compound is prepared by the pigment dispersion method, the amount of the pigment derivative and dispersant required is significantly reduced. Therefore, it is possible to increase the colorant compound or the pigment content in the coloring composition by the above-mentioned ratio, thereby facilitating the production of the thin film collinear filter.

Specific examples of the above-described colorant compound include the compounds represented by the following formulas (6) to (47), but the present invention is not limited thereto.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

The method of synthesizing the colorant compound of the above formula (1) can be widely used without any limitations. For example, the colorant compound of formula (1) may be prepared by firstly introducing phthalimide or 1,8-naphthalimide into pigment yellow, and then adding an alkylthiol ), For example, 1-butanthiol.

Coloring composition

According to one embodiment of the present invention, there is provided a coloring composition comprising the colorant compound.

According to an embodiment of the present invention, the coloring composition may further include at least one of a dye (Dye) and a pigment (Pigment), wherein the dye and the pigment may be any one selected from yellow, red and green May be one containing at least one compound which exhibits color.

According to an embodiment of the present invention, the yellow compound may be a metal-complex compound, an azo compound, a quinophthalone compound, an isoindoline compound, , And a styryl-based compound. The term " compound "

According to another embodiment of the present invention, the red color compound may be a metal-complex series Wherein the compound is selected from the group consisting of an azo compound, a xanthene compound, a diketopyrrolopyrrole compound, an anthraquinone compound, and a perylene compound Or one or more compounds.

According to another embodiment of the present invention, the green compound may be a metal-complex series A triarylmethane-based compound, and an anthraquinone-based compound may be included in the composition of the present invention.

Meanwhile, according to one embodiment of the present invention, the pigment includes a yellow pigment group including PY129, PY138, PY139, PY150, and PY185; A red pigment group including PR 48, PR 48: 1, PR 48: 2, PR 48: 3, PR 48: 4, PR 177, PR 179, PR 207, PR 254, PR 255, PR 264 and PR 269; And green pigment groups including PG 7, PG 36, PG 58, and PG 59; And the like.

The coloring composition according to one embodiment of the present invention may further contain, in addition to the colorant compound, a binder resin, a polyfunctional monomer, a photoinitiator, and a solvent.

The coloring agent compound may be contained in the coloring composition in an amount of 20 parts by weight or more, specifically 25 parts by weight or more, based on 100 parts by weight of the coloring composition, 50 parts by weight or less, specifically 40 parts by weight or less.

When the content of the colorant compound is less than the above range, it is difficult to realize a deep color. If the content of the colorant compound exceeds the above range, the curing reaction of the resin composition may not be performed properly.

On the other hand, 100 parts by weight of the coloring composition may be 100 parts by weight of the total of the colorant compound, the binder resin, the polyfunctional monomer and the photoinitiator contained in the coloring composition. When a solvent is additionally included, May be based on 100 parts by weight of solid contents.

Meanwhile, in the coloring composition according to one embodiment of the present invention, the colorant compound of Formula 1 may be used alone or as a mixture of two or more kinds thereof. In addition, the coloring composition according to one embodiment of the present invention may optionally include other known coloring agents in addition to the coloring agent compound of the above-mentioned formula (1).

On the other hand, when the coloring composition is mixed with a known coloring agent, it is possible to further prevent the re-aggregation of pigments or to prevent foreign matters from being formed. In addition, Effects may exist.

The binder resin is not particularly limited and those generally used in the technical field to which the present invention belongs may be used, and resins which are preferably soluble in alkali may be used.

Specifically, as the alkali-soluble resin, a (meth) acrylic resin, an acrylamide resin, a novolac resin or the like can be used, and preferably a weight average molecular weight (Mw) of 3,000 to 150,000 g / The present invention is not limited thereto. On the other hand, the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) using polystyrene as a standard material.

The binder resin may be contained in the coloring composition in an amount of 3 parts by weight or more, specifically 5 parts by weight or more, more specifically 10 parts by weight or more, and 30 parts by weight or less with respect to 100 parts by weight of the coloring composition , Specifically 20 parts by weight or less, more specifically 15 parts by weight or less.

The multifunctional monomer is not particularly limited and those generally used in the technical field to which the present invention belongs can be used. The multifunctional monomer is a monomer having a role of forming a photoresist image by light, and specifically includes propylene glycol Methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate, tetraethylene glycol methacrylate , Bisphenoxy ethyl alcohol diacrylate, trishydroxy ethyl isocyanurate trimethacrylate, trimethyl propane trimethacrylate, diphenyl pentaerytholitol hexaacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate and dipentaerythritol tri Hexa may be a meta-alone or in combination of two or more thereof is selected from the group consisting of methacrylate.

The multifunctional monomer may be contained in the coloring composition in an amount of 30 parts by weight or more, specifically 40 parts by weight or more, more specifically 50 parts by weight or more, and 80 parts by weight or less, Specifically not more than 70 parts by weight, more specifically not more than 60 parts by weight.

The photoinitiator may be selected from the group consisting of 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) , 4-trichloromethyl- (phenylon) 6-triazine, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2- hydroxy) propyl ketone, benzophenone, 2,4,6-trimethylaminobenzophenone, and the like can be used, but the present invention is not limited thereto.

The photopolymerization initiator may be contained in the coloring composition in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the coloring composition.

Meanwhile, the coloring composition according to one embodiment of the present invention may further include a solvent for improving the applicability and workability.

According to an embodiment of the present invention, the solvent may include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene Propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, At least one compound selected from propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate or dipropylene glycol monomethyl ether, But is not limited thereto.

The content of the solvent is not particularly limited as it is adjustable in consideration of coating properties and workability. For example, the solvent may be contained in an amount of 50 to 500 parts by weight based on 100 parts by weight of the coloring composition.

According to one embodiment of the present invention, the coloring composition may further contain, in addition to the above-mentioned components, a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorbent, a leveling agent, a photosensitizer, a plasticizer, An additive that can be included in the coloring composition for a conventional color filter such as an activator.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris And trimethylol ethane tris (3-mercaptopropionate). However, the present invention is not limited thereto, and may include those generally known in the art.

On the other hand, the coloring composition according to one embodiment of the present invention can be used for producing a color filter by a method generally known in the technical field of the present invention, for example, a printing method or a photolithography method.

For example, according to the photolithography method, the colored composition is applied onto a transparent substrate by a method such as spray coating, spin coating, slit coating, roll coating, or dipping. An exposure process is selectively performed on the coating film through a mask having a predetermined pattern. Meanwhile, the pre-exposure baking and / or post-baking may be further performed. After exposure, the coloring composition is developed to form the desired photoresist pattern. The developed substrate is washed and dried to obtain a color filter in which a desired type of photoresist pattern is formed. On the other hand, the obtained color filter can be utilized in a display device or the like.

As described above, the colorant compound of the present invention is a compound of a novel structure which is not known in the prior art and contains a specific group, and can exhibit stable color reproducibility and excellent heat resistance and solubility. In addition, since the solubility of the pigment derivative and the dispersant in the solvent is excellent compared to the conventional art, the amount of the pigment derivative and the dispersant can be reduced when the pigment dispersion method is used.

Therefore, the color filter according to the present invention can provide a high-resolution color filter having high color reproduction rate and high brightness and contrast ratio due to excellent color reproducibility and heat resistance. In addition, it is possible to increase the pigment content in the coloring composition due to the excellent solubility of the novel colorant compound, thereby making it possible to manufacture a thin film color filter.

Best Mode for Carrying Out the Invention Hereinafter, the operation and effects of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Production Example 1: Synthesis of Compound 1

Compound A was obtained by the method described in U.S. Patent No. 6,849,116 B2. Concretely, 25.5 g of phthalimide and 7.4 g of paraformaldehyde were stirred and added to 560 g of fuming sulfuric acid at 3.6% by weight at 25 캜. The mixture was heated to 50 DEG C and stirred for 30 minutes.

100 g of Pigment Yellow 138 (BASF) was added thereto, and then the mixture was heated to 100 占 폚 and stirred for 3 hours. The mixture was then added to 3500 g of water and stirred for 30 minutes at 60 < 0 > C. The thus-precipitated product was filtered, washed with water to neutrality, and then dried at 90 DEG C in a vacuum drying rack to obtain a compound (A).

Next, 3 g (3.417 mmol) of the compound (A), 0.52 g (7.033 mmol) of 1-butanthiol and 1.94 g (14.06 mmol) of K ₂ CO ₃ were added to 500 ml 1-neck RBF and stirred at 60 ° C. for 24 hours . The reaction solution was cooled to room temperature, and then filtered under reduced pressure. The solvent was removed under reduced pressure and the residue was purified by column to obtain Compound 1. As a result of APCI negative MS analysis, the molecular weight 907 of Compound 1 was confirmed.

Production Example 2: Synthesis of Compound 2

Compound B was obtained in the same manner as in Production Example 1 except that 1,8-naphthalimide was used instead of phthalimide according to the method described in U.S. Patent No. 6,849,116 B2.

Next, 3 g (3.32 mmol) of the compound (B), 0.49 g (6.65 mmol) of 1-butanthiol and 1.83 g (13.28 mmol) of K ₂ CO ₃ were added to 500 ml 1-neck RBF and stirred at 60 ° C. for 24 hours . The reaction solution was cooled to room temperature, and then filtered under reduced pressure. The solvent was removed under reduced pressure, and the residue was purified by column to obtain Compound (2). As a result of APCI negative MS analysis, the molecular weight 957 of Compound 2 was confirmed.

Production Example 3: Synthesis of Compound 3

Compound C was obtained according to the synthesis method described in Korean Patent Laid-Open Publication No. 2013-0137028, and Compound D was obtained by the method described in U.S. Patent No. 6,849,116 B2.

Next, 3 g (3.92 mmol) of the compound (D), 0.58 g (7.84 mmol) of 1-butanthiol and 2.17 g (15.69 mmol) of K ₂ CO ₃ were added to a 500 ml 1-neck RBF and stirred at 60 ° C. for 24 hours . The reaction solution was cooled to room temperature, and then filtered under reduced pressure. The solvent was removed under reduced pressure and the residue was purified by column to obtain the above compound 3. As a result of APCI negative MS analysis, the molecular weight 819 of Compound 3 was confirmed.

Production Example 4: Synthesis of Compound 4

Compound C was obtained according to the synthesis method described in Korean Patent Laid-Open Publication No. 2013-0137028, and the method described in USP 6849116 B2 was used, except that 1,8-naphthalimide was used instead of phthalimide To obtain Compound (E).

Next, 3 g (3.68 mmol) of the compound (E), 0.54 g (7.36 mmol) of 1-butanthiol and 2.03 g (14.72 mmol) of K ₂ CO ₃ were added to 500 ml 1-neck RBF and stirred at 60 ° C. for 24 hours . The reaction solution was cooled to room temperature, and then filtered under reduced pressure. The solvent was removed under reduced pressure and the residue was purified by column to obtain the above compound 4. As a result of APCI negative MS analysis, the molecular weight of Compound 4 was found to be 869.

Production Example 5: Synthesis of Compound 5

Compound F was used instead of PY138 in Preparation Example 1, and Compound 5 was synthesized using Compound G instead of Compound A.

As a result of APCI negative MS analysis, molecular weight 753 of Compound 5 was confirmed.

Production Example 6: Synthesis of Compound 6

Compound H was used instead of PY138 in Preparation Example 1, and Compound 6 was synthesized using Compound H instead of Compound A.

As a result of APCI negative MS analysis, the molecular weight 803 of Compound 6 was confirmed.

Production Example 7: Synthesis of Compound 7

Compound (7) was synthesized by using Compound (J) instead of PY138 and Compound (K) instead of Compound (A)

As a result of APCI negative MS analysis, the molecular weight 803 of Compound 7 was confirmed.

Production Example 8: Synthesis of Compound 8

Compound L was used instead of PY138 in Preparation Example 1, and Compound 8 was synthesized using Compound M instead of Compound A. [

As a result of APCI negative MS analysis, the molecular weight 853 of Compound 7 was confirmed.

Production Example 9: Synthesis of Compound 9

Compound O was synthesized in Preparation Example 1 using Compound N instead of PY138. Next, the compound (O) 2.231 (3.68 mmol), 0.814 g (7.36 mmol) of 1-thiophenol and 2.03 g (14.72 mmol) of K2CO3 were added to 500 ml 1-neck RBF and stirred at 60 ° C for 24 hours. The reaction solution was cooled to room temperature, and then filtered under reduced pressure. The solvent was removed under reduced pressure and the residue was purified by column to obtain Compound 9. As a result of APCI negative MS analysis, the molecular weight 735 of Compound 9 was confirmed.

Production Example 10: Synthesis of Compound 10

Compound O was prepared by the same method as Preparation Example 9, and Compound 10 was synthesized by using cyclopentyl thiol instead of thiophenol in Production Example 9. As a result of APCI negative MS analysis, the molecular weight 722 of Compound 10 was confirmed.

Preparation Example 11: Synthesis of Compound 11

Compound O was prepared in the same manner as in Preparation Example 9, and Compound 11 was synthesized in Production Example 9 using Benzyl Mercaptan instead of thiophenol. As a result of APCI negative MS analysis, the molecular weight 749 of Compound 11 was confirmed.

Comparative Manufacturing Example

Generally, Pigment Yellow 138 (BASF) used as a coloring material in the photosensitive resin composition was prepared.

Experiment 1: Solubility evaluation

The compounds according to Preparation Examples 1 to 11 and Comparative Preparation Examples were prepared and their solubility in 100 g of dimethylformamide (DMF) was measured. The results are shown in Table 1 below. Concretely, when the solubility is 1% or more, it is indicated by O, and when it is less than 1%, the solubility is indicated by X.

division Manufacturing example
One Manufacturing example
2 Manufacturing example
3 Manufacturing example
4 Manufacturing example
5 Manufacturing example
6 Manufacturing example
7 Manufacturing example
8 Manufacturing example
9 Manufacturing example
10 Manufacturing example
11 compare
Manufacturing example Solubility O O O O O O O O O O O X

Example  One

5.554 g of the compound 1 synthesized according to Preparation Example 1, a copolymer of benzyl methacrylate and methacrylic acid (having a molar ratio of 70:30, an acid value of 113 KOH mg / g as a binder resin, a weight average molecular weight of 20,000 ), 2.018 g of a photoinitiator, 12.443 g of a DPHA (Japanese explosive) as a photo-polymerizable compound, 12.443 g of a solvent (trade name: 68.593 g of PGMEA (polypropylene glycol monomethyl ether acetate) and 1.016 g of DIC F-475 as an additive were mixed to prepare a photosensitive resin composition.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 2 synthesized according to Preparation Example 2 was used.

Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 3 synthesized according to Preparation Example 3 was used.

Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 4 synthesized according to Preparation Example 4 was used.

Example 5

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 5 synthesized according to Preparation Example 5 was used.

Example 6

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 6 synthesized in Preparation Example 6 was used.

Example 7

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 7 synthesized in Preparation Example 7 was used.

Example 8

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 8 synthesized in Preparation Example 8 was used.

Example 9

A photosensitive resin composition was prepared in the same manner as in Example 1 except that Compound 9 synthesized according to Preparation Example 9 was used.

Example 10

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 10 synthesized in Preparation Example 10 was used.

Example 11

A photosensitive resin composition was prepared in the same manner as in Example 1 except that Compound 11 synthesized according to Production Example 11 was used.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound of Comparative Preparation Example was used.

Board Fabrication

The photosensitive resin compositions according to Examples 1 to 11 and Comparative Example 1 were used for the substrate production, respectively. Specifically, the photosensitive resin compositions according to the Examples and Comparative Examples were spin-coated on glass (5 × 5 cm) and pre-baked at 100 ° C. for 100 seconds to form a film.

The distance between the substrate on which the film was formed and the photo mask was set to 250 mu m, and an exposure dose of 40 mJ / cm < ² > was irradiated onto the entire substrate using an exposure machine. Subsequently, the exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds and post baked at 230 캜 for 20 minutes to prepare a substrate.

Experiment 2: Evaluation of heat resistance

The substrate produced according to the above-described substrate manufacturing method was used to obtain a transmittance spectrum in a visible light range of 380 nm to 780 nm using a spectroscope (MCPD-Otsuka). In addition, the prebake substrate was post-baked at 230 ° C for 20 minutes to obtain a transmittance spectrum in the same equipment and measurement range.

The color change (hereinafter referred to as "? Eab ") was calculated using the obtained transmittance spectrum and the C light source backlight using the obtained value E (L *, a *, b *) and shown in Table 2 below.

Specifically, the formula for calculating? Eab is as follows.

(L *, a *, b *) = {(? L *) 2 + (? A *) 2 +

The smaller value of DELTA E in the above formula means that the color heat resistance is excellent, and when it has a value of DELTA Eab < 3, it can be said that it is an excellent color material excellent in heat resistance.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 ΔEab 0.91 1.22 0.58 0.61 0.87 1.03 1.41 1.37 1.59 1.69 1.80 0.29

In Table 2, it is confirmed that the colorant compound of Comparative Example 1 is a commercial material having a color change (ΔEab) as small as 0.29. In addition, each of the colorant compounds applied to Examples 1 to 11 was also excellent in color heat resistance so that the color change ([Delta] Eab) was smaller than 3 and could reach a level similar to that of the colorant compound of Comparative Example 1, As shown in FIG.

Experiment 3: Contrast evaluation

The photosensitive resin compositions of Examples 12 to 22 and Comparative Example 2 were prepared by mixing the components and the composition ratios (unit: g) shown in Table 3 below. Using the photosensitive resin composition thus prepared, a substrate was prepared according to the above-described substrate manufacturing method.

Using the contrast meter (Tsubosaka), the thus-prepared substrate was measured for brightness when the polarizing plates above and below the substrate were parallel and orthogonal, and the contrast ratio was calculated by the following equation.

Contrast ratio (CR) = Brightness when the polarizer is parallel to the top and bottom of the substrate / Brightness when the top and bottom polarizers of the substrate are orthogonal

Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Comparative Example 2 G58 3.650 3.372 3.774 3.660 3.660 3.660 3.660 3.660 3.660 3.660 3.660 3.06 Y138 0.485 0.574 0.50 0.621 0.621 0.621 0.621 0.621 0.621 0.621 0.621 2.04 Compound 1 0.965 - - - - - - - - - - - Compound 2 - 1.154 - - - - - - - - - - Compound 3 - - 0.826 - - - - - - - - - Compound 4 - - - 0.819 - - - - - - - - Compound 5 - - - - 0.819 - - - - - - - Compound 6 - - - - - 0.819 - - - - - - Compound 7 - - - - - - 0.819 - - - - - Compound 8 - - - - - - - 0.819 - - - - Compound 9 - - - - - - - - 0.819 - - - Compound 10 - - - - - - - - - 0.819 - - Compound 11 - - - - - - - - - - 0.819 - Binder resin 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 Photoinitiator 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 1.19 additive 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 Photopolymerizable compound 5.865 5.865 5.865 5.865 5.865 5.865 5.865 5.865 5.865 5.865 5.865 5.865 solvent 70 70 70 70 70 70 70 70 70 70 70 70 Total content 100 100 100 100 100 100 100 100 100 100 100 100 Binder resin: Copolymer of benzyl methacrylate and methacrylic acid (molar ratio 70:30, acid value 113 KOH mg / g, weight average molecular weight 20,000 as measured by GPC, molecular weight distribution (PDI) 2.0, solids content 25% D-F-475 as an additive, DPHA (glacial acetic acid) g as a photopolymerizable compound, PGMEA (polypropylene glycol monomethyl ether acetate) as a photoinitiator,

The contrast ratios of the substrates made of the photosensitive resin compositions of Examples 12 to 22 and Comparative Example 2 are shown in Table 4 below.

Constrast ratio (CR) Example 12 9770 Example 13 9740 Example 14 9560 Example 15 9510 Example 16 9640 Example 17 9760 Example 18 9690 Example 19 9710 Example 20 9660 Example 21 9570 Example 22 9740 Comparative Example 2 9370

Referring to the results shown in Table 4, the substrate using the photosensitive resin composition according to Examples 12 to 22 of the present invention is a substrate using a photosensitive resin composition containing a pigment (PY 138) having a low solubility in an organic solvent 2) Contrast ratio was improved by reducing light scattering.

Claims (16)

A colorant compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, an N-alkylene-piperidine dione in which at least one aromatic ring having 6 to 20 carbon atoms is bonded, - pyrrolidine dione;
R &lt; ₆ &gt;
Each of R ₇ to R ₁₀ is independently selected from the group consisting of hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group) or an alkoxy group having 1 to 30 carbon atoms;
(2)

(3)

In the above Formulas 2 and 3,
R ₁₁ to R ₂₀ each independently represent hydrogen, halogen, an aliphatic group having 1 to 10 carbon atoms, a ring or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms group) or an alkoxy group having 1 to 30 carbon atoms;
At least one of R ₇ to R ₂₀ is a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms, an aryl thio group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms to be. The method according to claim 1,
R ₁ , R ₂ , R _4, and R ₅ in Formula 1 are each hydrogen or halogen;
Wherein R &lt; ₃ &gt; is a functional group of the following formula 4 or a functional group of the following formula 5:
[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)
R _21, R _22, and R ₂₃ is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C1-C20 alkoxy group; A substituted or unsubstituted hydroxyalkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; A substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; A substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms;
Wherein n, n ₁ and n ₂ is an _{integer, 0≤n≤4, 0≤n 1 ≤3, 0≤n} 2 ≤3. The method according to claim 1,
At least one of R ₇ to R ₁₀ is a cyclic or straight-chain alkyl thio group having 1 to 30 carbon atoms or an aryl thio group having 1 to 30 carbon atoms,
Wherein each of R ₁₁ to R ₂₀ is hydrogen, halogen, or an aliphatic group having 1 to 10 carbon atoms. The method according to claim 1,
Each of R ₇ to R ₁₀ is hydrogen, halogen, or an aliphatic group having 1 to 10 carbon atoms,
_At least one of R ₁₁ to R ₁₄ or at least one of R ₁₅ to R ₂₀ is a cyclic or linear alkylthio group having 1 to 30 carbon atoms or an arylthio group having 1 to 30 carbon atoms thio group. The method according to claim 1,
Wherein at least one of R ₇ to R ₂₀ is a cyclic or straight-chain alkyl thio group having 3 to 6 carbon atoms. The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the group consisting of compounds represented by Chemical Formulas 6 to 47:
[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

A coloring composition comprising the colorant compound of any one of claims 1-6. 8. The method of claim 7,
Wherein the coloring composition further comprises at least one of a dye (Dye) and a pigment (Pigment). 9. The method of claim 8,
Wherein the dye (Dye) and the pigment (Pigment) each contain at least one compound exhibiting any one of hues selected from among yellow, red and green. 10. The method of claim 9,
The yellow indicating compound may be a metal-complex compound, an azo compound, a quinophthalone compound, an isoindoline compound, and a Styryl compound. &Lt; / RTI &gt; and at least one compound selected from the group comprising &lt; RTI ID = 0.0 &gt; 10. The method of claim 9,
The red color-indicating compound may be a metal-complex series Wherein the compound is selected from the group consisting of an azo compound, a xanthene compound, a diketopyrrolopyrrole compound, an anthraquinone compound, and a perylene compound A coloring composition comprising at least one compound. 10. The method of claim 9,
The green indicating compound is a metal-complex series Wherein the coloring composition comprises at least one compound selected from the group consisting of a compound, a triarylmethane-based compound, and an anthraquinone-based compound. 10. The method of claim 9,
Wherein the pigment is selected from the group consisting of yellow pigments comprising PY129, PY138, PY139, PY150, and PY185; A red pigment group including PR 48, PR 48: 1, PR 48: 2, PR 48: 3, PR 48: 4, PR 177, PR 179, PR 207, PR 254, PR 255, PR 264 and PR 269; And green pigment groups including PG 7, PG 36, PG 58, and PG 59; &Lt; / RTI &gt; 8. The method of claim 7,
A binder resin, a polyfunctional monomer, a photoinitiator and a solvent. A color filter comprising the coloring composition of claim 7. A display device comprising the color filter of claim 15.