Magenta pigment composition containing novel organic compounds

Abstract

The present invention relates to a magenta pigment composition comprising a novel organic compound, which has excellent water dispersibility and lightfastness, thereby suppressing color change over a long period of time, and can be applied to inkjet recording ink.

Description

Technology Field

[0001] The present invention relates to a magenta pigment composition comprising a novel organic compound. Background Technology

[0002] Inkjet recording refers to a recording method that obtains characters or images by directly ejecting ink droplets from very fine nozzles onto a recording material and attaching them to the material. It is currently widely used as it offers numerous advantages, such as high-speed recording, ease of colorization, and the ability to use ordinary paper as the recording material, as well as being inexpensive and having non-contact characteristics for the printed material.

[0003] Inkjet inks used in this inkjet recording method (hereinafter referred to simply as ink) include "dye-based inks" and "pigment-based inks." However, pigment-based inks, which are superior in terms of weather resistance, color density, and the occurrence of bleeding, are widely used recently. In particular, coupled with the proliferation of digital cameras, there is a rising demand in the field of photographic printing, where high print density (colorability) is required, due to the high durability of the printed materials.

[0004] Furthermore, in the above-mentioned inkjet recording method, various media are used as the recording medium for inkjet. Specifically, in addition to inkjet-specific paper, commercially available ordinary paper, high-quality paper, coated paper, and art paper are used, and high-quality image quality is required for these printing media.

[0005] Specifically, as mentioned earlier, it is desirable to use pigments rather than dyes as ink colorants to impart durability properties, such as water resistance and lightfastness, to ordinary paper or printing media. Accordingly, development of water-based pigment inks that possess various performance characteristics while reducing costs is being pursued in various fields, taking into account cost considerations as well. Meanwhile, regarding the development of yellow pigments for inkjet recording, research on azo pigment compounds is currently being actively conducted.

[0006] Azo pigments are widely used in printing inks, inkjet inks, and electrophotographic materials because of their excellent color and tinting properties. Among these, the most typically used azo pigments are yellow diarylide pigments and red naphthol azo pigments. Examples of diarylide pigments include CI Pigment Yellow 12, 13, and 17. Examples of naphthol azo pigments include CI Pigment Red 208 and 242.

[0007] However, because these pigments have very poor durability, especially lightfastness, the pigments decompose and fade when the printed material is exposed to light, making them unsuitable for long-term preservation of the printed material.

[0008] In order to improve these defects, azo pigments with improved fastness have been disclosed by increasing the molecular weight or introducing groups with strong intermolecular interactions. However, even in such improved pigments, there are some defects, such as the fact that lightfastness is improved but still insufficient, and the coloring power is low and the color characteristics are inferior.

[0009] Accordingly, there is a need to develop a new pigment that compensates for the aforementioned drawbacks and not only exhibits excellent coloring power but also has excellent lightfastness. Prior art literature

[0010] (Patent Document 0001) KR 10-1935322 B1 The problem to be solved

[0011] The object of the present invention is to provide a magenta pigment composition comprising a novel organic compound.

[0012] Another objective of the present invention is to provide a magenta pigment composition comprising a novel organic compound that has excellent water dispersibility and lightfastness, thereby suppressing color change over a long period of time.

[0013] Another objective of the present invention is to provide an inkjet recording ink comprising the magenta pigment composition. means of solving the problem

[0014] To achieve the above objective, a magenta pigment composition according to one embodiment of the present invention may include a compound represented by the following chemical formula 1 or chemical formula 2:

[0015] [Chemical Formula 1]

[0016]

[0017] [Chemical Formula 2]

[0018]

[0019] Here,

[0020] m is an integer from 0 to 5, and

[0021] n and o are identical or different from each other, and each is independently an integer from 0 to 4, and

[0022] X1 is C(R5) or R6N + is,

[0023] X2 is O, S, N(R 15 ) and C(R 16 )(R 17 Selected from a group consisting of ),

[0024] X3 is C or N + is,

[0025] L1 is selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkenylene group having 3 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms.

[0026] Ar1 is selected from the group consisting of a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms.

[0027] R1 to R 17The groups are identical or different from one another and are each independently hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C60 heteroaryl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to Selected from the group consisting of 30 alkylamino groups, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino groups having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, and substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms.

[0028] The above L1, Ar1, and R1 to R 17In the case of this substitution, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, aralkylamino group having 6 to 30 carbon atoms, heteroalkylamino group having 2 to 24 carbon atoms It is substituted with a substituent selected from the group consisting of an arylamino group, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with multiple substituents, these are identical or different from each other.

[0029] An inkjet recording ink according to another embodiment of the present invention comprises the above composition.

[0030] In the present invention, “hydrogen” is hydrogen, light hydrogen, deuterium, or tritium.

[0031] In this specification, “halogen group” is fluorine, chlorine, bromine, or iodine.

[0032] In the present invention, “alkyl” refers to a monovalent substituent derived from a straight-chain or side-chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0033] In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0034] In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or side-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0035] In the present invention, "alkylthio" refers to the alkyl group described above bonded through a sulfur linkage (-S-).

[0036] In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, consisting of a single ring or a combination of two or more rings. Additionally, forms in which two or more rings are simply pendent or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, etc.

[0037] In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Additionally, forms in which two or more rings are simply pendent or condensed with each other may be included, and furthermore, forms condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0038] In the present invention, “aryloxy” refers to a monovalent substituent represented by RO-, where R means an aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0039] In the present invention, “alkyloxy” refers to a monovalent substituent represented by R’O-, where R’ means an alkyl group having 1 to 40 carbon atoms, and may include a linear, branched, or cyclic structure. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, etc.

[0040] In the present invention, the “alkoxy” may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms in the alkoxy is not particularly limited, but it is preferred to have 1 to 20 carbon atoms. Specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but is not limited thereto.

[0041] In the present invention, "aralkyl" refers to an aryl-alkyl group such as aryl and alkyl as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl, and naphthalenylmethyl. Bonding to the parent residue is made through alkyl groups.

[0042] In the present invention, “arylamino group” means an amine substituted with an aryl group having 6 to 30 carbon atoms.

[0043] In the present invention, “alkylamino group” means an amine substituted with an alkyl group having 1 to 30 carbon atoms.

[0044] In the present invention, “aralkylamino group” means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

[0045] In the present invention, “heteroarylamino group” means an amine group substituted with an aryl group having 6 to 30 carbon atoms and a heterocyclic group.

[0046] In the present invention, “heteroaralkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

[0047] In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0048] In the present invention, “heterocycloalkyl” refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, wherein one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Examples of such heterocycloalkyls include, but are not limited to, morpholine and piperazine.

[0049] In the present invention, “alkylsilyl” means a silyl substituted with an alkyl group having 1 to 40 carbon atoms, and “arylsilyl” means a silyl substituted with an aryl group having 6 to 60 carbon atoms.

[0050] In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

[0051] In the present invention, “forming a ring by combining with adjacent groups” means combining with adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heteroring; a substituted or unsubstituted aromatic heteroring; or a condensed ring thereof.

[0052] In this specification, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution location is not limited to the location where the hydrogen atom is substituted, that is, any location where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other. The above substituent may be substituted with one or more substituents selected from the group consisting of hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, and a heteroarylamino group having 2 to 24 carbon atoms, and a plurality of substituents When substituted, they may be identical or different from one another and are not limited to the examples above. Effects of the invention

[0053] According to the magenta pigment composition containing the novel organic compound of the present invention, not only can it exhibit an excellent coloring effect to magenta, but it also has excellent water dispersibility and lightfastness, thereby having the effect of suppressing color change for a long period of time. Brief explanation of the drawing

[0054] FIG. 1 is according to an embodiment of the present invention of the compound represented by chemical formula 5 1 This is the result of the H-NMR Spectra analysis. FIG. 2 is a compound represented by Chemical Formula 5 according to one embodiment of the present invention. 13 This is the result of the C-NMR Spectra analysis. Figure 3 is the HRMS Spectra analysis result of a compound represented by Chemical Formula 5 according to one embodiment of the present invention. FIG. 4 is a compound represented by Chemical Formula 6 according to one embodiment of the present invention. 1 This is the result of the H-NMR Spectra analysis. FIG. 5 is a compound represented by Chemical Formula 6 according to one embodiment of the present invention. 13 This is the result of the C-NMR Spectra analysis. Figure 6 is the HRMS Spectra analysis result of a compound represented by Chemical Formula 6 according to one embodiment of the present invention. Figure 7 is the result of visually observing the state of a compound in the solid state according to one embodiment of the present invention and the color that appears when it is dissolved in a solvent. Figure 8 shows the results of visual observation and UV-Vis absorption spectrum measurement after dissolving a compound according to one embodiment of the present invention in a solvent. Figure 9 shows the results of visual observation and UV-Vis absorption spectrum measurement after dissolving a compound according to one embodiment of the present invention in a solvent. Specific details for implementing the invention

[0055] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0056] A magenta pigment composition according to one embodiment of the present invention may include a compound represented by the following chemical formula 1 or chemical formula 2:

[0057] [Chemical Formula 1]

[0058]

[0059] [Chemical Formula 2]

[0060]

[0061] Here,

[0062] m is an integer from 0 to 5, and

[0063] n and o are identical or different from each other, and each is independently an integer from 0 to 4, and

[0064] X1 is C(R5) or R6N + is,

[0065] X2 is O, S, N(R 15 ) and C(R 16 )(R 17 Selected from a group consisting of ),

[0066] X3 is C or N + is,

[0067] L1 is selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkenylene group having 3 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms.

[0068] Ar1 is selected from the group consisting of a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms.

[0069] R1 to R 17 The groups are identical or different from one another and are each independently hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, substituted or unsubstituted C1 to C4 alkylthio group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C24 alkynyl group, substituted or unsubstituted C7 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C60 heteroaryl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to Selected from the group consisting of 30 alkylamino groups, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino groups having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, and substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms.

[0070] The above L1, Ar1, and R1 to R 17In the case of this substitution, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, aralkylamino group having 6 to 30 carbon atoms, heteroalkylamino group having 2 to 24 carbon atoms It is substituted with a substituent selected from the group consisting of an arylamino group, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with multiple substituents, these are identical or different from each other.

[0071] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 3:

[0072] [Chemical Formula 3]

[0074]

[0075] Here,

[0076] m, L1, R1 to R3 and R6 is as defined in Chemical Formula 1 above.

[0077] The compound represented by the above chemical formula 2 may be a compound represented by the following chemical formula 4:

[0078] [Chemical Formula 4]

[0079]

[0080] Here,

[0081] Ar1 and R8 to R 14 is as defined in the above Chemical Formula 2, and

[0082] R 18 and R 19 The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms.

[0083] The above R 18 and R 19 When substituted, it is substituted with a substituent selected from the group consisting of hydrogen, cyano group, nitro group, halogen group, hydroxyl group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and alkynyl group having 2 to 24 carbon atoms, and when substituted with multiple substituents, they are the same or different from each other.

[0084] Meanwhile, the above L1 may be a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms.

[0085] The above Ar1 may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0086] Preferably, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 5:

[0087] [Chemical Formula 5]

[0088]

[0089] In addition, preferably, the compound represented by the above chemical formula 2 may be a compound represented by the following chemical formula 6:

[0090] [Chemical Formula 6]

[0091]

[0092] More preferably, the composition of the present invention may exhibit a sharp single absorption peak in the wavelength range of 550 to 600 nm, which exhibits a distinct magenta color.

[0093] That is, the absorption wavelength range of 550 to 600 nm is a wavelength range capable of producing a distinct magenta color intended in the present invention, and a distinct magenta color can be confirmed when a single absorption peak is shown in the above wavelength range. However, there is a disadvantage that the color change is dull or murky compared to the compound of the present invention when the maximum absorption wavelength is recorded outside the above wavelength range, or when an additional absorption peak appears outside the above wavelength range even if the absorption peak is recorded within the above wavelength range.

[0094] Meanwhile, "magenta" refers to purple or fuchsia, and colors referred to as bright pink (hot pink) or flower pink are close to the aforementioned magenta color.

[0095] The "distinct magenta color" intended in the present invention refers to a magenta color close to purple or a magenta color close to fluorescent pink.

[0096] More specifically, the pigment composition can exhibit excellent light resistance to ultraviolet rays.

[0097] Pigments are molecules that are tightly bound to each other by cohesive energy resulting from strong interactions between pigment molecules. In order to create this state, intermolecular van der Waals forces and intermolecular hydrogen bonding are required.

[0098] To strengthen intermolecular van der Waals forces, it is required to introduce aromatic groups, polar groups, and / or heteroatoms into the molecule. Additionally, to form intermolecular hydrogen bonds, it is necessary to introduce substituents containing hydrogen atoms bonded to heteroatoms into the molecule and / or electron-donating substituents. It is more desirable for the overall polarity of the molecule to be high; for this purpose, for example, it is desirable for chain-like groups such as alkyl groups to be short, and it is considered desirable for the molecular weight to a small value of azo groups.

[0099] From their perspective, it is desirable that pigment molecules contain amide bonds, sulfonamide bonds, ether bonds, sulfonyl groups, oxycarbonyl groups, imide groups, carbamoylamino groups, heterocyclic rings, benzene rings, etc.

[0100] Accordingly, the pigment composition of the present invention is characterized by including a compound represented by the above-mentioned formula 1 or formula 2, and the compound represented by the above-mentioned formula 1 or formula 2 has the characteristic that it is easy to form intermolecular interactions of pigment molecules due to its specific structure, so it can be used as a pigment.

[0101] Unlike dyes, which are used by dissolving them in a molecularly dispersed state in water or organic solvents, pigments are used by finely dispersing them as solid particles, such as molecular aggregates, in a solvent.

[0102] Specifically, the compound represented by Chemical Formula 1 or Chemical Formula 2 has a specific structure, so it can not only exhibit excellent characteristics in terms of color properties such as coloring power and color, but also exhibit excellent durability properties such as light resistance and ozone resistance, and in particular, the pigment composition has the advantage of exhibiting excellent light resistance to ultraviolet rays.

[0103] Meanwhile, the pigment composition of the present invention may specifically be a pigment dispersion, and the pigment dispersion is characterized by comprising a compound represented by Chemical Formula 1 or Chemical Formula 2. By doing so, it can be used as a pigment dispersion with excellent color properties, durability, and dispersion stability.

[0104] The pigment composition or pigment dispersion of the present invention may be water-based or non-water-based, but it is preferable that it be a water-based pigment dispersion. In the water-based pigment dispersion or pigment composition of the present invention, the aqueous liquid for dispersing the pigment may have water as the main component, and furthermore, a mixture to which a hydrophilic organic solvent is added may be used.

[0105] Examples of the above hydrophilic organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, and ethylene glycol diacetate. Glycol derivatives such as ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, and ethylene glycol monophenyl ether; ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine; amines such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone, etc. may be used.

[0106] In addition, the water-based pigment dispersion of the present invention may include an aqueous resin. As aqueous resins, water-soluble resins that dissolve in water, water-dispersible resins that disperse in water, colloidal dispersion resins, or mixtures thereof are listed. Specifically, as aqueous resins, acrylic, styrene-acrylic, polyester, polyamide, polyurethane, fluorine resins, etc. may be used.

[0107] In the present invention, when the water-based pigment dispersion contains an aqueous resin, there is no particular limitation on the content ratio. For example, it can be 0 to 100 mass% with respect to the pigment.

[0108] In addition, surfactants and dispersants may be used to improve the dispersion of pigments and the quality of the image. As surfactants, anionic, nonionic, cationic, and amphoteric surfactants are listed, and any of the surfactants may be used, but it is preferable to use anionic or nonionic surfactants.

[0109] In the present invention, when the water-based pigment dispersion or composition contains a surfactant, the content is not particularly limited. For example, it can be 0 to 100 mass% with respect to the pigment.

[0110] Meanwhile, as anionic surfactants, examples include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate ester salts, glycerol borate fatty acid esters, polyoxyethylene glycerol fatty acid esters, etc.

[0111] Examples of nonionic surfactants that may be used include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based surfactants, silicone-based surfactants, etc.

[0112] The non-aqueous pigment dispersion or composition of the present invention is formed by dispersing a compound represented by Formula 1 or Formula 2 in a non-aqueous vehicle. Resins used in non-aqueous vehicles may include, for example, petroleum resin, casein, shellac, rosin-modified maleic acid resin, rosin-modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cycloretin, chlorinated rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluoropolymer, drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin, chlorinated polypropylene, butyral resin, vinylidene chloride resin, etc. Meanwhile, photocurable resins may be used as non-aqueous vehicles.

[0113] In addition, solvents used in non-aqueous vehicles include, for example, aromatic solvents such as toluene, xylene, and methoxybenzene; acetic acid ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol and ethanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, and pyridine; and lactone solvents such as γ-butyrolactone. Carbamic acid esters, such as a 48:52 mixture of methyl carbamate and ethyl carbamate, may be used.

[0114] An inkjet recording ink according to one embodiment of the present invention may include the magenta pigment composition.

[0115] Specifically, the inkjet recording ink of the present invention may include the pigment dispersion or composition described above, and is preferably prepared by mixing a water-soluble solvent, water, etc. However, if there is no particular problem, the pigment dispersion or composition of the present invention may be used as is.

[0116] Considering the color, color density, color, transparency, etc. of an image formed on a recording medium, the content ratio of the pigment dispersion or composition in the ink of the present invention is preferably 0.1 parts by weight or more and 20 parts by weight or less of the pigment of the present invention in 100 parts by weight of the ink of the present invention, more preferably 0.2 parts by weight or more and 10 parts by weight or less, and even more preferably 1 to 10 parts by weight.

[0117] In addition, other pigments may be used in combination with the pigment of the present invention in the ink of the present invention, and when two or more types of pigments are used in combination, it is preferable that the total content of the pigments be within the above range.

[0118] As water-soluble solvents used in the inkjet recording ink of the present invention, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents, etc., may be used.

[0119] Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerin, etc.

[0120] Meanwhile, as the above polyalcohol derivatives, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene oxide adduct of diglycerin, etc. may be used.

[0121] In addition, as the nitrogen-containing solvent, pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, triethanolamine, etc. may be used; as the alcohol, alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol may be used; and as the sulfur-containing solvent, thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide, etc. may be used. Meanwhile, additionally, propylene carbonate, ethylene carbonate, etc. may be used.

[0122] The water-soluble solvent used in the present invention may be used alone or in a mixture of two or more types. The content of the water-soluble solvent is used in an amount of 1 mass% or more and 60 mass% or less of the total ink, preferably 5 mass% or more and 40 mass% or less.

[0123] When the amount of water-soluble solvent in the ink is less than 1 mass%, there are cases where sufficient optical concentration is not obtained, and conversely, when it is more than 60 mass%, the viscosity of the liquid increases and the spraying characteristics of the ink liquid become unstable.

[0124] Meanwhile, the preferred physical properties of the inkjet recording ink of the present invention are as follows.

[0125] It is preferable that the surface tension of the ink be 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, and even more preferably, 25 mN / m or more and 35 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow onto the nozzle surface of the recording head, making it impossible to print normally. On the other hand, if it exceeds 60 mN / m, the penetration into the recording medium after printing is slow, and the drying time may be delayed.

[0126] In addition, the surface tension was measured using the same Wilhelmy Surface Tension Balance as above under conditions of 23°C and 55% RH.

[0127] It is preferable that the viscosity of the ink be 1.2 mPa·s or higher and 8.0 mPa·s or lower, more preferably 1.5 mPa·s or higher and less than 6.0 mPa·s, and even more preferably 1.8 mPa·s or higher and less than 4.5 mPa·s. If the viscosity is greater than 8.0 mPa·s, the discharge performance may decrease. On the other hand, if it is less than 1.2 mPa·s, the long-term spray performance may deteriorate.

[0128] In addition, the above viscosity was measured using a rheomat 115 rotary clay meter (manufactured by Contraves Co.) at 23℃ with a shear rate of 1400s -1 ...did so as to.

[0129] Meanwhile, in addition to each of the above components, water may be added to the ink within the range of the above-mentioned desirable surface tension and viscosity. The amount of water added is not particularly limited, but preferably it may be 10 mass% or more and 99 mass% or less with respect to the total ink, and more preferably 30 mass% or more and 80 mass% or less.

[0130] Additionally, if necessary, for the purpose of controlling characteristics such as improving dischargeability, polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, cellulose derivatives such as ethylcellulose and carboxymethylcellulose, polysaccharides and their derivatives, other water-soluble polymers, acrylic polymer emulsions, polyurethane emulsions, polymer emulsions such as hydrophilic latex, hydrophilic polymer gels, cyclodextrin, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, silicone surfactants, fluorine surfactants, etc. may be used.

[0131] In addition, to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, nitrogen-containing compounds such as ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, and 2-amino-2-methyl-1-propanol, compounds of alkaline earth metals such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid, and nitric acid, and salts of strong acids and weak alkalis such as ammonium sulfate may be used.

[0132] Meanwhile, components that a person skilled in the art can include as components of the ink, such as pH buffers, antioxidants, antifungal agents, viscosity modifiers, conductive agents, and ultraviolet absorbers, are defined as components that may be additionally included.

[0134] Preparation Example

[0135] Preparation and Analysis Methods of Experimental Materials

[0136] The intermediate materials, solvents, etc. used for the preparation of the novel organic compound of the present invention were purchased from Sigma Aldrich and Tokyo Chemical Industries and used without purification.

[0137] H-NMR and C-NMR of the compound according to one embodiment of the present invention were analyzed using a Bruker 600 instrument, and HRMS was recorded on a 1290 Infinity II / Triple TOF 5600 plus mass spectrometer. Chemical shifts were analyzed in ppm. Meanwhile, multiplicity was indicated as s (single), d (double), t (triple), m (multiple), and dd (double of a double).

[0138] Meanwhile, the ultraviolet-visible (UV-Visible) spectroscopic spectrum was analyzed using an Agilent 8453 device.

[0139] Preparation of the compound of the present invention (CNU-magenta 1)

[0140] [scheme 1]

[0141]

[0142] Under nitrogen atmosphere conditions, 2 to 3 drops of piperidine were added to a solution of 4-(dimethylamino)benzaldehyde (2.5 g, 16.7 mmol) and 5-carboxy-1,2,3,3-tetramethyl-3H-indol-1-ium iodide (5.8 g, 16.7 mmol) mixed in 25 ml of ethanol. Then, the reaction mixture was stirred overnight at 80°C.

[0143] Subsequently, when the above reaction mixture was cooled, a precipitate was formed, which was washed with cold ethanol and completely dried to obtain 5.1 g of the compound represented by the following chemical formula 5 (CNU-magenta 1), with a yield of 63.9%:

[0144] [Chemical Formula 5]

[0145]

[0146] Specifically, according to FIGS. 1 to 3, the analysis results of the following numerical values ​​were confirmed, and when combined, the structure of the compound represented by the chemical formula 5 above can be confirmed.

[0147] 1 H-NMR (600 MHz, DMSO-d6): 13.19 (1H, s); 8.38 (1H, d, J= 15.6 Hz); 8.29 (1H, d, J= 1.8 Hz); 8.09 (3H, m); 7.75 (1H, d, J= 8.4 Hz); 7.24 (1H, d, J= 15.6 Hz); 6.90 (2H, d, J= 9.0 Hz); 3.97 (3H, s); 3.20 (6H, s); 1.79 (6H, s).

[0148] 13 C-NMR (150 MHz DMSO-d6): δ 181.05; 167.20; 155.80; 155.45; 146.05, 143.03; 135.25; 130.85; 129.70; 123.97; 123.02; 113.70; 112.93; 105.30; 51.08; 33.67; 26.73.

[0149] HRMS (m / z) calcd. for C 22 H 25 N2O2[M] + :349.1911, found 349.1918.

[0150] Preparation of the compound of the present invention (CNU-magenta 2)

[0151] [scheme 2]

[0153]

[0154] 2-(4-(diethylamino)-2-hydroxy benzoyl)benzoic acid (1 g, 3.2 mmol) was dissolved in 5 mL of methane sulfonic acid as a solvent, and 1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-8-ol (0.6 g, 3.2 mmol) was added and mixed. Afterward, the mixture was stirred at 100°C for 3 hours, and then a pre-cooled 20% sodium hydroxide solution was added to the reaction mixture at room temperature. Subsequently, water and ethyl acetate were added to separate the organic layer. The crude material obtained after drying the separated organic layer and removing the solvent under vacuum was purified by silica gel column chromatography (methanol / dichloromethane as solvent) to obtain 0.6 g of a compound represented by the following chemical formula 6 (CNU-magenta 2) as a pure purple crystalline solid, and the yield was 40.2%.

[0155] [Chemical Formula 6]

[0156]

[0157] Specifically, according to FIGS. 4 to 6, the analysis results of the following numerical values ​​were confirmed, and when combined, the structure of the compound represented by the chemical formula 6 can be confirmed.

[0158] 1 H-NMR: δ (ppm); (CDCl3; 600 MHz): 8.01 (d, J = 7.8 Hz, 1H); 7.47 (m, 2H); 7.08 (d, J = 7.8 Hz, 1H); 6.62 (d, J = 9.0 Hz, 1H); 6.43 (s, 1H); 6.34 (d, J = 9.0, 1H); 6.24 (s, 1H); 3.31 (q, 4H); 3.15 (m, 4H); 2.90 (m, 2H); 2.42 (m, 2H); 1.94 (m, 2H); 1.79 (m, 2H); 1.11 (t, J = 7.2 Hz, 6H).

[0159] 13 C-NMR: δ (ppm); (DMSO-d6; 600 MHz): 169.1; 153.8; 150.4; 148.8; 145.9; 135.0; 130.2; 129.3; 128.5; 126.0; 125.6; 125.0; 118.8; 109.6; 107.0; 106.6; 97.3; 55.4; 49.8; 49.4; 44.4; 27.2; 21.5; 20.9; 20.8; 12.9.

[0160] HRMS [m / z], calculated for C30H 31 N2O3 + (M + ): 467.2329, found:467.2330.

[0162] Experimental Example

[0163] Visual observation experiment

[0164] To confirm the ability of the novel organic compound of the present invention to be used as a magenta color pigment, a visual observation experiment was conducted, and the results are as shown in Fig. 7.

[0165] Specifically, each of the compounds represented by Chemical Formula 5 and Chemical Formula 6 is mixed in an ethanol solvent to obtain 1.5 x 10 -5 After preparing solutions of concentration M, the color change was observed. As a result, a clear color change to magenta was confirmed in both of the aforementioned compounds.

[0166] More specifically, the compound represented by chemical formula 5 exhibited a magenta color close to purple, and the compound represented by chemical formula 6 exhibited a magenta color close to fluorescent pink.

[0167] Through this, it was confirmed that the novel organic compound of the present invention can be utilized as a magenta pigment composition.

[0168] UV-Visible Spectra Analysis Experiment

[0169] To confirm the results of the above visual observation experiment as concrete data, a UV-Visible spectrum analysis experiment was conducted.

[0170] Referring to FIGS. 8 and 9, it can be seen that the novel organic compound of the present invention contained in an ethanol solution exhibits a sharp single absorption peak in the range of 550 to 600 nm.

[0171] More specifically, it was confirmed that the absorption peak of the compound represented by chemical formula 5 exhibits a maximum peak at 563 nm, and the absorption peak of the compound represented by chemical formula 6 exhibits a maximum peak at 555 nm.

[0172] Meanwhile, referring to FIGS. 8 and 9, it was visually confirmed that although color changes could be observed in the case of PR122 and C1 to C4 compounds, which are commercially available magenta pigments, they exhibited dull or turbid color changes compared to the compounds of the present invention.

[0173] Meanwhile, it can be confirmed that the absorption peaks of the PR122 compound exhibit two maximum peaks at 541 and 570 nm, while the C1 compound exhibits one maximum peak at 528 nm, and the C2 compound exhibits two maximum peaks at 525 and 555 nm. Additionally, the C3 compound exhibits one maximum peak at 535 nm, and the C4 compound exhibits one maximum peak at 549 nm.

[0174] That is, in experiments confirming absorption peaks, the PR122 and C1 to C4 compounds exhibit maximum absorption peak values ​​outside the 550 to 600 nm wavelength range, which is the wavelength range exhibiting a distinct magenta color, or even if they exhibit peak values ​​within the 550 to 600 nm range, additional absorption peaks appear outside the range, thereby confirming that the color change effect to a distinct magenta color is relatively inferior compared to the compounds of the present invention.

[0175] Lightfastness test

[0176] For the light resistance test of the compound of the present invention, a comparative test was conducted on the light resistance of the PR122 compound, C3 compound, and C4 compound of FIG. 8 and FIG. 9, which were used in the UV-Visible spectra analysis test, and the compound of the present invention.

[0177] Specifically, 1.5 x 10⁻⁶ of the PR122 compound, C3 compound, and C4 compound of FIGS. 8 and 9 dissolved with the compound represented by Formulas 5 and 6 of the present invention. -5 An ethanol solution with a concentration of M was prepared. The sample was forcibly exposed to UV light at 30-minute intervals, and the absorbance and fluorescence intensity were measured. Since glass is well known to absorb energy in the UV region, whereas quartz completely transmits the entire UV light, a quartz cuvette was used instead of a glass vial.

[0178] Specifically, the time until the compound dissolved in ethanol was completely decomposed and turned colorless without showing any magenta color was measured, and the results are shown in Table 1 below.

[0179] Hours (minutes) PR122 89 C3 compounds 92 C4 compound 91 Compound represented by Chemical Formula 5 210 Compound represented by chemical formula 6 205

[0180] (Unit: min) Referring to Table 1 above, it can be seen that PR122, C3, and C4 compounds were completely decomposed in 89 minutes, 92 minutes, and 91 minutes, respectively, whereas the compounds represented by Chemical Formulas 5 and 6 of the present invention took 210 minutes and 205 minutes, respectively, to be completely decomposed.

[0181] In other words, it has been confirmed that the compound of the present invention possesses excellent lightfastness against ultraviolet rays. Consequently, when the compound of the present invention is applied to inkjet recording inks, etc., not only can visibility be improved, but the enhanced lightfastness also has the effect of maintaining high readability of printed type for a long time.

[0183] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

Claims

Claim 1 A magenta pigment composition comprising a compound represented by the following Chemical Formula 5 or Chemical Formula 6, exhibiting excellent lightfastness against ultraviolet rays: [Chemical Formula 5] [Chemical Formula 6] Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 Inkjet recording ink comprising a composition according to claim 1.

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