TW201925358A - Colorant composition, colorant dispersed solution, photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Abstract

This invention is related to a colorant composition comprising a first xanthene dye having the same number of positive and negative charges; and a complex comprising a second xanthene dye having a number of negative charges larger than that of a positive number by 1 or more and a dispersant whose an amine value of 0 to 200 mgKOH/g comprising an ammonium structure ion-bonded to the second xanthene dye, and this invention is also related to a colorant dispersion, a photosensitive resin composition, a color filter and a liquid crystal display device.

Description

Colorant composition, colorant dispersion liquid, photosensitive resin composition, color filter, and liquid crystal display

This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0160315 filed with the Korean Patent Office on November 28, 2017, and incorporates all its contents into this specification. The present invention relates to a colorant composition, a colorant dispersion liquid, a photosensitive resin composition, a color filter, and a liquid crystal display device.

Recently, as a light source of a liquid crystal display (LCD), a light emitting diode (LED) or an organic light emitting diode (Organic Light Emitting Diode) that emits light by itself, which is neither a driver nor a liquid crystal, is often used. (OLED) element to replace the existing Cold Cathode Fluorescent Lamp (CCFL). If LED or OLED is used as the light source, it does not need other color filters because it emits red, green and blue light.

However, in general, it is difficult to match or adjust the required color coordinates using light emitted from LED or OLED light sources.

On the other hand, in order to realize a color filter, a pigment dispersion method using a pigment as a colorant is generally used. However, in the case of a pigment dispersion liquid, not only the pigment exists in a particle state and scatters light, but also the pigment surface area is rapidly increased by the miniaturization of the pigment, and uneven pigments are generated due to the deterioration of dispersion stability caused by the pigment. particle. Therefore, in order to achieve the high brightness, high light-darkness ratio, and high resolution that have recently been required, research is being conducted to use dyes as colorants instead of pigments.

However, in general, the solubility of the dye is low, and therefore the dispersion cannot be performed properly, and the brightness of the color filter cannot be sufficiently satisfied.

[Problems to be Solved by the Invention] The present invention is intended to provide a toner composition capable of providing a toner dispersion liquid having excellent dispersion, a toner dispersion liquid produced using the same, and a photosensitive resin composition. The present invention also intends to provide a color filter manufactured using the above-mentioned photosensitive resin composition and a liquid crystal display device including the same.

[Means for Solving the Problem] An embodiment of the present invention provides a toner composition including: first xanthracene dyes having the same number of positive and negative charges; and the number of negative charges is greater than the number of positive charges A complex in which one or more second xanthracene dyes are ion-bonded with a dispersant having an amine value of 0 mgKOH / g to 200 mgKOH / g and containing an ammonium structure.

Another embodiment of the present invention provides a colorant dispersion liquid including the colorant composition, a dispersant, a binder resin, and a solvent.

Another embodiment of the present invention provides a photosensitive resin composition including the colorant dispersion liquid, a binder resin, a polyfunctional monomer, and a photopolymerization initiator.

Another embodiment of the present invention provides a color filter, which is a color filter including a transparent substrate and a coloring layer included on the transparent substrate, and the coloring layer includes the photosensitive resin composition. Hardened.

Another embodiment of the present invention provides a liquid crystal display device including the color filter.

[Effects of the Invention] According to the embodiment of the present invention, it is possible to prevent disaggregation of the dye and improve dispersibility, thereby obtaining a colorant dispersion liquid having high brightness and stability. In addition, when the toner composition and the toner dispersion liquid according to some embodiments of the present invention are used, they are excellent in storage stability, transmittance, and heat resistance, and are excellent in use in the use of a color filter.

An embodiment of the present invention provides a toner composition including: a first xanthracene dye having the same number of positive and negative charges; and a number of negative charges that is one or more than the number of positive charges. A complex made of a 2 xanthracene dye and an amine value of 0 mgKOH / g to 200 mgKOH / g and a dispersant containing an ammonium structure.

Previously, when two or more kinds of dyes were mixed, the purpose was to adjust the color to be achieved, but the embodiment is related to a combination of a dye and a dispersant that maximizes dispersion stability. Specifically, according to the embodiment, the first xanthracene dye and the second xanthracene dye are both xanthene dyes and have similar structures. The first xanthracene-based dye has the same number of positive and negative charges, while the second xanthracene-based dye has more than one positive charge than the number of positive charges.

However, when only the first xanthracene-based dye is present, dispersion stability may be reduced by re-aggregation between particles due to π-π interaction of the xanthene-based dye. However, according to the embodiment, a part or all of the second xanthracene-based dye may be adjacent to each other by including the first xanthene-based dye and the second xanthracene-based dye having the general characteristics described above. It is located between two or three adjacent first xanthracene dyes, or the end of the first xanthracene dye.

As a result, the first xanthracene-based dye mainly functions as a xanthracene-based dye to develop color. In contrast, the second xanthracene-based dye not only develops color, but also makes the first xanthracene-based dye exhibit color. The aspect of dispersion plays a role, thereby improving dispersion stability.

In particular, the dispersant is cationic because it contains an ammonium structure, whereby the negative charge of the second xanthracene dye can be ion-bonded with the dispersant to form a composite. The presence of such a second xanthracene dye greatly improves dispersion stability. This can prevent reaggregation of the first xanthracene-based dye, and can provide a colorant dispersion liquid having small dispersed particles, good brightness, and excellent dispersion stability.

According to another embodiment of the present invention, the first xanthracene dye has a maximum absorption wavelength between 500 nm and 580 nm, and the maximum absorption wavelength of the first xanthracene dye is the same as that of the second xanthracene dye. The difference between the maximum absorption wavelengths of xanthene dyes is 100 nm or less.

According to another embodiment of the present invention, the first xanthracene dye has a maximum absorption wavelength between 500 nm and 580 nm, and the maximum absorption wavelength of the first xanthracene dye is the same as that of the second xanthracene dye. The difference between the maximum absorption wavelengths of xanthene dyes exceeds 0 nm and is 100 nm or less. It is preferably more than 0 nm and 50 nm or less, and most preferably more than 0 nm and 20 nm or less. According to the embodiment, when only the first xanthracene-based dye is present, the dispersion stability is not good, but by using a second xanthene-based dye with a similar chemical structure and absorption characteristics, the original can be realized. The color desired by the first xanthracene-based dye, and the dispersion stability can be greatly improved.

In the present specification, the first xanthene dye is described as the first dye, and the second xanthene dye is described as the second dye.

In this specification, the amine value of the dispersant containing an ammonium structure is 0 mgKOH / g to 200 mgKOH / g. Preferably, the amine value may be 0 mgKOH / g to 100 mgKOH / g, and may further be more than 0 mgKOH / g and 100 mgKOH / g. According to an example, the amine value of the dispersant containing an ammonium structure may be more than 0 mgKOH / g and 160 mgKOH / g.

According to another embodiment of the present invention, the first xanthracene-based dye includes a dye represented by the following Chemical Formula 1 and has the same number of positive and negative charges, and the second xanthracene-based dye includes the following The dye represented by the chemical formula 2 and the number of negative charges is one or more more than the number of positive charges.

[Chemical Formula 1] In the chemical formula 1, R ₁ to R ₄ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, anionic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted alkane In the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a dianhydride group containing a nitrogen atom; R ₅ to R ₉ are the same or different from each other, and are each Independently selected from the group consisting of hydrogen, deuterium, anionic, hydroxyl, sulfonamido, sulfonate, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted In the group consisting of substituted heteroaryl groups, at least one of R ₅ to R ₉ is an anionic group, a sulfonate group, or a sulfonamido group; R ₁₀ and R ₁₁ are the same as each other or Are different, and are each independently hydrogen, deuterium, halogen, nitro, or substituted or unsubstituted alkyl, r ₁₀ and r ₁₁ are integers of 0 to 3, and r ₁₀ and r ₁₁ are In the case of 2 or more, the structures in parentheses are the same or different.

[Chemical Formula 2] In the chemical formula 2, R ₂₁ to R ₂₄ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, anionic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted alkane In the group consisting of a group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a dianhydride group containing a nitrogen atom, at least one of R ₂₁ to R ₂₄ is Anionic, sulfonate, or sulfonamido substituted or unsubstituted anionic, sulfonate, or sulfonamido, alkyl, anionic, sulfonate, or sulfonium Amine-substituted aryl groups, or heteroaryl groups substituted with anionic groups, sulfonate groups, or sulfonamido groups; R ₂₅ to R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, and anions Basic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group, and substituted the group consisting of heteroaryl or unsubstituted aryl group in which the R ₂₅ ~ R ₂₉ in at least one anionic group Sulfonate group, acyl or a sulfo group; R ₃₀ and R ₃₁ are the same or different, and each independently hydrogen, deuterium, a halogen group, a nitro group, or a substituted or unsubstituted alkyl group from each other, r ₃₀ and r ₃₁ is an integer from 0 to 3, and when r ₃₀ and r ₃₁ are each 2 or more, the structures in parentheses are the same or different from each other.

In an embodiment of the present specification, the R ₁ to R ₄ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl. And a dianhydride group containing a nitrogen atom, the R ₂₁ to R ₂₄ are the same as or different from each other, and are independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl, and substituted In the group consisting of an unsubstituted aryl group and a dianhydride group containing a nitrogen atom, the remaining substituents are as defined above.

In the chemical formula 1 of the present specification, R ₁ to R ₄ are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a nitrogen-containing group. Atomic dianhydride group.

In the chemical formula 1 of the present specification, R ₁ to R ₄ are the same or different from each other, and are each independently hydrogen, an aryl group substituted with an anionic group or an alkyl group, or a dianhydride group substituted with a nitrogen atom or An alkyl group substituted without a dianhydride group containing a nitrogen atom.

In the chemical formula 1 of the present specification, R ₁ to R ₄ are the same or different from each other, and are each independently hydrogen, a phenyl group substituted with a methyl group, and selected from the group consisting of a methyl group and an anionic group. Phenyl, ethyl, propyl, or propyl substituted with a dianhydride group containing a nitrogen atom.

In the chemical formula 1 of the present specification, R ₅ to R ₉ are the same or different from each other, and are each independently a hydrogen or an anionic group.

In the present specification, the chemical formula 1, R ₅ ~ R ₉ are the same or different and each is independently hydrogen or SO ₃ ^-.

In the chemical formula 1 of the present specification, R ₁₀ and R ₁₁ are the same or different from each other, and are each independently hydrogen or deuterium, r ₁₀ and r ₁₁ are integers of 0 to 3, and in the r ₁₀ and r ₁₁ When the number is 2 or more, the structures in parentheses are the same or different.

In the chemical formula 2 of the present specification, R ₂₁ to R ₂₄ are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a group containing a nitrogen atom. Dianhydride group.

In the chemical formula 2 of the present specification, R ₂₁ to R ₂₄ are the same as or different from each other, and are each independently an alkyl group substituted with a dianhydride group containing a nitrogen atom or an alkyl group not substituted with a dianhydride group containing a nitrogen atom, or An aryl group substituted with one or more types selected from the group consisting of an anionic group and an alkyl group.

In the chemical formula 2 of the present specification, R ₂₁ to R ₂₄ are the same or different from each other, and are each independently an ethyl group, a propyl group, a propyl group substituted with a dianhydride group containing a nitrogen atom, and a benzene group substituted with a methyl group. Group, or a phenyl group substituted with one or more types selected from the group consisting of a methyl group and an anionic group.

In this specification, the term "substituted or unsubstituted" means that the group is selected from the group consisting of deuterium, halo, alkyl, alkenyl, alkoxy, cycloalkyl, arylalkenyl, aryl, and aryl. Oxy, arylalkyl, arylalkenyl, alkylamino, aralkylamino, arylamine, heteroaryl, hydroxyl, cyano, containing one of N, O, S or P atoms The above heterocyclic group, dianhydride group containing nitrogen atom, sulfonate group, sulfonamido group, and anionic group are substituted with one or more substituents, or do not have any substituents. In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, third butyl, pentyl, hexyl, and heptyl.

In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples are preferably alkenyl groups in which aryl groups such as stylbenyl and styrenyl are substituted, but they are not limited thereto.

In the present specification, the alkoxy group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.

In the present specification, the alkenyloxy group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30.

In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 20 carbon atoms, and particularly preferably cyclopentyl and cyclohexyl.

In this specification, examples of the halogen group are fluorine, chlorine, bromine or iodine.

In this specification, as for the said arylalkyl group, specifically, an aryl part is 6-30 carbon number, and an alkyl part is 1-30 carbon number. Specific examples are: benzyl, p-methylbenzyl, m-methylbenzyl, p-ethylbenzyl, m-ethylbenzyl, 3,5-dimethylbenzyl, α-methylbenzyl, α, α-dimethylbenzyl, α, α-methylphenylbenzyl, 1-naphthylbenzyl, 2-naphthylbenzyl, p-fluorobenzyl, 3,5-difluorobenzyl, α, α -Di-trifluoromethylbenzyl, p-methoxybenzyl, m-methoxybenzyl, α-phenoxybenzyl, α-benzyloxybenzyl, naphthylmethyl, naphthylethyl , Naphthylisopropyl, pyrrolylmethyl, pyrrolylethyl, aminobenzyl, nitrobenzyl, cyanobenzyl, 1-hydroxy-2-phenylisopropyl, 1-chloro-2- Phenyl isopropyl and the like are not limited thereto.

In this specification, the description related to the aryl group mentioned later can be applied to the aryl part of the arylalkenyl group, and the description related to the alkenyl group can be applied to the alkenyl part.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group.

In the case where the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be phenyl, biphenyl, bitriphenyl, or the like, but is not limited to these.

In the case where the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, and preferably 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may have a substituent, and the substituent may be bonded to form a spiro ring structure.

In the present specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a singular atom, and the number of carbons is not particularly limited, but preferably 2 to 30. Examples of heterocyclic groups are: thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, Pyridazinyl, quinolinyl, quinazolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, diphenyl A benzothienyl group, a benzofuranyl group, a dibenzofuranyl group, etc. are not limited to these.

In this specification, the carbon number of the dianhydride group containing a nitrogen atom is not specifically limited, It is preferably 4-20. For example, it may be isoindolin-1,3-dione.

In the present specification, an alkylene group means one having two bonding positions in an alkane. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms of the alkylene group is not particularly limited, and is, for example, 1 to 30 carbon atoms.

In the present specification, the sulfonate group may be represented as —SO ₃ X ′, and X ′ may be hydrogen or a Group 1 element. For example, there is a sulfonate group -SO ₃ Na.

In the present specification, the sulfonamide group may be represented as -SO ₂ NRxRy. For example, Rx and Ry are the same or different from each other, and are each independently a substituted or unsubstituted linear or branched chain of 1 to 30 carbon atoms Alkyl, substituted or unsubstituted monocyclic or polycyclic aryl having 6 to 30 carbons, or substituted or unsubstituted monocyclic or polycyclic heteroaryl having 2 to 30 carbons.

In this specification, the anionic group has a chemical bond with the structure of Chemical Formula 1. The anionic group is not particularly limited. For example, U.S. Patent No. 7,939,644, Japanese Patent Laid-Open No. 2006-003080, and Japanese Patent Laid-Open No. 2006-001917, Japanese Patent Laid-Open No. 2005-159926, Japanese Patent Laid-Open No. 2007-7028897, Japanese Patent Laid-Open No. 2005-071680, Korean Application Publication No. 2007-7000693, Japanese Patent Laid-Open No. 2005 Anion described in -111696, Japanese Patent Laid-Open No. 2008-249663, and Japanese Patent Laid-Open No. 2014-199436. Specific examples of the anionic group include trifluoromethanesulfonate anion, bis (trifluoromethylsulfonyl) sulfonium anion, bistrifluoromethanesulfonimide anion, and bisperfluoroethylsulfonimide anion. , tetraphenyl borate anion, tetrakis (4-fluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tri - trifluoromethanesulfonic methide _{^{acyl, SO 3 -, CO 2 -}} , SO ₂ N ^- SO ₂ CF ₃ , SO ₂ N ^- SO ₂ CF ₂ CF ₃ , a halogen group, such as a fluoro group, an iodo group, and a chloro group, are not limited to these.

In the present specification, the anionic group itself may have an anion, and may also exist in the form of a wrong compound together with other cations. Therefore, depending on the number of substituted anionic groups, the total charge of the compound molecule of the present invention as a whole can be changed. Since the compound of the present invention has a cation in one amine group, the total charge of the entire molecule may have a value ranging from anion to 0 corresponding to a value obtained by subtracting 1 from the number of substituted anionic groups.

In the present specification, a singular body means a repeating unit constituting a polymer, and the singular body may be contained in a main chain in the polymer to constitute the polymer.

In the present specification, the unit refers to an overlapping structure in which a single body is contained in a polymer, and means a structure in which a single body is bonded to a polymer through the polymer.

According to another embodiment of the present invention, the first xanthracene-based dye includes a dye represented by the following Chemical Formula 3 and has the same number of positive and negative charges, and the second xanthracene-based dye includes the following The dye represented by the chemical formula 4 and the number of negative charges is one or more more than the number of positive charges.

[Chemical Formula 3]

[Chemical Formula 4] In Chemical Formula 3 and Chemical Formula 4, R ₁₂ , R ₁₃ , R _32, and R ₃₃ are the same or different from each other, and are each independently hydrogen, deuterium, halo, nitro, substituted or unsubstituted alkyl, and anionic Group, sulfonate group, or sulfonamido group, r ₁₂ and r ₁₃ are integers of 0 to 5, r ₃₂ is an integer of 0 to 5, r ₃₃ is an integer of 0 to 4, and r ₁₂ , r ₁₃ , When r ₃₂ and r ₃₃ are 2 or more, the structures in parentheses are the same or different from each other; R ₆₁ and R ₆₂ are the same or different from each other, and are each independently hydrogen, deuterium, substituted or unsubstituted alkyl Or a dianhydride group containing a nitrogen atom; X is an anionic group, a sulfonate group, or a sulfonamide group; and the remaining substituents are as defined in Chemical Formula 1 and Chemical Formula 2.

According to an example, R ₆₁ and R ₆₂ may be hydrogen.

When the second xanthracene dye containing the dye of the chemical formula 4 is used, the colorant composition may further include a dye of the following chemical formula 4-1.

[Chemical Formula 4-1] In Chemical Formula 4-1, R ₅₀ to R ₅₃ are the same as or different from each other, and are each independently hydrogen, deuterium, halo, nitro, or substituted or unsubstituted alkyl, and r ₅₀ and r ₅₁ are 0 to Integers of 4, r ₅₂ and r ₅₃ are integers of 0 to 3, and when r ₅₀ to r ₅₃ are respectively 2 or more, the structures in the brackets are the same or different from each other; Xa and Xb are the same or different from each other and are independent of each other Is an anionic group, a sulfonate group, or a sulfonamido group; R ₄₅ to R ₄₉ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, anionic group, hydroxyl group, sulfonamido group, and sulfonic acid A group consisting of a salt group, a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group In this group, at least one of R ₄₅ to R ₅₉ is an anionic group, a sulfonate group, or a sulfonamide group.

According to another embodiment of the present invention, the first xanthracene-based dye includes a dye represented by the following Chemical Formula 5 and has the same number of positive and negative charges, and the second xanthracene-based dye includes the following The dye represented by the chemical formula 6 and the number of negative charges is one or more more than the number of positive charges.

[Chemical Formula 5]

[Chemical Formula 6] In Chemical Formula 5 and Chemical Formula 6, R ₁₄ to R ₁₇ and R ₃₄ to R ₃₇ are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group; R ₆₁ and R ₆₂ are the same or different from each other, and Each independently is hydrogen, deuterium, a substituted or unsubstituted alkyl group, or a dianhydride group containing a nitrogen atom; X1 to X3 are the same as or different from each other, and are each independently an anionic group, a sulfonate group, or Sulfonamide.

According to an example, R ₁₄ to R ₁₇ and R ₃₄ to R ₃₇ may be a methyl group.

According to one example, R ₆₁ and R ₆₂ may be hydrogen.

According to an example, when a second xanthracene dye containing the dye of the chemical formula 6 is used, the colorant composition may further include a dye of the following chemical formula 6-1.

[Chemical Formula 6-1] In Chemical Formula 6-1, R ₃₈ to R ₄₁ are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group; X4 to X6 are the same or different from each other, and are each independently an anionic group and a sulfonic acid Base, or sulfonamide.

In one embodiment of the present specification, the first xanthracene dye may have any one of the following structures.

In one embodiment of the present specification, the second xanthracene dye may have any of the following structures.

According to an embodiment of the present invention, the dispersant may include 3 mol% to 50 mol%, preferably 4 mol% to 40 mol% of a single amount containing an ammonium structure, based on 100 mol% of the entire unit unit. Body unit.

According to an embodiment of the present invention, the second xanthene dye may further include a counter cation. The toner composition according to an embodiment of the present invention may further include a number of counter cations in the second xanthracene-based dye corresponding to the number of negative charges more than the number of positive charges. The counter cation may be a hydrogen ion, a sodium ion, or a cationic group, and these may include, for example, 1 to 7 per molecule of the second xanthracene dye.

According to another embodiment of the present invention, the dispersant may further include a counter anion. The counter anion may be an inorganic or organic anion, and specifically a Cl ^- like halogen group. The dispersant may contain only counter anions in a number corresponding to the number of positive charges of the dispersant.

The toner composition according to one embodiment of the present invention can be cleaned as described later. In this case, the counter cation or counter anion is removed, and the cationic structure contained in the dispersant can exert the second xanthracene The counter-cation effect of the series dye.

According to another embodiment of the present invention, the dispersant is represented by the following Chemical Formula 7.

[Chemical Formula 7] In Chemical Formula 7, Ra to Rd are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Substituted or unsubstituted arylalkyl, -L-NHCO-R, or -L-OCO-R, or two of Ra to Rd are bonded to each other to form a substituted or unsubstituted ring; R is Hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl; L is substituted or unsubstituted alkylene.

According to an example, in the chemical formula 7, one or more, and more preferably two or more of Ra to Rd include a long chain having 5 or more carbon atoms. In this case, the dispersion stability using a dispersant can be further increased.

According to another embodiment of the present invention, the dispersant includes a unit of Chemical Formula 8 below.

[Chemical Formula 8] In Chemical Formula 8, Rb to Rd are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or A substituted or unsubstituted arylalkyl group, or two of Rb to Rd are bonded to each other to form a substituted or unsubstituted ring; Z is an alkylene group, an alkylene group, -L-NHCO-, Or -L-OCO-, L is an alkylene group; Re to Rg are the same or different from each other, and are each independently hydrogen or an alkyl group.

According to another embodiment of the present invention, a weight average molecular weight of the dispersant is 1,000 to 10,000. It is preferably 3,000 to 8,000, more preferably 5,000 to 7,000.

According to an example, the terminal of the dispersant is hydrogen, a halogen group, or an alkyl group.

According to another embodiment of the present invention, the dispersant further includes at least one of the following Chemical Formulas 9 to 12 in addition to the units of Chemical Formula 8.

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12] In Chemical Formulas 9 to 12, Rh, Ri, Rj, Rl, Rm, Rn, Rp, Rq, Rr, Rt, Ru, and Rv are the same or different from each other, and are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms. Rk and Rs are the same or different from each other and are each independently an alkyl group having 1 to 20 carbons; Ro is an arylalkyl group having 7 to 20 carbons; Rw and Rx are the same or different from each other and are each independently hydrogen , An alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; L ₁ and L ₂ are the same or different from each other, and are each independently an alkylene group having 1 to 6 carbon atoms, and m is 1 Integer to 6.

As a specific example, the dispersant may include the following units, and must include the rightmost unit among them.

In the structure, a to g are mole ratios based on the entire repeating unit constituting the dispersant, and may be a: 40 mol% to 50 mol%, b: 10 mol% to 20 mol%, and c: 5 mol% -10 mol%, d: 3 mol% -6 mol%, e: 1 mol% -5 mol%, f: 15 mol% -20 mol%, g: 2 mol% -6 mol%, but not Only for this.

According to another embodiment of the present invention, the colorant composition further includes a solvent.

The solvent may be one or more selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1, 4-Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether , Chloroform, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethylene, hexane , Heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, tertiary butanol, 2-ethoxypropanol, 2-methoxy Propanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ether acetate, 3-methoxybutyl acetate, 3-ethoxypropionic acid Ethyl ester, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether are not limited thereto.

If necessary, the colorant composition may further include a salt. This salt has the effect of miniaturizing the dispersed particles in the miniaturization step described later. The salt can be removed by washing with a solvent such as distilled water, and is not particularly limited as long as it is a component useful for miniaturization. For example, a NaCl-like material can be used. In the case of using a salt, the amount used can be determined according to need. For example, it can be 2 to 8 times, and more preferably 2 to 8 times the total weight of the first xanthracene dye and the second xanthracene dye. Use about 3 to 5 times. The salt can be removed by washing as described above. In this case, the solvent can be removed together. The cleaning may be performed once or several times as needed.

Based on 100 parts by weight of the first xanthracene dye, the second xanthene dye may be contained in an amount of 3 to 30 parts by weight, preferably 5 to 50 parts by weight.

The dispersant may be contained in an amount of 1.5 to 8 times, and preferably 2 to 6 times the weight of the second xanthracene-based dye.

When the solvent is contained, the solvent may be contained in a weight of 1/15 to 1/5 of the weight of the solid content. Here, when the solid content weight is used with the first xanthracene-based dye and the second xanthracene-based dye, it means the weight of the solid content including the content of the salt.

According to another embodiment of the present invention, the colorant composition may further include one or more of a dye and a pigment. As an example, the colorant composition may further include a phthalocyanine pigment, for example, may include PB15: 6. In addition, it may further include one or more pigments or dyes selected from the group consisting of pigments or dyes: metal-free phthalocyanine pigments or dyes, and metal-substituted phthalocyanine pigments or dyes. (Metal phthalocyanine) pigments or dyes, Triarylmethane pigments or dyes, Quinophthalone pigments or dyes, Isoindoline pigments or dyes, Azo pigments or Dyes, Azo-metal complex pigments or dyes, Perylene pigments or dyes, Diketopyrrolo-pyrrole pigments or dyes, Anthraquinone Pigments or dyes, Dipyrromethene pigments or dyes, Porphyrin pigments or dyes, Tetra aza porphyrin pigments or dyes, Rhodamine pigments or Dyes and Xanthene pigments or dyes. The dyeing agent and the pigment may be added to the coloring agent composition in an amount of 1 to 50 parts by weight, and preferably 10 to 40 parts by weight, based on 100 parts by weight of the colorant composition.

Another embodiment of the present invention provides a colorant dispersion liquid including the colorant composition, a dispersant, a binder resin, and a solvent. In this specification, a colorant dispersion liquid may be replaced with the term millbase. Here, the coloring agent composition contained in a coloring agent dispersion liquid shows the state which removed the solvent. When a salt is used for the colorant composition, the salt is removed together with the solvent by washing and then included in the colorant dispersion liquid.

According to one embodiment, the colorant dispersion liquid may further include beads. As the beads, a particle diameter of 0.05 mm to 1.5 mm can be used. As a specific example, beads having a particle diameter of 0.1 mm, 0.3 mm, 0.5 mm, 0.8 mm, and / or 1 mm can be used. As the material of the beads, one or more of aluminum oxide, aluminum silicate, zirconium oxide, and / or silicon nitride can be used. The amount of use of the beads is not particularly limited, and can be used 10 to 40 times compared to the total weight of the coloring agent composition and the dispersant. Such beads can exert a function of dispersing the constituent components on the composition contained in the colorant dispersion liquid.

According to another embodiment of the present invention, the colorant dispersion liquid may further include one or more of a dye and a pigment. Examples of the additional dyes and pigments are the same as those exemplifying the additional dyes and pigments in the colorant composition.

Before the colorant composition is contained in the colorant dispersion liquid, it may also be subjected to a miniaturization step. The miniaturization step means a step of miniaturizing by applying a physical force. According to an example, the diameter of the particles dispersed in the colorant composition through the miniaturization step is 40 nm to 100 nm. Here, the diameter refers to the maximum length of the dispersed particles.

The diameter of the micronized particles can be measured using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Specific examples of the SEM measurement method are described below. First, 0.01 g of a toner dispersion liquid containing finely divided particles was added to a chloroform solvent. Ultrasonic equipment JAC-5020 from Kodo Co. was used and treated at an intermediate intensity for 10 minutes. Well separated. After that, about one drop was dropped on the glass, and then a heat treatment was performed on a 50-degree hot plate for 5 minutes to remove the solvent. After coating the particles so that the thickness of Pt is about 100 Å to 200 Å, the diameter of the particles was observed by SEM.

After the colorant dispersion is manufactured, a propylene glycol monomethyl ether Ether Acetate (PGMEA) solvent having a height of about 1/4 is added to a 1 cm × 5 cm cell (Cell), and dripped therein. Drop 1 or 2 drops of dispersion (Millbase). After being well diluted in the solvent, the particle size was measured using a Malvern particle size analyzer. The particle size distribution is measured by measuring an angle change corresponding to the intensity of light that penetrates and scatters in a fine particle sample in which a laser beam is dispersed.

When the diameter of the particles dispersed in the colorant dispersion exceeds 100 nm, there is a problem that the light-dark ratio (Contrast Ratio) is reduced by light scattering. When the size of the dispersed particles is too small, The re-condensation of each other reduces the stability of the light-dark ratio (Contrast Ratio) and dispersion (Millbase), so it is preferably in the range of 40 nm to 100 nm, and more preferably in the range of 40 nm to 80 nm. .

According to an example, the dispersed particle size of the colorant composition is 40 nm to 80 nm, and the viscosity is 2.5 cP to 6.5 cP.

The viscosity measurement method is to add about 1 mL of the manufactured toner dispersion liquid (Millbase) to the chamber of the viscosity measurement machine. When the motor is turned on, the spindle ( Spindle) spins and obtains a stable viscosity value to a steady flow.

As the solvent, those exemplified in the colorant composition can be used.

The binder resin is not particularly limited as long as it shows physical properties such as strength and developability of a film produced from a resin composition.

The binder resin may be a copolymer resin of a polyfunctional monomer that imparts mechanical strength and a monomer that imparts alkali solubility, and may further include a binder generally used in this technical field.

The polyfunctional monomer that imparts mechanical strength to the film may be any one or more of unsaturated carboxylic acid esters, aromatic vinyls, unsaturated ethers, unsaturated sulfonimines, and acid anhydrides.

Specific examples of the unsaturated carboxylic acid esters can be selected from the group consisting of benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, fluorenyl octyloxy-2 (meth) acrylate -Hydroxypropyl ester, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (methyl Base) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiacrylate Ethylene glycol (meth) acrylate, p-nonylbenzene Polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, (meth) 1,1,1,3,3,3-hexafluoroisopropyl acrylate, octafluoropentyl (meth) acrylate, heptafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, α-hydroxymethyl methacrylate, α-hydroxymethacrylate, α-hydroxymethacrylate, and α-hydroxymethacrylate are not limited to these.

Specific examples of the aromatic vinyl monomers include free styrene, α-methylstyrene, (o-, m-, p-)-vinyltoluene, (o-, m-, p-)-methoxybenzene The group consisting of ethylene and (ortho, meta, p) -chlorostyrene is not limited to these.

Specific examples of the unsaturated ethers can be selected from the group consisting of vinyl methyl ether, vinyl ether, and allyl glycidyl ether, but are not limited to these.

Specific examples of the unsaturated fluorene imines can be selected from N-phenylcis butylene diimide, N- (4-chlorophenyl) cis butylene diimide, and N- (4-hydroxybenzene Group), but is not limited to this group consisting of maleimide diimide and N-cyclohexylmaleimide.

The acid anhydride includes maleic anhydride, methyl maleic anhydride, tetrahydrophthalic anhydride, and the like, but is not limited to these.

The monomer for imparting alkali solubility is not particularly limited as long as it contains an acid group. For example, it is preferred to use a monomer selected from (meth) acrylic acid, butenoic acid, itaconic acid, maleic acid, and fumaric acid. Diacid, monomethylmaleic acid, 5-norbornene-2-carboxylic acid, phthalic acid mono-2-((meth) acrylfluorenyloxy) ethyl ester, succinic acid mono- One or more members of the group consisting of 2-((meth) acrylfluorenyloxy) ethyl ester and ω-carboxy polycaprolactone mono (meth) acrylate are not limited thereto.

According to an embodiment of the present specification, the acid value of the binder resin is 50 KOHmg / g to 130 KOHmg / g, and the weight average molecular weight is 1,000 to 50,000.

The content of the coloring agent composition in the colorant dispersion liquid containing the first xanthracene-based dye and the complex of the second xanthracene-based dye and the dispersant may be 5 to 20% by weight. In the colorant dispersion liquid, the binder resin may be 1% to 60% by weight, the dispersant may be 1% to 40% by weight, and the solvent may be 10% to 80% by weight.

One embodiment of the present specification provides a photosensitive resin composition including the colorant dispersion liquid, a binder resin, a polyfunctional monomer, and a photopolymerization initiator.

Here, the binder resin and the solvent can be described in association with the colorant dispersion liquid and the colorant composition.

The polyfunctional monomer is a monomer that exhibits a photoresist effect formed by light, and may be specifically selected from propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl Alcohol diacrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxyethanol diacrylate, trihydroxyethyl isocyanurate A group of trimethacrylate, trimethylpropane trimethacrylate, diphenyl pentaerythritol hexaacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate One or a mixture of two or more of them.

The photopolymerization initiator is not particularly limited as long as it is an initiator that promotes crosslinking by generating radicals by light. For example, the photopolymerization initiator may be selected from acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds. One or more of the group consisting of a compound and an oxime-based compound.

The acetophenone-based compounds include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-ketone, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ether, benzoin isobutyl ether , Benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholinyl-1-propane-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one, 2- (4-bromo-benzyl-2-dimethylamino) -1- (4-morpholinylphenyl) -butane-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, etc. Is not limited to these.

The biimidazole-based compounds include: 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- 4,4 ', 5,5'-tetra (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, etc. Is not limited to these.

The triazine-based compound includes: 3- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} propanoic acid, 3- {4- [2,4 -Bis (trichloromethyl) -mesytriazin-6-yl] phenylthio} propanoic acid 1,1,1,3,3,3-hexafluoroisopropyl ester, 2- {4- [2,4 -Bis (trichloromethyl) -mesytriazin-6-yl] phenylthio} ethyl acetate, 2- {4- [2,4-bis (trichloromethyl) -mesytriazin-6-yl ] Phenylthio} 2-epoxyethyl acetate, 2- {4- [2,4-bis (trichloromethyl) -trisazine-6-yl] phenylthio} cyclohexyl acetate, 2 -{4- [2,4-bis (trichloromethyl) -mesytriazin-6-yl] phenylthio} benzyl acetate, 3- {chloro-4- [2,4-bis (trichloromethyl) ) -Mesytriazine-6-yl] phenylthio} propanoic acid, 3- {4- [2,4-bis (trichloromethyl) -mesytriazin-6-yl] phenylthio} propanyl Amine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylamine Phenyl) -1,3, -butadienyl-mesytriazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-mesytriazine, etc. are not limited to Yes.

The oxime-based compounds are: 1,2-octanedione, 1- (4-phenylthio) phenyl, 2- (o-benzoylhydrazine) (Ciba-Geigy) Company, CGI124), ethyl ketone, -1- (9-ethyl) -6- (2-methylbenzylidene-3-yl)-, 1- (O-acetamidooxime) (CGI242), N-1919 (ADEKA) is not limited to these.

According to an embodiment of the present specification, the content of the binder resin is 1% to 60% by weight, and preferably 10% to 25% by weight based on the total weight of solid components in the photosensitive resin composition. The content of the photoinitiator is 0.1% to 20% by weight, preferably 1% to 7% by weight, and the content of the polyfunctional monomer is 0.1% to 50% by weight. It is preferably 5 to 20% by weight. The content of the solvent may include 10% to 85% by weight, and preferably 35% to 65% by weight based on the entire weight of the composition. The colorant dispersion liquid contains 5% to 35% by weight based on the entire weight of the composition, and the first xanthracene dye and the second xanthracene dye and dispersant in the colorant dispersion liquid The content may be 5% to 20% by weight.

The total weight of the solid content means the total of the total weight of the components in the resin composition other than the solvent. The solid content and the basis weight percentage of each component based on the solid content can be measured by a general analysis method used in the art such as liquid chromatography or gas chromatography.

According to another embodiment of the present invention, the photosensitive resin composition may further include one or more of a dye and a pigment. Examples of the additional dyes and pigments are the same as those exemplifying the additional dyes and pigments in the colorant composition.

The photosensitive resin composition may further include a surface additive. As a surface additive, a hardening accelerator, an adhesion promoter, an adhesion promoter, a surfactant, a thermal polymerization inhibitor, an ultraviolet absorber, a dispersant, a leveling agent, an antioxidant, a photocrosslinking sensitizer, and a multicomponent can be used. Multi-thiol and so on. The surface additive may contain about 0.1% by weight to 5% by weight, and preferably about 0.5% by weight to 1% by weight based on the total amount of the photosensitive resin composition. The content of the surface additive may be 0.1% by weight to 20% by weight based on the total weight of the solid content in the photosensitive resin composition.

As the photocrosslinking sensitizer, one or more members selected from the group consisting of benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4- Bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl benzoate, 3,3-dimethyl- Benzophenone compounds such as 4-methoxybenzophenone, 3,3,4,4-tetrakis (third butylperoxycarbonyl) benzophenone; 9-fluorenone, 2-chloro-9 -Fluorenone compounds such as fluorenone, 2-methyl-9-fluorenone; thioanthrone, 2,4-diethylthioxanthone, 2-chlorothiaxanthone, 1-chloro-4- Thioxanthone-based compounds such as propyloxythioxanthone, isopropylthioxanthone, and diisopropylthioxanthone; xanthracenes such as xanthone and 2-methylxanthone Ketone compounds; anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, third butyl anthraquinone, 2,6-dichloro-9,10-anthraquinone and other anthraquinone compounds; 9-benzene Acridine, 1,7-bis (9-acridyl) heptane, 1,5-bis (9-acridylpentane), 1,3-bis (9-acridyl) propane, and other acridines Compounds; benzoin, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrene And other dicarbonyl compounds; 2,4,6-trimethylbenzylidenediphenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentane Phosphine oxide compounds such as phosphine oxide; methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl Benzoate compounds such as methyl-4- (dimethylamino) benzoate; 2,5-bis (4-diethylaminobenzylidene) cyclopentanone, 2,6-bis ( 4-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4-diethylaminobenzylidene) -4-methyl-cyclopentanone and other amine synergists; 3, 3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzylidene- 7- (diethylamino) coumarin, 3-benzylidene-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2 , 3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzopyrano [6,7,8-ij] -quinazin-11-one and other coumarin compounds; 4-di Chalcone compounds such as ethylaminochalcone, 4-azidobenzylideneacetophenone; 2-benzylidenemethylene, 3-methyl-b-naphthothiazoline.

The hardening accelerator is used for improving hardening and mechanical strength. Specifically, one or more members selected from the group consisting of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2- Mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), Pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetra (2-mercaptoacetate), pentaerythritol-tri (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate) ), And trimethylolpropane-tris (3-mercaptopropionate).

The adhesion promoter used in this specification may be selected from methacrylfluorenyloxypropyltrimethoxysilane, methacrylfluorenyloxypropyldimethoxysilane, and methacrylfluorenyloxypropyl One or more of methacrylfluorenylsilane coupling agents such as triethoxysilane, methacrylmethyloxypropyldimethoxysilane, and the like can be used. The alkyltrimethoxysilane can be obtained from octyltrimethoxysilane. , Dodecyltrimethoxysilane, octadecyltrimethoxysilane, etc., one or more are selected and used.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, the silicone-based surfactant can be used: BYK-077, BYK-085, BYK-Chemie, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK- 333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc., Fluorine-based surfactants can be used: F-114, F-177, F-410, F-410 of Dai Nippon Ink & Chemicals 411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF- 1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc., but not only Limited to these.

The antioxidant may be one or more selected from the group consisting of a hindered phenol antioxidant, an amine antioxidant, a sulfur antioxidant, and a phosphine antioxidant, but is not limited thereto.

Specific examples of the antioxidant include phosphoric acid-based thermal stabilizers such as phosphoric acid, trimethyl phosphate, or triethyl phosphate; 2,6-di-third-butyl-p-cresol, and octadecyl -3- (4-hydroxy-3,5-di-third-butylphenyl) propionate, tetrabis [methylene-3- (3,5-di-third-butyl-4-hydroxybenzene) Propyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene, 3,5-di -Third-butyl-4-hydroxybenzyl diethyl phosphite, 2,2-thiobis (4-methyl-6-third-butylphenol), 2,6-g, t-butylphenol 4,4'-butylene-bis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), or bis [3 1,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] diol ester (Bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoicacid [Hindered phenol] -like primary antioxidants; phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N'-diphenyl-p-phenylenediamine or N , N'-bis-β-naphthyl-p-phenylenediamine-like secondary antioxidants; dilauryl disulfide, dilauryl thiopropionate, distearylsulfide Thio-based secondary antioxidants such as propionate, mercaptobenzothiazole or tetramethylthiuram disulfide tetrabis [methylene-3- (laurylthio) propionate] methane; Or triphenyl phosphite, tri (nonylphenyl) phosphite, triisodecyl phosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4 -ditbutylphenyl) Pentaerythritol Diphosphite) or (1,1'-biphenyl) -4,4'-diylbisphosphonic acid tetra [2,4-bis (1,1-dimethylethyl) phenyl] ester ((1,1'-Biphenyl) -4,4'-Diylbisphosphonous acidtetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester) -like secondary antioxidants.

The ultraviolet absorber can be used: 2- (3-third butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxybenzophenone, etc., but It is not limited to these, and can be generally used by users in the art.

The thermal polymerization inhibitor may include, for example, one or more members selected from the group consisting of p-anisole, hydroquinone, pyrocatechol, and tert-butylcatechol. (Tert-butyl catechol), N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, p-methoxyphenol, di-third-butyl-p-cresol, o-benzene Triphenol, benzoquinone, 4,4-thiobis (3-methyl-6-third butylphenol), 2,2-methylenebis (4-methyl-6-third butylphenol) , 2-mercaptoimidazole, and phenothiazine, but are not limited to these, and may include those generally known in the technical field.

The leveling agent may be polymeric or non-polymeric. Specific examples of the polymerizable leveling agent include polyethyleneimine, polyamidoamine, a reaction product of an amine and an epoxide. Specific examples of the non-polymeric leveling agent include a non-polymer sulfur compound. As well as non-polymeric nitrogen-containing compounds, it is not limited thereto, and users in the art can generally use it.

Another embodiment of the present invention provides a color filter, which is a color filter including a transparent substrate and a coloring layer included on the transparent substrate, and the coloring layer includes the photosensitive resin composition. Hardened.

The color filter can be manufactured using the photosensitive resin composition. The photosensitive resin composition is coated on a substrate to form a coating film, and the coating film is exposed, developed, and cured to form a color filter.

The coating method is not particularly limited, and a spray method, a roll coating method, a spin coating method, or the like can be used, and a spin coating method is generally widely used. In addition, after the coating film is formed, a part of the residual solvent can be removed under reduced pressure as appropriate.

The light source for hardening the resin composition of the present specification includes, for example, mercury vapor arc (arc), carbon arc, Xe arc, and the like that emit light having a wavelength of 250 nm to 450 nm, but it is not necessarily limited to this.

The resin composition according to an embodiment of the present specification is excellent in heat resistance, and has little color change due to heat treatment. The color reproduction rate is high even through a hardening process during the manufacture of a color filter, and it is possible to provide a high brightness and brightness ratio. Color filters.

The substrate may be a glass plate, a silicon wafer, a plate of a plastic substrate such as polyethersulfone (PES), polycarbonate (PC), or the like, and the type thereof is not particularly limited.

The color filter may include a red pattern, a green pattern, a blue pattern, and a black matrix.

According to another embodiment, the color filter may further include an overcoat layer.

Between the color pixels of the color filter, for the purpose of improving the contrast, a grid-like black pattern called a black matrix can be arranged. The material of the black matrix can use chromium. In this case, a method can be used in which chromium is deposited on the entire glass substrate and a pattern is formed by an etching process. However, in consideration of high cost in steps, high reflectance of chromium, and environmental pollution caused by chromium waste liquid, a resin black matrix using a pigment dispersion method capable of fine processing can be used.

The black matrix according to the embodiment of the present specification may use a black pigment or a black dye as a color material. For example, carbon black can be used alone, or carbon black can be mixed with colored pigments. In this case, mixing colored pigments with insufficient light-shielding properties has the following advantages: even if the amount of color material is relatively increased, the strength of the film or the adhesion to the substrate Sex will not decrease.

A liquid crystal display device including a color filter in this specification is provided. The liquid crystal display device may have a configuration known in the technical field in addition to the color filter. [Example]

Hereinafter, the present specification will be described in detail with examples. The following embodiments are used to describe the present specification. The scope of the present specification includes the scope described in the scope of the patent application and the substitutions and changes thereof, and is not limited to the scope of the embodiments.

[Manufacturing method of a dispersant containing a resin having a cationic group in a side chain] (Production Example 1: Production of a resin A-1 having a cationic group in a side chain) In a case including a thermometer, a stirrer, a distillation tube, and a cooler In a four-neck separable flask, 56.7 parts by weight of propylene glycol monomethyl ether acetate was added based on 100 parts by weight of the total weight of a dispersant containing a resin having a cationic group in a side chain, and the temperature was increased to 75 under a nitrogen stream. ℃. Based on 100 parts by weight of the total weight of separately added monomers or polymerization initiators, 45.8 parts by weight of methyl methacrylate, 14.8 parts by weight of n-butyl methacrylate, and 2-ethylhexyl methacrylate 7.8 Parts by weight, 5.0 parts by weight of benzyl methacrylate, 3.0 parts by weight of triethylene glycol methyl ether methacrylate, 18.9 parts by weight of 2-dimethylaminoethyl methacrylate, and 4.7 parts by weight of benzyl chloride salt After homogenization, it was put into a dropping funnel, and then attached to a four-neck separable flask, and the dropwise addition was performed over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98.7% or more based on the solid content, the weight average molecular weight (Mw) was 5,500, and the temperature was cooled to 50 ° C. Thereafter, based on 100 parts by weight of the total weight of the dispersant containing the resin having a cationic group in the side chain, 10 parts by weight of propylene glycol monomethyl ether was added to produce 5 mol% of a resin component having a cationic group in the side chain. Resin. The amine value of the obtained resin was 30 mgKOH / g.

The weight-average molecular weight (Mw) of the resin having a cationic group in the side chain is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. In addition, the amine valence was calculated using a 0.1 N hydrochloric acid aqueous solution by a potentiometric titration method, and then converted into an equivalent of potassium hydroxide.

(Production Example 2 to Production Example 8: Production of Resin A-2 to Resin A-8 having cationic properties in the side chain) Except for changing the monomer, the polymerization initiator, and the reaction temperature to the compositions shown in Table 1, Resin A-2 to resin A-8 having a cationic group in a side chain were obtained in the same manner as in Production Example 1.

[Table 1]

In Table 1, MMA means methyl methacrylate, nBMA means n-butyl methacrylate, EHMA means ethylhexyl methacrylate, BzMA means benzyl methacrylate, and TEGMA means formic acid. Triethylethylaminoacrylate, DMAEMA is dimethylaminoethyl methacrylate, BC is benzyl chloride salt, ST is styrene, and MDGMA is diethylene glycol methyl ether methyl Acrylate, EG means ethylene glycol methacrylate.

[Manufacturing method of colorant composite] The composition shown in Table 1 was added to a bench kneader (Bench Kneader) together with a solvent 7.5 g of diethylene glycol (Diethylene Glycol) and 40 g of ground salt (NaCl) ( Irie shokai co.ltd. (Model: PBV-01) was refined for 4 hours. After 4 hours, the finely divided toner composition was added to 1 L of distilled water at 60 ° C. and stirred for 30 minutes, and then the pressure was reduced to remove the distilled water. When the distilled water was removed under reduced pressure, about 7 L of distilled water at 60 ° C. was further added to completely remove the salt (NaCl), and the complexes B-1 to B-21 in Table 2 below were obtained. The first xanthene dye and the second xanthene dye have the following structures.

[Table 2]

In the said Table 2, the Mol ratio (%) means the ratio of the ammonium salt introduced according to the ratio of EG (ethylene glycol methacrylate) in the said Table 1.

[Manufacturing method of colorant dispersion liquid] A mixture of the complex B-1 to complex B-21 of the toner composition produced as described above with 8.4 g of propylene glycol monomethyl ether acetate is shown in Table 3 below. After stirring in a uniform manner, zirconia beads having a diameter of 0.3 mm were used, and dispersion treatment was performed using a paint shaker for 2 hours. After that, it was replaced with 0.1 mm zirconia beads, and dispersed for an additional 2 hours using a paint shaker. After the dispersion treatment, 12.6 g of propylene glycol monomethyl ether acetate was added for each composition, and then filtered through a 1.0 μm filter to obtain a colorant dispersion liquid.

[table 3]

In Table 3, the binder A is a copolymer having a mass ratio of benzyl methacrylate: N-phenylcis butylene diimide: styrene: methacrylic acid = 55: 9: 11: 25.

[Production of photosensitive coloring composition] The components and the blending amounts shown in Table 4 below were used to produce a photosensitive coloring composition. Based on 100 parts by weight of the total weight of the photosensitive coloring composition, 16.74 parts by weight of one of the previously prepared colorant dispersion liquid C-1 to colorant dispersion liquid C-21, and phthalocyanine (B15: 6) dispersion liquid 22.33 parts by weight, 11.73 parts by weight of adhesive A, 9.88 parts by weight of dipentaerythritol hexaacrylate (DIPENTAERYTHRITOL HEXAACRYLATE, DPHA) of Miwon Corporation, 1.16 parts by weight of initiator PBG-3057, and photosensitizer 4,4 0.39 parts by weight of '-bis (diethylamino) benzophenone (4,4'-Bis (diethylamino) benzophenone (EMK)), surface additive B (leveling agent, F-554 of DIC) ) 0.1 parts by weight, surface additive C (adhesion agent KBM-503) 0.19 parts by weight, surface additive D (antioxidant, Songnox-1010 of Songwon Industry) 0.14 parts by weight, surface additive E ( 0.44 parts by weight of Muti-thiol (SQ-506), 29.5 parts by weight of solvent PGMEA (propylene glycol monomethyl ether acetate), 3-Methoxy butyl acetate, 3- MBA) 17.4 parts by weight.

The binder A is the same as that used in the production of the colorant dispersion.

The adhesive A is a copolymer having a mass ratio of benzyl methacrylate: N-phenylcis butylene diimide: styrene: methacrylic acid = 55: 9: 11: 25.

[Table 4]

In Table 4, in Comparative Examples 1 to 4, and Comparative Examples 6 to 8, the colorant dispersion was gelated and could not be evaluated.

[Evaluation of colorant dispersion liquid] The obtained colorant dispersion liquids (C-1 to C-21) were subjected to particle size and storage stability by the following methods.

(Particle size evaluation method) A 1 cm × 5 cm quartz cell (Cell) is filled with PGMEA (propylene glycol monomethyl ether acetate) having a height of about 1/4, and then about 1 to 2 drops are produced.剂 溶液 液 Liquid dispersion. The measurement was performed using a particle size analyzer (Zetasizer nano-ZS90 from Malvern). Based on the particle size measurement results, the degree of miniaturization was evaluated. The particle size measurement results are shown in Table 5 below.

[table 5]

Dispersion liquids C-9 to C-21, which were refined by using the first xanthracene dye and the second xanthene dye, and a dispersant containing an ammonium structure, were not gelled. To obtain a colorant dispersion with a particle size of 40 nm to 80 nm.

(Evaluation method of storage stability) For the colorant dispersion liquid, the initial viscosity at 25 ° C. of the day when the colorant dispersion liquid was manufactured was measured using a viscometer (Toki Sangyo Viscometer TV-25) at 100 rpm. And the viscosity after 7 days in a convection oven at 40 ° C. Based on the following equation, the measured viscosity was used to calculate the rate of change in viscosity over time. Based on the calculated change rate of viscosity over time, the storage stability was evaluated on the following basis. The evaluation results are shown in Table 6 below. (Change rate of viscosity over time) = [{(initial viscosity)-(time viscosity)} / (initial viscosity)] × 100 ◎: less than 5%, △: 5% to less than 10%, X: 10% or more

[TABLE 6]

A dispersion was prepared using a first xanthene dye, a second xanthene dye, and a dispersant containing an ammonium structure, and a dispersion liquid C-9 prepared by applying a dispersant containing an ammonium structure and a dispersion thereof. In the case of the liquid C-12 to the dispersion liquid C-21, the viscosity stability is excellent, and it is a range that can be preferably used as a color filter.

(Evaluation method of transmittance) The comparative examples 5 and 1 to 13 of the manufactured photosensitive coloring composition were spin-coated on a 5 cm × 5 cm glass at 110 ° C. A heat treatment (Pre-bake) was performed for 75 seconds to form a film. The interval between the film-formed substrate and a photo mask was set to 250 μm, and irradiation was performed using an exposure device at an exposure amount of 40 mJ / cm ² .

The exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds, and subjected to a post-heat treatment at 230 ° C. for 20 minutes to obtain a color pattern. The color patterns were measured with a spectrophotometer (MCPD), and transmittances of Comparative Examples 1 to 8 and Examples 1 to 13 were obtained. The transmittance value is a value obtained by comparing By = 0.051.

(Evaluation method of heat resistance) For a substrate subjected to post-heat treatment (Post-bake) at 230 ° C for 20 minutes and color characteristics confirmed using a spectrophotometer, a 230 ° C convection oven was additionally used. After 5 hours and 30 minutes of heat treatment, the color characteristics were confirmed again with a spectrophotometer, and a ΔEab value was confirmed. Transmittance improvement rate (%) = Transmittance of composition / Transmittance of Comparative Example 5

The transmittance and heat resistance evaluation results are shown in Table 7 below.

[TABLE 7]

Examples 1 to 13 in which the first xanthracene dye, the second xanthracene dye, and the dispersant containing an ammonium structure were combined and refined were excellent in transmittance, and were used in the manufacture of colorants In the case of a dispersion liquid, the composition having an ammonium structure-containing dispersant is also excellent in heat resistance.

If the first xanthracene dyes with the same number of positive and negative charges are used, and the second xanthene dyes with more than one positive charge than the number of positive charges, and a dispersant containing an ammonium structure When a colorant dispersion liquid is produced by the ion-bonded composite, the dispersibility is improved, and the viscosity stability and the brightness of the coating film are high.

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Claims (20)

A toner composition comprising: a first xanthracene dye having the same number of positive and negative charges; and a second xanthracene dye having a number of negative charges more than the number of positive charges, A complex formed by ion bonding with a dispersant having an amine value of 0 mgKOH / g to 200 mgKOH / g and containing an ammonium structure. The coloring agent composition according to item 1 of the scope of patent application, wherein a part or all of the second xanthracene dyes are adjacent to each other and two or three or more first xanthene dyes are adjacent to each other. Or the terminal of the first xanthracene dye. The coloring agent composition according to item 1 of the scope of patent application, wherein the first xanthracene dye has a maximum absorption wavelength between 500 nm and 580 nm, and the maximum of the first xanthene dye is The difference between the absorption wavelength and the maximum absorption wavelength of the second xanthracene dye is 100 nm or less. The toner composition according to item 1 of the scope of patent application, wherein the first xanthracene-based dye contains a dye represented by the following chemical formula 1 and having the same number of positive and negative charges, and the second oxygen The heteroanthracene-based dye contains a dye represented by the following Chemical Formula 2 and the number of negative charges is one or more more than the number of positive charges; [Chemical Formula 1] In the chemical formula 1, R ₁ to R ₄ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, anionic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted alkane In the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a dianhydride group containing a nitrogen atom; R ₅ to R ₉ are the same or different from each other, and are each Independently selected from the group consisting of hydrogen, deuterium, anionic, hydroxyl, sulfonamido, sulfonate, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted In the group consisting of substituted heteroaryl groups, at least one of R ₅ to R ₉ is an anionic group, a sulfonate group, or a sulfonamido group; R ₁₀ and R ₁₁ are the same as each other or Are different, and are each independently hydrogen, deuterium, halogen, nitro, or substituted or unsubstituted alkyl, r ₁₀ and r ₁₁ are integers of 0 to 3, and r ₁₀ and r ₁₁ are In the case of 2 or more, the structures in parentheses are the same or different from each other; [Chemical Formula 2] In the chemical formula 2, R ₂₁ to R ₂₄ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, anionic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted alkane In the group consisting of a group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a dianhydride group containing a nitrogen atom, at least one of R ₂₁ to R ₂₄ is Anionic, sulfonate, or sulfonamido substituted or unsubstituted anionic, sulfonate, or sulfonamido, alkyl, anionic, sulfonate, or sulfonium Amine-substituted aryl groups, or heteroaryl groups substituted with anionic groups, sulfonate groups, or sulfonamido groups; R ₂₅ to R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, and anions Basic group, hydroxyl group, sulfonamido group, sulfonate group, substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group, and substituted the group consisting of heteroaryl or unsubstituted aryl group in which the R ₂₅ ~ R ₂₉ in at least one anionic group Sulfonate group, acyl or a sulfo group; R ₃₀ and R ₃₁ are the same or different, and each independently hydrogen, deuterium, a halogen group, a nitro group, or a substituted or unsubstituted alkyl group from each other, r ₃₀ and r ₃₁ is an integer from 0 to 3, and when r ₃₀ and r ₃₁ are each 2 or more, the structures in parentheses are the same or different from each other. The toner composition according to item 4 of the scope of the patent application, wherein the R ₁ to R ₄ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl, and substituted Or a group consisting of an unsubstituted aryl group and a dianhydride group containing a nitrogen atom; the R ₂₁ to R _{2 4} are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted In the group consisting of a substituted alkyl group, a substituted or unsubstituted aryl group, and a dianhydride group containing a nitrogen atom; the remaining substituents are the same as defined in item 4 of the scope of patent application. The coloring agent composition according to item 1 of the scope of the patent application, wherein the dispersant comprises 3 mol% to 50 mol% of a single body unit including an ammonium structure based on a total single body unit of 100 mol%. The coloring agent composition according to item 1 of the scope of patent application, wherein the second xanthracene dye further contains a counter cation. The toner composition according to item 1 of the patent application scope, wherein the dispersant further comprises a counter anion. The coloring agent composition according to item 1 of the scope of patent application, wherein the dispersant is represented by the following Chemical Formula 7; [Chemical Formula 7] In Chemical Formula 7, Ra to Rd are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Substituted or unsubstituted arylalkyl, -L-NHCO-R, or -L-OCO-R, or two of Ra to Rd are bonded to each other to form a substituted or unsubstituted ring; R is Hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl; L is substituted or unsubstituted alkylene. The coloring agent composition according to item 1 of the scope of patent application, wherein the dispersant includes a unit of the following Chemical Formula 8; [Chemical Formula 8] In Chemical Formula 8, Rb to Rd are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or A substituted or unsubstituted arylalkyl group, or two of Rb to Rd are bonded to each other to form a substituted or unsubstituted ring; Z is an alkylene group, an alkylene group, -L-NHCO-, Or -L-OCO-, L is an alkylene group; Re to Rg are the same or different from each other, and are each independently hydrogen or an alkyl group. The coloring agent composition according to item 10 of the patent application range, wherein the weight average molecular weight of the dispersant is 1,000 to 10,000. The coloring agent composition according to item 1 of the scope of patent application, wherein the coloring agent composition further comprises one or more of a dye and a pigment. The coloring agent composition according to item 1 of the scope of the patent application, wherein the diameter of the particles dispersed in the coloring agent composition is 40 nm to 100 nm. The coloring agent composition according to item 1 of the scope of patent application, wherein the coloring agent composition further comprises a solvent. A colorant dispersion liquid, comprising: the colorant composition according to any one of claims 1 to 13 of the scope of application for a patent, a dispersant, a binder resin, and a solvent. The colorant dispersion liquid according to item 15 of the scope of patent application, wherein the diameter of the particles dispersed in the colorant dispersion liquid is 40 nm to 80 nm, and the viscosity of the colorant dispersion liquid is 2.5 cP to 6.5 cP. . A photosensitive resin composition, comprising: the toner dispersion liquid, the binder resin, the polyfunctional monomer, and the photopolymerization initiator according to item 15 of the scope of the patent application. The photosensitive resin composition according to item 17 of the scope of application for a patent, wherein the photosensitive resin composition further comprises a surface additive. A color filter is a color filter including a transparent substrate and a coloring layer included on the transparent substrate, and the coloring layer includes the photosensitive resin composition according to item 17 of the scope of patent application. Hardened. A liquid crystal display device includes a color filter according to item 19 of the scope of patent application.