TWI725631B - Photosensitive resin composition, photoresist, color filter and display device - Google Patents

Abstract

This specification provides a photosensitive resin composition comprising a binder resin represented by chemical formula 1, a photoresist, a color filter and a display device.

Description

Photosensitive resin composition, photoresist, color filter and display Display device

This application claims priority from the filing date of Korean Patent Application No. 10-2018-0146358 filed to the Korean Intellectual Property Office on November 23, 2018, and the contents of which are all included in this specification.

This specification relates to a photosensitive resin composition, photoresist, color filter, and display device.

Currently, in order to realize a color filter, a pigment dispersion method in which a pigment is used as a colorant is generally applied. However, in the case of a pigment dispersion, the pigment exists in the state of particles, which not only scatters light, but also increases the surface area of the pigment drastically due to the miniaturization of the pigment, resulting in the deterioration of the dispersion stability caused by this, resulting in uneven pigment formation. particle. Therefore, in order to achieve the recently required high brightness, high contrast, and high resolution, it has recently been studied to use dyes instead of pigments as colorants.

Generally, dyes have the advantage of higher transmittance than pigments. However, it has the disadvantage of insufficient heat resistance compared with pigments. In addition, compared with existing pigments, it has better solubility in organic solvents, and therefore has the disadvantage of insufficient chemical resistance.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Open Document JP 9-87534

This specification provides a photosensitive resin composition, photoresist, color filter, and display device.

An embodiment of this specification provides a photosensitive resin composition, the photosensitive resin composition comprising: dibenzopyran dye; a binder resin comprising the following structure represented by Chemical Formula 1; a multifunctional monomer; Photoinitiator; and solvent.

是指與其他取代基或鍵結部連接的部分，X'為O或NH，L1及L2彼此相同或不同，分別獨立地為直接鍵、經取代或 未經取代的伸烷基、-C(=O)-、或-L'-O(C=O)-，L'為經取代或未經取代的伸烷基，T1至T3彼此相同或不同，分別獨立地為氫、羥基、或者經取代或未經取代的烷基，t2為0至4的整數，在t2為2以上的情況下，T2彼此相同或不同，t3為0至5的整數，在t3為2以上的情況下，T3彼此相同或不同。 In the chemical formula 1,

Refers to the part connected to other substituents or bonding parts, X'is O or NH, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted alkylene group, -C( =O)-, or -L'-O(C=O)-, L'is a substituted or unsubstituted alkylene group, T1 to T3 are the same or different from each other, and are independently hydrogen, hydroxyl, or A substituted or unsubstituted alkyl group, t2 is an integer from 0 to 4, when t2 is 2 or more, T2 is the same or different from each other, t3 is an integer from 0 to 5, and when t3 is 2 or more, T3 Same or different from each other.

One embodiment of this specification provides a photoresist manufactured using the photosensitive resin composition.

An embodiment of this specification provides a color filter including the photoresist.

An embodiment of this specification provides a display device including the color filter.

Since the photosensitive resin composition according to an embodiment of the present specification includes a binder resin containing a structure represented by Chemical Formula 1, it has the advantage of excellent chemical resistance to migration and elution.

Hereinafter, this specification will be described in more detail.

In this specification, when a component is described as being "on" another component, the case includes not only the case where a certain component is connected to another component, but also the case where there is another component between the two components.

In this specification, when it is described that a certain part "includes" a certain component, as long as there is no description to the contrary in particular, that case means that other components are not excluded, and other components may be further included.

是指與其他取代基或鍵結部鍵結的部位。 In this manual,

It refers to the site of bonding with other substituents or bonding parts.

In this specification, "derivatized unit" refers to a unit molecule or a repeating structure that forms a polymer.

An embodiment of this specification provides a photosensitive resin composition, the photosensitive resin composition comprising: dibenzopyran dye; a binder resin comprising the following structure represented by Chemical Formula 1; a multifunctional monomer; Photoinitiator; and solvent.

是指與其他取代基或鍵結部連接的部分，X'為O或NH，L1及L2彼此相同或不同，分別獨立地為直接鍵、經取代或未經取代的伸烷基、-C(=O)-、或-L'-O(C=O)-，L'為經取代或未經取代的伸烷基，T1至T3彼此相同或不同，分別獨立地為氫、羥基、或者經取代或未經取代的烷基，t2為0至4的整數，在t2為2以上的情況下，T2彼此相同或不同，t3為0至5的整數，在t3為2以上的情況下，T3彼此相同或不同。 In the chemical formula 1,

Refers to the part connected to other substituents or bonding parts, X'is O or NH, L1 and L2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted alkylene group, -C( =O)-, or -L'-O(C=O)-, L'is a substituted or unsubstituted alkylene group, T1 to T3 are the same or different from each other, and are independently hydrogen, hydroxyl, or A substituted or unsubstituted alkyl group, t2 is an integer from 0 to 4, when t2 is 2 or more, T2 is the same or different from each other, t3 is an integer from 0 to 5, and when t3 is 2 or more, T3 Same or different from each other.

The photosensitive resin composition of one embodiment of the present specification includes a binder resin having the structure represented by the chemical formula 1, so that the structure represented by the chemical formula 1 promotes a radical reaction during the exposure process, and Increasing the degree of polymerization of the binder resin and the polyfunctional monomer in the photosensitive resin composition can increase the degree of curing of the film. As the degree of curing of the film becomes higher, the heat resistance and chemical resistance of the color filter manufactured using the photosensitive resin composition of this specification are improved.

Examples of the structure represented by the chemical formula, the dye, or the substituent of the compound in this specification are described below, but are not limited thereto.

In this specification, the term "substituted or unsubstituted" refers to a term selected from the group consisting of deuterium, halogen, nitrile, nitro, -OH, carbonyl, ester, -COOH, and Imino groups, amide groups, anionic groups, alkoxy groups, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aralkyl groups, phosphine groups, sulfonate groups, amino groups, aryl groups, heteroaryl groups Group, silyl group, boron group, (meth)acrylic group, (meth)acrylate group, ether group, heterocyclic group containing more than one N, O, S or P atom, and anionic group One or more substituents in the group are substituted or do not have any substituents.

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

In this specification, the alkyl group may be linear or branched, and the carbon number is not particularly limited, but the carbon number of the alkyl group may be 1-30. According to another embodiment, the carbon number of the alkyl group is 1-20. According to another embodiment, the carbon number of the alkyl group is 1-10. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Etc., but not limited to this.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has a carbon number of 3 to 30, and particularly preferably a cyclopentyl group and a cyclohexyl group, but is not limited thereto.

In the present specification, an alkylene group refers to a group having two bonding positions in an alkane (alkane). The alkylene group may be linear, branched or cyclic. The carbon number of the alkylene group is not particularly limited, but the carbon number may be 1-30, for example. In addition, the carbon number may be 1-20, and the carbon number may be 1-10.

In this specification, the alkylene group may be an alkanediyl group, and the description of the alkylene group may be applied to the alkanediyl group.

In the present specification, the cycloalkyl group is not particularly limited, but according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkane The carbon number of the group is 3-20. According to another embodiment, the carbon number of the cycloalkyl group is 3-6. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but it is not limited to these.

基、芴基等，但不限定於此。 In this specification, the aryl group is not particularly limited, but preferably has a carbon number of 6 to 60, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6-30. According to one embodiment, the carbon number of the aryl group is 6-20. As the monocyclic aryl group, the aryl group may be a phenyl group, a biphenyl group, a triphenyl group, etc., but is not limited thereto. As the polycyclic aryl group, naphthyl, anthryl, indenyl, phenanthryl, pyrenyl, perylene, triphenyl,

Base, fluorenyl, etc., but not limited to this.

In the present specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a heterogeneous atom, and may be aromatic or aliphatic. The carbon number of the heterocyclic group is not particularly limited, but the carbon number is 2-30, specifically, the carbon number is 2-20. Examples of heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, triazinyl, and acridinyl. (acridyl), pyridazinyl, quinolinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophene Group, dibenzothienyl, benzofuranyl, dibenzofuranyl, etc., but not limited to these.

In this specification, the explanation about the heterocyclic group can be applied except that the heteroaryl group is aromatic.

In this specification, the alkoxy group may be linear or branched, and the carbon number is not particularly limited, but it may be 1 to 30, specifically 1 to 20, and more specifically 1 to 10. .

In this specification, the anionic group has a chemical bond with the structure of Chemical Formula 1, and the chemical bond may refer to an ionic bond. The anionic group is not particularly limited. For example, it can be used in U.S. Patent No. 7,939,644, Japanese Patent Application Publication No. 2006-003080, Japanese Patent Application Publication No. 2006-001917, Japanese Patent Application Publication No. 2005-159926, and Japanese Patent Application Publication No. 2006-003080. Japanese Patent Application Publication No. 2007-7028897, Japanese Patent Application Publication No. 2005-071680, Korean Application Publication No. 2007-7000693, Japanese Patent Application Publication No. 2005-111696, Japanese Patent Application Publication No. 2008-249663, and Japanese Patent Application Publication No. 2014- The anion described in 199436.

As specific examples of the anionic group, there are trifluoromethanesulfonate anion, bis(trifluoromethylsulfonyl)amide anion, bistrifluoromethanesulfonimide anion, and bisperfluoroethylsulfonimide anion. , tetraphenyl borate anion, tetrakis (4-fluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tris trifluoromethane sulfonic methide _{^{acyl, SO 3 -, CO 2 -}} , SO 2 N ^- SO ₂ CF ₃ , SO ₂ N ^- SO ₂ CF ₂ CF ₃ , and halogen groups such as fluoro, iodo, and chloro groups, but not limited to these.

In this specification, the anionic group itself may have an anion, or may exist in the form of a complex compound together with other cations. Therefore, according to the number of substituted anionic groups, the sum of charges of the entire molecule of the compound of the present invention may be different. The compound of the present invention has a cation in one amine group, and therefore, the total charge of the entire molecule may have an anion value obtained by subtracting 1 from the number of substituted anion groups to 0.

In this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expression of "(meth)acrylic acid" is also Have the same meaning.

In one embodiment of the present specification, the binder resin including the structure represented by the chemical formula 1 further includes a unit derived from an unsaturated compound having a cyclic ether structure having a carbon number of 2 to 4.

The unsaturated compound having a cyclic ether structure having a carbon number of 2 to 4 may be any one of the following structures, but is not limited to this.

In the structure, R is hydrogen, or a substituted or unsubstituted alkyl group with a carbon number of 1 to 4, and X3 and X4 are the same or different from each other, and are respectively a direct bond, -Rz-, -Rz-O- , -Rz-S-, or -Rz-NH-, where Rz is a substituted or unsubstituted alkanediyl group with a carbon number of 1 to 6.

In an embodiment of the present specification, the R may be an alkyl group having 1 to 4 carbon atoms substituted by -OH.

In an embodiment of the present specification, the photosensitive resin composition may further include a binder resin: the binder resin includes an unsaturated compound derived from a cyclic ether structure having a carbon number of 2 to 4 unit.

For the unsaturated compound having a cyclic ether structure having a carbon number of 2 to 4, the above description can be applied.

In one embodiment of the present specification, in addition to the binder resin including the structure represented by the chemical formula 1, the photosensitive resin composition may further include a binder resin commonly used in the corresponding technical field.

In one embodiment of the present specification, the dibenzopiperan dye is represented by the following chemical formula 2.

In the chemical formula 2, R1 to R6 are the same or different from each other, and are each independently selected from hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl, and substituted or unsubstituted alkoxy. , Substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, R7 to R11 are the same or different from each other, and are independently selected from hydrogen, deuterium, -OH, -SO ^{_{3 -, -SO 3 H, -SO}} 3 - Z +, -COO -, -COOH, -COO - Z +, -COORa, -SO 3 Rb, -SO 2 NRcRd, -CONRe, a substituted or unsubstituted The group consisting of alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, Z ⁺ represents ⁺ N(Rf) ₄ , Na ⁺ , or K ⁺ , Ra to Rf are the same or different from each other, and are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, Rc and Rd can be bonded to each other to form a heterocyclic ring containing a nitrogen atom, an Rf can be the same or different, R7 to R11 in the at least one of ^{_{-SO 3 -, -SO 3 H,}} -SO 3 - Z +, ^{-COO -, -COO - Z +,} -COORa, -SO 3 Rb, or -SO ₂ NRcRd, R12 to R15 are the same or different, each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl group , Substituted or unsubstituted aryl groups, and substituted or unsubstituted heteroaryl groups, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, or substituted or unsubstituted Rx is an anionic group or ammonium structure, and a is 0 or 1.

In one embodiment of this specification, R1 to R6 are the same or different from each other. Same, each independently selected from hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl having 1 to 30 carbons, and substituted or unsubstituted alkoxy having 1 to 30 carbons Group, a substituted or unsubstituted aryl group having 6 to 30 carbons, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbons.

In one embodiment of the present specification, R1 to R6 are the same or different from each other, and are independently selected from hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl having 1 to 20 carbons, and carbon A substituted or unsubstituted alkoxy group having a number of 1 to 20, a substituted or unsubstituted aryl group having a carbon number of 6 to 20, and a substituted or unsubstituted heterocyclic group having a carbon number of 2 to 20 A group of aryl groups.

In one embodiment of the present specification, R1 to R6 are the same or different from each other, and are independently selected from hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl having 1 to 20 carbons, and carbon A substituted or unsubstituted alkoxy group having a number of 1 to 20, a substituted or unsubstituted aryl group having a carbon number of 6 to 20, and a substituted or unsubstituted heterocyclic group having a carbon number of 2 to 20 A group of aryl groups.

In one embodiment of this specification, R1 to R6 are hydrogen, or substituted or unsubstituted methyl.

In one embodiment of this specification, R1 to R6 are hydrogen or methyl.

In an embodiment of the present specification, R7 to R11 are the same or different and each independently selected from the group consisting of hydrogen, ^{_{deuterium, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -COO -, -COOH, -COO ^- Z ⁺ , -COORa, -SO ₃ Rb, -SO ₂ NRcRd, -CONRe, substituted or unsubstituted alkyl with 1 to 30 carbons, and 6 to 30 carbons A group consisting of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

In an embodiment of the present specification, R7 to R11 are the same or different and each independently selected from the group consisting of hydrogen, ^{_{deuterium, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -COO -, -COOH, -COO ^- Z ⁺ , -COORa, -SO ₃ Rb, -SO ₂ NRcRd, -CONRe, substituted or unsubstituted alkyl with 1 to 20 carbons, and 6 to 20 carbons A group consisting of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups having 2 to 20 carbon atoms.

In an embodiment of the present specification, R7 to R11 are the same or different, each independently selected from the group consisting of ^{_{hydrogen, -SO 3 -, -SO 3 H}} , -SO 3 - Z +, -COO -, -COO - Z + , -COORa, -SO ₃ Rb, and -SO ₂ NRcRd.

In an embodiment of the present specification, R7 to R11 are the same or different, each independently selected from the group consisting of hydrogen, -SO ₃ ^- consisting of Z ^+, and the -COORa ^{_{-, -SO 3 H, -COO -}} , -COO Group.

In one embodiment of this specification, Z ⁺ is ⁺ N(Rf) ₄ , Na ⁺ , or K ⁺ .

In one embodiment of this specification, Z ⁺ is Na ⁺ .

In one embodiment of this specification, Ra to Rf are the same or different from each other, and are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 30 carbons, and substituted 6 to 30 carbons. Or an unsubstituted aryl group and a substituted or unsubstituted heteroaryl group with a carbon number of 2 to 30. Rc and Rd can bond with each other to form a heterocyclic ring containing a nitrogen atom, and Rf can Same or different.

In one embodiment of the present specification, Ra to Rf are the same or different from each other, and are independently selected from hydrogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, A group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, Rc and Rd can be formed by bonding to each other For heterocycles containing nitrogen atoms, Rf may be the same or different.

In one embodiment of this specification, Ra to Rf are the same or different from each other, and are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbons, and substituted 6 to 20 carbons. Or an unsubstituted aryl group and a substituted or unsubstituted heteroaryl group with a carbon number of 2 to 20, Rc and Rd can bond with each other to form a heterocyclic ring containing a nitrogen atom, and Rf can Same or different.

In one embodiment of this specification, Ra is a substituted or unsubstituted methyl group.

In one embodiment of this specification, Ra is a methyl group.

In one embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms.

In an embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen or a linear or branched alkyl group having 3 to 20 carbon atoms.

In one embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen or a branched alkyl group having 3 to 20 carbon atoms.

In one embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of this specification, Rc and Rd are the same or different from each other, Each is independently hydrogen, or a linear or branched alkyl group having 1 to 10 carbon atoms.

In one embodiment of this specification, Rc and Rd are the same or different from each other, and each independently is hydrogen or a branched alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, Rc and Rd are the same or different from each other, and are each independently hydrogen, or substituted or unsubstituted 2-ethylhexyl.

In one embodiment of this specification, Rc and Rd are the same or different from each other, and each independently is hydrogen or 2-ethylhexyl.

In one embodiment of this specification, -SO ₂ NRcRd can be _{represented by -SO 2} NY, and the definitions of Rc and Rd can be applied to the Y.

In one embodiment of this specification, R12 to R15 are the same or different from each other, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 30 carbons, and 6 to 30 carbons. A group consisting of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

In one embodiment of this specification, R12 to R15 are the same or different from each other, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbons, and 6 to 20 carbons. A group consisting of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups having 2 to 20 carbon atoms.

In one embodiment of the present specification, R12 to R15 are the same or different from each other, and are independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbons, and alkyl having 6 to 12 carbons. A group of substituted or unsubstituted aryl groups.

In one embodiment of this specification, R12 and R14 are the same or different from each other, and are each independently hydrogen, substituted or unsubstituted ethyl, or substituted or unsubstituted Substituted propyl.

In one embodiment of this specification, R12 and R14 are the same or different from each other, and are each independently hydrogen, ethyl, n-propyl, or isopropyl.

In one embodiment of the present specification, R13 and R15 are the same or different from each other, and are each independently a substituted or unsubstituted ethyl group or a substituted or unsubstituted phenyl group.

In one embodiment of this specification, R13 and R15 are the same or different from each other, and are each independently an ethyl group, or are selected from the group consisting of methyl, -SO ₂ NHY, -SO ₃ ^- and -SO ₃ H For the phenyl group substituted by more than one substituent in the group, Y is the same as described above.

In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.

In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

In one embodiment of this specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In an embodiment of this specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted ethylene group. Unsubstituted propylene.

In one embodiment of this specification, Q1 and Q2 are the same or different from each other, and each independently is a direct bond, a methylene group, an ethylene group, or a propylene group.

In one embodiment of this specification, Rx is an anionic group or an ammonium structure.

In an embodiment of the present specification, the Rx is an anionic group, said anionic group is chloro (Cl ^-).

In one embodiment of this specification, Rx is an ammonium structure, and the ammonium structure can be represented by the following chemical formula A.

In the chemical formula A, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group.

In one embodiment of this specification, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of this specification, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In an embodiment of this specification, A1 to A4 are the same or different from each other, and are divided into Each is independently hydrogen, or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.

In one embodiment of this specification, a is 0 or 1.

In one embodiment of this specification, a is 0.

In one embodiment of this specification, a is 1.

In an embodiment of this specification, the chemical formula 2 may be any of the following structures.

In the structure, Y is a branched alkyl group having 3 to 20 carbon atoms. Specifically, the Y is 2-ethylhexyl.

表示的含義是指在

的苯基所包含的碳中，在除由甲基取代的部分以外的碳中的任一者可經-SO₂NHY取代。 In the structure, by

The meaning is to refer to

Among the carbons contained in the phenyl group, any one of the carbons other than the part substituted by the methyl group may be _{substituted by -SO 2} NHY.

表示的含義是指在

的苯基所包含的碳中，在除由甲基取代的部分以外的碳中的任一者可經-SO₃ ^-取代。 In the structure, by

The meaning is to refer to

Among the carbons contained in the phenyl group, any one of the carbons other than the part substituted with a methyl group may be substituted _{with -SO 3} ^-.

In one embodiment of this specification, X'is O.

In one embodiment of this specification, X'is NH.

In one embodiment of this specification, L1 is a direct bond, a substituted or unsubstituted alkylene group, or -C(=O)-.

In one embodiment of this specification, L1 is a direct bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or -C(=O)-.

In one embodiment of this specification, L1 is a direct bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or -C(=O)-.

In one embodiment of this specification, L1 is a direct bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or -C(=O)-.

In one embodiment of this specification, L1 is a direct bond.

In one embodiment of this specification, L1 is substituted or unsubstituted methylene, substituted or unsubstituted ethylene, or substituted or unsubstituted ethylene.

In one embodiment of the present specification, L1 is methylene, ethylene, or ethylene.

In one embodiment of this specification, L1 is -C(=O)-.

In one embodiment of this specification, L2 is a direct bond, -C(=O)-, or -L'-O(C=O)-.

In one embodiment of this specification, L2 is a direct bond.

In one embodiment of this specification, L2 is -C(=O)-.

In one embodiment of this specification, L2 is -L'-O(C=O)-.

In one embodiment of the present specification, L'is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.

In one embodiment of the present specification, L'is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

In one embodiment of the present specification, L'is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of this specification, L'is a substituted or unsubstituted methylene group.

In one embodiment of this specification, L'is a methylene group.

In one embodiment of the present specification, T1 to T3 are the same or different from each other, and are each independently hydrogen, a hydroxyl group, and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, T1 to T3 are the same or different from each other, and are each independently hydrogen, a hydroxyl group, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of this specification, T1 to T3 are the same or different from each other, and are each independently hydrogen, a hydroxyl group, and a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In an embodiment of the present specification, T1 to T3 are the same or different from each other, and are each independently hydrogen, a hydroxyl group, and a substituted or unsubstituted methyl group.

In one embodiment of this specification, T1 is hydrogen or methyl.

In one embodiment of this specification, T2 is hydrogen.

In one embodiment of this specification, T3 is hydrogen, a hydroxyl group, or a methyl group substituted with an amino group.

According to an embodiment of this specification, the chemical formula 1 can be represented by the following chemical formula 3.

是指與其他取代基或鍵結部連接的部分，X'、L1、L2、T1至T3、t2及t3與在所述化學式1中定義的內容相同。 In the chemical formula 3,

It refers to a part connected to other substituents or bonding parts, and X', L1, L2, T1 to T3, t2, and t3 are the same as those defined in the chemical formula 1.

In an embodiment of this specification, the chemical formula 1 can be formed by the following Any one of the structure is shown, but it is not limited to this. The chemical formula 1 is a polymerized part formed by any one of the following structures.

In one embodiment of the present specification, the binder resin may further include one or more structures represented by any one of the following Chemical Formula 4 to Chemical Formula 7.

是指與其他取代基或鍵結部連接的部分，L41、L51、L52、及L61彼此相同或不同，分別獨立地為經取代或未經取代的伸烷基，X1、X2、Y1、Y2、Z1及Z2彼此相同或不同，分別獨立地為氫、經取代或未經取代的烷基、經取代或未經取代的環烷基、或者經取代或未經取代的芳基，x2為0至5的整數，在x2為2以上的情況下，X2彼此相同或不同。 In the chemical formula 4 to the chemical formula 7,

Refers to the part connected to other substituents or bonding parts, L41, L51, L52, and L61 are the same or different from each other, and are each independently a substituted or unsubstituted alkylene group, X1, X2, Y1, Y2, Z1 and Z2 are the same or different from each other, and are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl, x2 is 0 to An integer of 5, and when x2 is 2 or more, X2 is the same as or different from each other.

In one embodiment of the present specification, L41, L51, L52, and L61 are the same or different from each other, and are each independently a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.

In one embodiment of the present specification, L41, L51, L52, and L61 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

In one embodiment of the present specification, L41, L51, L52, and L61 are the same or different from each other, and are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of this specification, L41, L51, L52, and L61 are the same or different from each other, and each independently is a substituted or unsubstituted methylene group.

In one embodiment of this specification, L41, L51, L52, and L61 are mutually The same or different, each independently is a methylene group.

In one embodiment of this specification, X1, X2, Y1, Y2, Z1, and Z2 are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a carbon number It is a substituted or unsubstituted cycloalkyl group of 3 to 30, or a substituted or unsubstituted aryl group of 6 to 30 carbons.

In one embodiment of this specification, X1, X2, Y1, Y2, Z1, and Z2 are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a carbon number It is a substituted or unsubstituted cycloalkyl group of 3 to 20, or a substituted or unsubstituted aryl group of 6 to 20 carbons.

In one embodiment of this specification, X1, X2, Y1, Z1, and Z2 are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a carbon number of 3. A substituted or unsubstituted cycloalkyl group of to 10, or a substituted or unsubstituted aryl group of 6 to 12 carbons.

In one embodiment of this specification, X1 and Y1 are substituted or unsubstituted methyl groups.

In one embodiment of this specification, X1 and Y1 are methyl groups.

In one embodiment of this specification, X2 is hydrogen.

In one embodiment of this specification, Y2 is substituted or unsubstituted cyclohexyl, or substituted or unsubstituted phenyl.

In one embodiment of this specification, Y2 is cyclohexyl or phenyl.

In one embodiment of this specification, Z1 is a substituted or unsubstituted phenyl group.

In one embodiment of this specification, Z1 is a phenyl group.

In one embodiment of this specification, Z2 is a substituted or unsubstituted methyl group.

In one embodiment of this specification, Z2 is a methyl group.

In one embodiment of this specification, the chemical formula 4 can be represented by the following structure, but it is not limited to this.

In one embodiment of this specification, the chemical formula 5 can be represented by the following structure, but it is not limited to this.

In one embodiment of this specification, the chemical formula 6 can be represented by the following structure, but it is not limited to this.

In one embodiment of this specification, the chemical formula 7 can be represented by the following structure, but it is not limited to this.

In an embodiment of this specification, the binder resin may be a copolymer including one or more structures selected from the structure represented by the chemical formula 1 and the chemical formula 4 to the chemical formula 7 .

An embodiment of this specification provides a photosensitive resin composition, based on the total weight of the photosensitive resin composition, containing: 0.1% to 30% by weight of the dibenzopiperan dye; 1% by weight To 40% by weight of the binder resin including the structure represented by Chemical Formula 1; 1% to 40% by weight of the polyfunctional monomer; 0.1% to 10% by weight of the photoinitiator; And the balance is solvent.

When each component of the photosensitive resin composition satisfies the aforementioned ranges, a photosensitive resin composition for color filters having excellent heat resistance and chemical resistance can be obtained.

In an embodiment of this specification, the weight average molecular weight of the binder resin is 5,000 g/mol to 30,000 g/mol. Preferably, it may be 5,000 g/mol to 20,000 g/mol.

When the binder resin satisfies the weight average molecular weight range, a color filter film excellent in heat resistance and chemical resistance can be obtained.

The weight average molecular weight is one of the average molecular weights used based on the molecular weight of a certain polymer substance with non-uniform molecular weight, and is determined by using the weight fraction to determine the molecular weight of the component molecular species of the polymer compound having a molecular weight distribution. The value obtained by averaging.

The weight average molecular weight can be measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) analysis.

In one embodiment of this specification, the photosensitive resin composition may further include one selected from the group consisting of pigments and dyes.

That is, the photosensitive resin composition may further include at least one of a dye and a pigment in addition to the compound of the chemical formula 1. For example, the photosensitive resin composition may only include the compound of the chemical formula 1, but may also include the compound of the chemical formula 1 and one or more dyes, or the compound of the chemical formula 1 and one or more pigments, Or include the compound of the chemical formula 1, more than one dye and more than one pigment.

The dye may be an anthraquinone-based, azaporphyrin-based, azo-based, triarylmethane-based, phthalocyanine-based, or dipyrrolopyrrole-based dye, but is not limited thereto.

The pigment may be a copper phthalocyanine blue pigment or a purple pigment (Pigment violet 23), but it is not limited thereto. Specifically, the pigment may be C.I pigment blue (pigment blue) 15:6.

The binder resin may use a copolymer resin of a polyfunctional monomer that imparts mechanical strength to the film and a monomer that imparts alkali solubility, and may further include a binder commonly used in the corresponding technical field.

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

As specific examples of the unsaturated carboxylic acid esters, benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate, and (meth)acrylate can be selected as specific examples. Base) dimethylaminoethyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate Base) ethylhexyl 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, octyloxy-2-hydroxypropyl (meth)acrylate, glycerol (methyl) Base) acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethyl Glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, phenoxydiethylene Alcohol (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, ( Tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluoro(meth)acrylate Composed of decyl ester, tribromophenyl (meth)acrylate, α-hydroxymethyl methacrylate, α-hydroxy ethyl methacrylate, α-hydroxy propyl methacrylate and α-hydroxy butyl methacrylate In the group, but not limited to these.

As specific examples of the aromatic vinyl monomers, styrene, α-methylstyrene, (ortho, m, and p)-vinyl toluene, (ortho, m, and p)-methoxy But it is not limited to the group consisting of methyl styrene and (ortho, meta, p)-chlorostyrene.

As specific examples of the unsaturated ethers, it can be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but it is not limited to these.

As specific examples of the unsaturated imines, N-phenylmaleimines, N-(4-chlorophenyl)maleimines, and N-(4-hydroxyphenyl) can be selected. Maleimines and N-cyclohexylmaleimines are in the group, but they are not limited to these.

As the acid anhydride, there are maleic anhydride, methylmaleic anhydride, tetrahydrophthalic anhydride, etc., but it is not limited to these.

The monomer imparting alkali solubility is not particularly limited if it contains an acid group. For example, it is preferably selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, Monomethyl maleic acid, 5-norbornene-2-carboxylic acid, phthalic acid Mono-2-((meth)acryloyloxy) ethyl ester, succinic acid mono-2-((meth)acryloyloxy) ethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate There is more than one kind in the group, but it is not limited to these.

In one embodiment of this specification, the multifunctional monomer may be dipentaerythritol pentaacrylate.

According to an embodiment of the present specification, the acid value of the binder resin may be 70 mg KOH/g to 120 mg KOH/g.

The acid value of the binder resin can be determined by titration with a 0.1N potassium hydroxide (KOH) methanol solution.

The photoinitiator is not particularly limited as long as it is an initiator that generates free radicals by light to initiate crosslinking. For example, it may be selected from acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds. And one or more of the group consisting of oxime-based compounds.

The acetophenone 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-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Benzoin Butyl Ether, 2,2-Dimethoxy-2-phenylacetophenone, 2-Methyl-(4-methylthio)phenyl-2-morpholin-1-propan-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-morpholinopropane-1-one, etc. , Is not limited to this.

As the biimidazole-based compound, there are 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'-bi Imidazole, 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. are not limited to this.

The triazine compounds include 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4- Bis(trichloromethyl)-s-triazin-6-yl]phenylthio)propionic acid 1,1,1,3,3,3-hexafluoroisopropyl ester, 2-{4-[2,4- Bis(trichloromethyl)-s-triazin-6-yl]phenylthio) ethyl acetate, 2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] Phenylthio}2-epoxyethyl acetate, 2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}cyclohexyl acetate, 2- {4-[2,4-Bis(trichloromethyl)-s-triazin-6-yl]phenylthio}benzyl acetate, 3-{chloro-4-[2,4-bis(trichloromethyl) )-S-triazine-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propanamide , 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylamino) (Phenyl)-1,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, etc., and not limited to these .

The oxime compound includes 1,2-octanedione-1-(4-phenylthio)phenyl-2-(phthaloyl oxime) (Ciba-Geigy Company, CGI -124), ethyl ketone-1-(9-ethyl)-6-(2-methylbenzyl-3-yl)-1-(O-acetyloxime) (CGI-242), N -1919 (Adeka), etc., are not limited to this.

The photoinitiator may be SPI-03 of Samyang Corporation.

The solvent can be selected from 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 ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-tri Chloroethane, 1,1,2-trichloroethylene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, third Butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, 3 -Methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol mono One or more of the group consisting of methyl ether, but it is not limited to this.

In an embodiment of this specification, the solvent may be propylene glycol monomethyl ether acetate and/or 3-methoxybutyl acetate.

In one embodiment of this specification, the content of the dibenzopyran dye is 0.1% by weight to 30% by weight based on the total weight of the solid content in the photosensitive resin composition, including the formula represented by chemical formula 1. The content of the binder resin of the structure is 1% to 40% by weight, and the content of the photoinitiator is 0.1% to 10% by weight.

Based on the total weight of the solid content in the photosensitive resin composition, when each constituent element contained in the photosensitive resin composition satisfies the above range, there is an effect of excellent heat resistance and chemical resistance.

The total weight of the solid content refers to the total weight of the components other than the solvent in the photosensitive resin composition. The solid content and the weight% standard based on the solid content of each component can be measured by the usual analytical means used in this field, such as liquid chromatography or gas chromatography.

According to an embodiment of this specification, the photosensitive resin composition further includes an antioxidant, an adhesive auxiliary, a photocrosslinking sensitizer, a curing accelerator, an adhesion accelerator, a surfactant, and a thermal polymerization inhibitor. One or two or more additives in the group consisting of UV absorbers, adhesives, dispersants and leveling agents.

In an embodiment of the present specification, the additives can be specifically selected from the group consisting of antioxidants, surfactants, and adjuvants.

In addition, the photosensitive resin composition may further include a multi-thiol agent.

According to an embodiment of this specification, the content of the additive is 0.1% by weight to 20% by weight based on the total weight of the solid content in the photosensitive resin composition.

The photocrosslinking sensitizer can use one or more selected from the group consisting of the following compounds: benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4- Bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl phthalate, 3,3-dimethyl-4-methyl Benzophenone compounds such as oxybenzophenone, 3,3,4,4-tetra(tert-butylperoxycarbonyl)benzophenone; 9-fluorenone, 2-chloro-9-fluorenone , 2-methyl-9-fluorenone and other fluorenone compounds; thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyl oxygen Thioxanthone compounds such as thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone; xanthone compounds such as xanthone and 2-methylxanthone ; Anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tertiary butylanthraquinone, 2,6-dichloro-9,10-anthraquinone and other anthraquinone compounds; 9-phenyl acridine , 1,7- Acridine compounds such as bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane; benzyl, 1, Dicarbonyl compounds such as 7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione and 9,10-phenanthrenequinone; 2,4,6-trimethylbenzyl Phosphine oxide compounds such as diphenyl phosphine oxide and bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentyl phosphine oxide; 4-(dimethylamino) Benzoate compounds such as methyl benzoate, ethyl 4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2 ,5-bis(4-diethylaminobenzylidene)cyclopentanone, 2,6-bis(4-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4-di Ethylaminobenzylidene)-4-methyl-cyclopentanone and other amino synergists; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2- Benzothiazolyl)-7-(diethylamino)coumarin, 3-benzyl-7-(diethylamino)coumarin, 3-benzyl-7-methoxy -Coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzopyrano Coumarin compounds such as [6,7,8-ij]-quinazine-11-one; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzylidene acetophenone ; 2-benzyl methylene, 3-methyl-b-naphththiazoline.

The curing accelerator is used to improve curing and mechanical strength. Specifically, it can be selected from the group consisting of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2,5-dimercapto- 1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetra(3-mercaptopropionate), pentaerythritol-tris(3-mercaptopropionate), pentaerythritol -Tetra(2-mercaptoacetate), pentaerythritol-tris(2-mercaptoacetate), trimethylolpropane-tris(2-mercaptoacetate) and trimethylolpropane-tris(3-mercapto) One or more of the group consisting of propionate).

The adjuvant can be used by the users in the field, in one implementation In the form, the adhesive agent may be KBM-503.

The polythiol agent can be commonly used in the art. In one embodiment, the polythiol agent can be PE-01.

As the adhesion promoter, a group selected from the group consisting of methacryloxypropyltrimethoxysilane, methacryloxypropyldimethoxysilane, methacryloxypropyltriethoxy One or more of methacryloyl silane coupling agents such as methacryloyl silane, methacryloyl oxypropyl dimethoxy silane, etc. As the alkyl trimethoxy silane, a group selected from octyl trimethoxy silane, ten One or more of dialkyltrimethoxysilane, octadecyltrimethoxysilane, etc.

The surfactant is a silicon-based surfactant or a fluorine-based surfactant. Specifically, the silicon-based surfactant can be BYK-077 and BYK-Chemie (BYK-Chemie). BYK-085, 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 BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK BYK-375, BYK-380, BYK-390, etc. As a fluorine-based surfactant, DIC (DaiNippon Ink & Chemicals) can be used ))company's F-114, F-177, F-410, F-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-554, 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 limited to these.

In one embodiment of this specification, the surfactant may be a fluorine-based surfactant, and specifically may be F-554 of DIC Corporation.

The antioxidant may be one or more selected from the group consisting of hindered phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphine-based antioxidants, but it is not limited to these . Specific examples of the antioxidant include: phosphoric acid-based heat stabilizers such as phosphoric acid, trimethyl phosphate, or triethyl phosphate; such as 2,6-di-tert-butyl-p-cresol, octadecane 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate, tetrabis[methylene-3-(3,5-di-tert-butyl-4-hydroxy (Phenyl) propionate) methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,5- Di-tert-butyl-4-hydroxybenzyl diethyl phosphite, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-g,t-butyl Phenol 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol) or bis[ 3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]diol ester (Bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl) butanoicacid]glycol ester) and other hindered phenols are primary antioxidants; such as phenyl-α- Amine-based secondary antioxidants such as naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine or N,N'-bis-β-naphthyl-p-phenylenediamine ; Dilauryl disulfide, dilauryl thiopropionate, distearyl thiopropionate, mercaptobenzothiazole or tetramethylthiuram disulfide tetrabis[methylene-3- (Lauryl thio) propionate) sulfur (Thio) secondary antioxidants such as methane; or such as triphenyl phosphite, tris (nonyl phenyl) phosphite, triisodecyl phosphite, Bis(2,4-dibutylphenyl) Pentaerythritol Diphosphite (Bis(2,4-ditbutylphenyl)Pentaerythritol Diphosphite) or (1,1'-biphenyl)-4,4'-diyl diphosphite Tetrakis[2,4-bis(1,1-dimethylethyl)phenyl] phosphonate ((1,1'-Biphenyl)-4,4'-Diylbisphosphonous acid tetrakis[2,4-bis(1 ,1-dimethylethyl)phenyl]ester) and other secondary antioxidants.

In one embodiment of the present specification, the antioxidant may be a hindered phenol-based antioxidant, specifically, Songnox-1010 from Songyuan Industry.

As the ultraviolet absorber, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole, alkoxybenzophenone, etc. can be used, but It is not limited to this, and it can be used by any user in the field.

As the thermal polymerization inhibitor, for example, it may be selected from the group consisting of p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, and N-nitroso Benzyl phenyl hydroxylamine ammonium salt, N-nitrosophenyl hydroxylamine aluminum salt, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, benzoquinone, 4,4-sulfur Bis (3-methyl-6-tertiary butyl phenol), 2,2-methylene bis (4-methyl-6-tertiary butyl phenol), 2-mercaptoimidazole and phenothiazine (phenothiazine) ) In a group There are more than one, but it is not limited to these, and may include those generally known in the technical field.

The dispersant can be used in the following methods: a method of internally adding to the pigment in a form in which the pigment is surface-treated in advance, or a method of externally adding to the pigment. As the dispersant, compound-type, nonionic, anionic, or cationic dispersants can be used, and examples thereof include fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These can be used individually or in combination of two or more types.

Specifically, the dispersant may be selected from polyalkylene glycols and their esters, polyoxyalkylene polyols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid One or more of the group consisting of salt, carboxylate, carboxylate, alkyl amine alkylene oxide adduct, and alkyl amine, but it is not limited to this.

The leveling agent can be polymeric or non-polymeric. Specific examples of polymeric leveling agents include polyethyleneimine, polyamide amines, and reaction products of amines and epoxides. Specific examples of non-polymeric leveling agents include non-polymer sulfur-containing products. Compounds and non-polymer nitrogen-containing compounds, but not limited to these, can be used by users generally in the field.

One embodiment of this specification provides a photoresist manufactured using the photosensitive resin composition.

In more detail, it provides a photoresist which can form a film or pattern form by applying the photosensitive resin composition of this specification to a base material and hardening by a suitable method.

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

As a light source for curing the photosensitive resin composition of this specification, there are, for example, mercury vapor arc (arc), carbon arc, xenon (Xe) arc, etc., which emit light having a wavelength of 250 nm to 450 nm, but it is not necessarily limited to these. .

The photosensitive resin composition in this specification can be used for pigment dispersion photoresist for thin film transistor liquid crystal display (TFT LCD) color filter manufacturing, thin film transistor liquid crystal display (TFT LCD) or Photoresist for black matrix formation of organic light-emitting diodes, photoresist for overcoat formation, colomn spacer photoresist, photocurable paint, photocurable ink, photocurable adhesive, printing plate , The use of photoresist for printed wiring board, plasma display panel (Plasma Display Panel, PDP), etc., is not particularly limited.

According to an embodiment of this specification, a color filter including the photoresist is provided.

The color filter can be manufactured using a photosensitive resin composition containing a binder resin containing the structure represented by the chemical formula 1. The photosensitive resin composition is coated on a substrate to form a coating film, and the coating film is exposed, developed, and cured, thereby forming a color filter.

The substrate can be glass plate, silicon wafer, polyethersulfone (PES), polycarbonate (PC) and other plastics. There are no particular restrictions on the type of rubber-based boards and the like.

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 outer coating.

Between the color pixels of the color filter, in order to improve the contrast, a grid-like black pattern called a black matrix can be arranged. As the material of the black matrix, chromium can be used. In this case, the following method can be used: chromium is vapor-deposited on the entire glass substrate, and a pattern is formed by etching. However, considering the high cost of the manufacturing process, the high reflectivity of chromium, and the environmental pollution caused by the waste liquid of chromium, a resin black matrix using a pigment dispersion method capable of fine processing can also be used.

The black matrix can use black pigments or black dyes as color materials. For example, carbon black can be used alone, or carbon black can be mixed with coloring pigments. In this case, since coloring pigments with insufficient light-shielding properties are mixed, it 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 will not decrease.

An embodiment of this specification provides a display device including the color filter.

The display device may be a plasma display panel (Plasma Display Panel, PDP), a light emitting diode (Light Emitting Diode, LED), an organic light emitting element (Organic Light Emitting Diode, OLED), a liquid crystal display device (Liquid Crystal Display, LCD), Thin Film Transistor-Liquid Crystal Display (LCD-TFT) and cathode ray Any of the tubes (Cathode Ray Tube, CRT).

Hereinafter, in order to specifically explain this specification, examples are given for detailed description. However, the embodiments of this specification can be modified into various other forms, and the scope of this specification is not construed as being limited to the embodiments described below. The examples of this specification are provided for more complete description of this specification for those with average knowledge in the field.

<Example>

1. Synthesis Example of Dibenzopyran Dyes

[Synthesis Example 1]

To 25g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) was added 5g of [A] (12.34mmol, 1eq), 7.48g of 2,6-dimethylaniline (2,6 -dimethylaniline) (61.692mmol, 5eq), heated to 150°C and stirred. After reacting at 150°C for a duration of 4 hours, it was allowed to cool to normal temperature, and then slowly added to 500 mL of 1M hydrochloric acid (HCl) aqueous solution. After stirring for a duration of 1 hour after the addition, the precipitate was filtered under reduced pressure. The filtrate was added to methanol (MeOH) solvent at 60°C for a duration of 1 hour After internal reflux (reflux), filtration under reduced pressure was performed. It dried in a vacuum oven to obtain 3.07 g of [A-1] (yield 43.0%).

Ionization mode: Atmospheric Pressure Chemical Ionization (APCI)+: m/z=574[M+H]+, Exact Mass: 574

2. Binder synthesis example

[Synthesis Example 2]

Add 51.75 mol% of benzyl methacrylate, 8.63 mol% of N-phenylmaleimide, 10.35 mol% of styrene, and 29.28 mol% of methacrylic acid to the reaction vessel and mix with the solvent, mix in a nitrogen environment and heat to 60°C. After that, 10 parts by weight of the thermal polymerization initiator V65 (2,2-azobis(2,4-dimethylvaleronitrile) (2,2-Azobis( 2,4-dimethylvaleronitrile))) and reacted for 16 hours to produce adhesive resin A.

The acid value of the produced adhesive resin A was 125 mg KOH/g, and the weight average molecular weight was 8,200. The produced adhesive resin A has the structural unit shown below.

[Synthesis Example 3]

17.7 mol% of methacrylic acid, 42.9 mol% of glycidyl methacrylate, and 39.4 mol% of styrene were added to the reaction vessel, mixed in a nitrogen environment, and heated to 60°C. The production was carried out in the same manner as in Synthesis Example 2 to produce the binder resin B.

The acid value of the produced adhesive resin B was 85 mg KOH/g, and the weight average molecular weight was 10,700.

The produced adhesive resin B has the structural unit shown below.

[Synthesis Example 4]

36.49 mol% of styrene, 39.62 mol% of glycidyl methacrylate, 18.80 mol% of methacrylate, and 5.10 mol% of benzophenone methacrylate were added, and the adhesive was manufactured by the same method as in Synthesis Example 2 Agent resin C.

The acid value of the produced adhesive resin C was 88 mg KOH/g, and the weight average molecular weight was 8,300.

The produced adhesive resin C has the structural unit shown below.

[Synthesis Example 5]

29.87mol% of styrene, 40.00mol% of glycidyl methacrylate, 20.02mol% of methacrylate, and 10.12mol% of benzophenone methacrylate were added, and the adhesive was manufactured in the same manner as in Synthesis Example 2 Agent resin D.

The acid value of the produced adhesive resin D was 88 mg KOH/g, and the weight average molecular weight was 9,200.

The produced adhesive resin D has the same structural unit as the adhesive resin C.

[Synthesis Example 6]

Input 36.49mol% styrene, 36.92mol% glycidyl methacrylate, 18.80mol% methacrylate, N-(4-benzoylphenyl) methacrylamide (N-(4-benzoylphenyl) methacrylamide) 5.10 mol%, and it was produced in the same manner as in Synthesis Example 2 to produce a binder resin E.

The acid value of the produced adhesive resin E was 78 mg KOH/g, and the weight average molecular weight was 7,900.

The produced adhesive resin E has the structural unit shown below.

[Synthesis Example 7]

Add 36.49 mol% of styrene, 36.92 mol% of cyclohexyl methacrylate, 18.80 mol% of methacrylate, and 5.10 mol% of benzophenone methacrylate, and manufacture the adhesive in the same manner as in Synthesis Example 2 Agent resin F.

The acid value of the produced adhesive resin F was 82 mg KOH/g, and the weight average molecular weight was 8,500.

The produced adhesive resin F has the structural unit shown below.

[Manufacturing of photosensitive resin composition]

[Comparative Example 1]

The composition shown in the following Table 1 was mixed, and the photosensitive resin composition of the comparative example 1 was manufactured.

[Production of photosensitive resin composition Comparative Example 2 to Comparative Example 4 and Example 1 to Example 4]

Except for the types and contents of the applied binder resin and photoinitiator described in Table 2 below, the same ingredients and contents as those described in Table 1 were used to manufacture Comparative Examples 2 to 4 and Examples 1 to the photosensitive resin composition of Example 4.

<Experimental example>

[Substrate production]

The photosensitive resin composition manufactured by the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 4 was spincoated on glass (5cm×5cm), and heat treatment was performed at 110°C for 70 seconds. And a film is formed. After exposing the film with a photo mask under a high-pressure mercury lamp with ^{an energy of 40 mJ/cm 2} , the pattern was developed with an alkaline aqueous solution of potassium hydroxide (KOH) and washed with distilled water. After removing the distilled water, post-heat treatment was performed at 230°C for 20 minutes to obtain a color pattern.

[Evaluation of heat resistance]

With respect to the post-heat-treated substrate manufactured under the conditions described above, an absorption spectrum in the wavelength range of 380 nm to 780 nm was obtained using a spectrophotometer (MCPD, Otsuka Co., Ltd).

The post-heat-treated substrate was additionally processed at 230°C for 120 minutes, and the transmittance spectrum was obtained under the same equipment and the same measurement range.

Using the values L*, a*, and b* obtained from the absorption spectrum obtained by using the C light source as the backlight, ΔEab (heat resistance) was calculated by the following formula 1 and shown in Table 3 below.

[Equation 1] △Eab(L*, a*, b*)={(△L*) ² +(△a*) ² +(△b*) ² } ^1/2

A small ΔEab value means a small color change, and indicates excellent heat resistance.

[Chemical resistance evaluation]

After cutting the substrate subjected to post-heat treatment to 1cm×5cm, measure 380nm with a spectrophotometer (MCPD, Otsuka Co., Ltd) Absorption spectrum to 780nm wavelength range.

After obtaining the spectrum, it was immersed in 16 g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) solvent, and then left to stand at room temperature for 10 minutes, and then cleanly washed with distilled water. Obtain the transmittance spectrum under the same equipment and the same measuring range.

The above-mentioned [Equation 1] was used for calculation using the spectrum before and after immersion, and ΔEab (chemical resistance) is shown in Table 3 below.

A small △Eab value means a small color change, which indicates excellent chemical resistance.

According to the table 3, it was confirmed that the ΔEab value of Examples 1 to 4 was smaller than that of Comparative Examples 1 to 4, and the photosensitive material with excellent heat resistance and chemical resistance was used in one embodiment of this specification. Color filters can be obtained from the resin composition.

Claims (9)

A photosensitive resin composition comprising: a dibenzopiperan dye; a binder resin comprising the following structure represented by Chemical Formula 1; a multifunctional monomer; a photoinitiator; and a solvent,

In chemical formula 1,

It refers to the part connected with other substituents or bonding parts, X'is O or NH, L1 is -C(=O)-, L2 is direct bond or -L'-O(C=O)-, L' Is a substituted or unsubstituted alkylene group, T1 to T3 are the same or different from each other, and are each independently hydrogen, a hydroxyl group, or a substituted or unsubstituted alkyl group, t2 is an integer from 0 to 4, and t2 is In the case of 2 or more, T2 is the same or different from each other, t3 is an integer from 0 to 5, and when t3 is 2 or more, T3 is the same or different from each other. The photosensitive resin composition according to the first item of the patent application, wherein the binder resin containing the structure represented by the chemical formula 1 further contains a non-volatile compound derived from a cyclic ether structure having a carbon number of 2 to 4 Saturated compound unit. The photosensitive resin composition described in item 1 of the scope of patent application, wherein the dibenzopyran dye is represented by the following chemical formula 2:

In Chemical Formula 2, R1 to R6 are the same or different from each other, and are independently selected from hydrogen, deuterium, halogen, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and the group consisting of a substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, R7 to R11 are the same or different and each independently selected from the group consisting of hydrogen, deuterium, -OH, -SO ₃ ^{- _{, -SO 3 H, -SO 3 -}} Z +, -COO -, -COOH, -COO - Z +, -COORa, -SO 3 Rb, -SO 2 NRcRd, -CONRe, a substituted or unsubstituted alkyl Group, substituted or unsubstituted aryl group, and substituted or unsubstituted heteroaryl group, Z ⁺ represents ⁺ N(Rf) ₄ , Na ⁺ , or K ⁺ , Ra to Rf are each other Same or different, each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, Rc and Rd can be bonded to each other to form a heterocyclic ring containing a nitrogen atom, Rf can be the same or different, R7 to R11, at least one of ^{_{-SO 3 -, -SO 3 H,}} -SO 3 - Z +, -COO -, -COO ^- Z ⁺ , -COORa, -SO ₃ Rb, or -SO ₂ NRcRd, R12 to R15 are the same or different from each other, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or A group consisting of an unsubstituted aryl group and a substituted or unsubstituted heteroaryl group, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, or a substituted or unsubstituted alkylene group , Rx is an anionic group or ammonium structure, and a is 0 or 1. The photosensitive resin composition according to item 1 of the scope of patent application, wherein based on the total weight of the photosensitive resin composition, it contains: 0.1% to 30% by weight of the dibenzopiperan dye; 1% by weight to 40% by weight containing the structure represented by the chemical formula 1 The binder resin; 1% to 40% by weight of the polyfunctional monomer; 0.1% to 10% by weight of the photoinitiator; and the balance being the solvent. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the binder resin is 5,000 g/mol to 30,000 g/mol. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further includes one selected from the group consisting of pigments and dyes. A photoresist manufactured using the photosensitive resin composition described in any one of items 1 to 6 of the scope of patent application. A color filter comprising the photoresist as described in item 7 of the scope of patent application. A display device includes the color filter as described in item 8 of the scope of patent application.