KR20200069059A - Colorant composition, photosensitive resin composition, photo resist, color filter, and display device - Google Patents

Abstract

The present invention relates to a color material composition comprising a polymer including a unit represented by chemical formula 1, to a photosensitive resin composition comprising the same, to a photosensitive material, to a color filter, and to a display device. The color material composition has excellent heat resistance and sensitivity.

Description

Colorant composition, photosensitive resin composition, photosensitive material, color filter, and display device {COLORANT COMPOSITION, PHOTOSENSITIVE RESIN COMPOSITION, PHOTO RESIST, COLOR FILTER, AND DISPLAY DEVICE}

This specification relates to a color material composition and a photosensitive resin composition. In addition, the present specification relates to a photosensitive material, a color filter, and a display device manufactured using the photosensitive resin composition.

In recent years, in color filters, performance characterized by high luminance and high contrast ratio is required. In addition, one of the main objectives of the development of a display device is to differentiate display device performance by improving color purity and to improve productivity in a manufacturing process.

Since the pigment type used as a color material of a color filter existed in a color photoresist in a particle dispersion state, it was difficult to control the brightness and contrast ratios according to the pigment particle size and distribution control. In the case of pigment particles, aggregation and dispersibility are poor in a color filter, and multiple scattering of light occurs due to large particles aggregated. Scattering of the polarized light has been pointed out as a main factor that lowers the contrast ratio. Efforts are being made to improve the luminance and contrast ratio through ultra-fine atomization and dispersion stabilization of the pigment, but the degree of freedom is limited in selecting a color material for realizing color coordinates for a high-purity display device. In addition, the pigment dispersion method using color materials, especially pigments, which has already been developed, has reached a limit in improving the color purity, brightness, and contrast ratio of color filters using the same.

Accordingly, there is a need to develop a new color material capable of improving color purity, improving color reproduction, brightness and contrast ratio.

Korean Patent Publication No. 2001-0009058

The present inventors intend to provide a colorant composition and a photosensitive resin composition, a photosensitive material prepared using the same, a color filter, and a display device.

An exemplary embodiment of the present specification provides a color material composition comprising a polymer comprising a unit represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

M is a transition metal or a metal after transition,

X is a halogen group; Nitrile group; O(C=O)CH ₃ ; ONO ₂ ; Or OSO ₂ ,

a is 0 or 1,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring,

x1 is an integer from 0 to 5, and when 2 or more, R1 is the same or different from each other,

x2 is an integer from 0 to 5, and when 2 or more, R2 is the same or different from each other,

x3 is an integer from 0 to 4, and when 2 or more, R3 is the same or different from each other,

y1 and y2 are the same as or different from each other, and each independently 0 or 1,

A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

* Is a site bonded to the polymer chain.

An exemplary embodiment of the present specification, a color material composition comprising a polymer comprising a unit represented by the formula (1); Binder resin; Polyfunctional monomers; And it provides a photosensitive resin composition comprising a photoinitiator.

One embodiment of the present specification provides a photosensitive material comprising the photosensitive resin composition or a cured product.

An exemplary embodiment of the present specification provides a color filter including the photosensitive material.

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

The composition comprising the polymer according to one embodiment of the present specification may be used as a color material for a display cultivator filter. The color material composition of the present invention is excellent in heat resistance and sensitivity, and is a new color material for color filters.

Hereinafter, the present specification will be described in more detail.

According to an exemplary embodiment of the present specification, to provide a color material composition comprising a polymer comprising a unit represented by the formula (1). When the compound represented by Chemical Formula 1 is used as a color material of a photosensitive resin composition, heat resistance and sensitivity can be improved, and a desired pattern can be formed.

The polymer containing the unit represented by the formula (1) is an organometallic compound, and the inventors have found that the performance is excellent when applied as a color filter for a photosensitive resin composition. The linkage of the aromatic ring-C-N=C-C-N=C-aromatic ring can shift the bandgap and shift the absorption spectrum through long conjugation. In addition, the polymer of the present invention is superior in heat resistance and chemical resistance compared to monomers.

According to an exemplary embodiment of the present specification, the polymer comprising a unit represented by the formula (1) is a random polymer, alternating polymer or block polymer.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification,'unit' is a repeating structure included in a polymer monomer, and refers to a structure in which the monomer is bonded to the polymer by polymerization.

In the present specification, the meaning of'comprising units' means being included in the main chain in the polymer.

은 연결되는 부위를 의미한다.In this specification,

Means a site to be connected.

In this specification, * is a site that is attached to the chain of the polymer.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Sulfonic acid group; Sulfonate groups; Nitrile group; Nitro group; Hydroxy group; -COOH; Alkyl groups; Cycloalkyl group; Haloalkyl group; Alkenyl group; Amine group; Aryl group; Heteroaryl group; Acryloyl group; Acrylate groups; And one or more substituents selected from the group comprising a heterocyclic group containing one or more of N, O, or S atoms, or having no substituents.

According to an exemplary embodiment of the present specification, the "substituted or unsubstituted" is, deuterium; Halogen group; Sulfonic acid group; Sulfonate groups; Nitrile group; Nitro group; -COOH; Alkyl groups; Cycloalkyl group; Haloalkyl group; Amine group; Aryl group; And one or more substituents selected from the group containing heteroaryl groups.

According to an exemplary embodiment of the present specification, the "substituted or unsubstituted" is, deuterium; Halogen group; Nitro group; Alkyl groups; Aryl group; And one or more substituents selected from the group containing heteroaryl groups.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In one embodiment of the present specification, the sulfonate group may be represented by -SO ₃ M, and M may be any one of the Group 1 elements of the periodic table, for example, Na, but is not limited thereto.

In one embodiment of the present specification, the amine group is -NH ₂ ; -ND ₂ ; -NDH; Alkylamine groups; Cycloalkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but may be 1 to 30 days. In addition, it may be 1 to 20, and may be 1 to 10. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, cycloalkylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl -Anthracenylamine group, diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenyl naphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenyl terphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenyl fluorenylamine group and the like, but is not limited thereto.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-ox Tilgi, and the like, but are not limited to these.

In the present specification, the alkenyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 2 to 25. As a specific example, an alkenyl group substituted with an aryl group such as a stylbenyl group or a styrenyl group is preferred, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, 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 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20, and may be 6 to 10. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylene group, triphenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, and S. The number of carbon atoms is not particularly limited, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; Furanyl group; Pyrrol group; Imidazolyl group; Thiazolyl group; Oxazolyl group; Oxadiazolyl group; Pyridyl group; Bipyridyl group; Pyrimidyl group; Triazinyl group; Triazolyl group; Acridil group; Pyridazinyl group; Pyrazinyl group; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazinyl group; Pyridopyrimidyl group; Pyridopyrazinyl group; Pyrazino pyrazinyl group; Isoquinolinyl group; Indole group; Carbazolyl group; Benzoxazolyl group; Benzimidazole group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; Phenanthrolinyl group; Isooxazolyl group; Thiadiazolyl group; Phenothiazinyl group; And a dibenzofuranyl group, but is not limited thereto.

In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. Can be. For example, two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.

In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for the non-monovalent.

In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group, except that it is not monovalent.

In the present specification, the heterocycle is a non-carbon atom, and contains one or more heteroatoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, and S. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group except that it is not monovalent.

In the present specification, the acryloyl group means a photopolymerizable unsaturated group, and examples thereof include (meth)acryloyl group, but are not limited thereto.

In the present specification, the acrylate group means a photopolymerizable unsaturated group, and examples thereof include (meth)acrylate groups, but are not limited thereto.

In the present specification,'(meth)acryloyl' refers to at least one selected from the group consisting of acryloyl and methacryloyl. The notation'(meth)acrylate' has the same meaning.

In the present specification, OAc means -O(C=O)CH ₃ , and-is a position connected to the compound.

In the present specification, NO ₃ means -ONO ₂ , and-is a position linked to a compound.

In the present specification, SO ₃ means -OSO ₂ , and-is a position linked to a compound.

In the present specification, transition metal refers to a metal element of group 3 to 12 on the periodic table, and post-transition metal refers to a metal element among elements of group 13 to 16 on the periodic table.

In one embodiment of the present specification, M is a transition metal or a transition metal.

In one embodiment of the present specification, M is a transition metal.

In one embodiment of the present specification, M is a metal after transition.

In one embodiment of the present specification, M is Zn, Co, Ni, Cu, Fe, Mn, Cr, Al, In, Sn or Ga.

In one embodiment of the present specification, M is Zn, Co, Ni, Cu, Fe, Mn, or Cr.

In one embodiment of the present specification, M is Al, In, Sn, or Ga.

In one embodiment of the present specification, M is Zn, Co, Cu, Fe, Mn, Cr, Al, In, or Ga.

In one embodiment of the present specification, X is a halogen group; Nitrile group; O(C=O)CH ₃ ; ONO ₂ ; Or OSO ₂ .

In one embodiment of the present specification, X is a halogen group; Nitrile group; O(C=O)CH ₃ ; ONO ₂ ; Or OSO ₂ .

In one embodiment of the present specification, a is 0.

In one embodiment of the present specification, a is 1.

In one embodiment of the present specification, M is Al, In, Cr, or Ga, and a is 1.

In one embodiment of the present specification, M is Zn, Co, Ni, Cu, Fe, Mn or Sn, and a is 0.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted haloalkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring. At this time, "substituted or unsubstituted", deuterium; Halogen group; Nitrile group; Nitro group; An alkyl group having 1 to 5 carbon atoms; Amine group; An aryl group having 6 to 13 carbon atoms; And one or more substituents selected from the group containing a heteroaryl group having 2 to 13 carbon atoms or having no substituent.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Halogen group; An alkyl group having 1 to 5 carbon atoms; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 13 carbon atoms; A heteroaryl group having 6 to 20 carbon atoms unsubstituted or substituted with an aryl group having 6 to 13 carbon atoms; Or an amine group substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 13 carbon atoms, or a ring substituted or unsubstituted by an adjacent substituent by combining with an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 13 carbon atoms. To form.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; Nitro group; Halogen group; Methyl group; Ethyl group; Propyl group; Isopropyl group; Butyl group; sec-butyl group; tert-butyl group; Phenyl group; Biphenyl group; Naphthyl group; Fluorenyl group; Carbazole; Phenyl carbazole group; Dibenzofuran group; Dibenzothiophene group; Dimethylamine group; Diethylamine group; Di-tert-butylamine group; Or a diphenylamine group, or adjacent substituents combine with each other to form a monocyclic or bicyclic ring.

In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Halogen group; Methyl group; tert-butyl group; Phenyl group; Or a diethylamine group, or adjacent substituents combine with each other to form a benzene ring.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Halogen group; Methyl group; tert-butyl group; Phenyl group; Or a diethylamine group, or adjacent substituents combine with each other to form a benzene ring.

In one embodiment of the present specification, the types and connection positions of R1 and R2 are the same.

In one embodiment of the present specification, R3 is hydrogen; heavy hydrogen; Or a nitro group.

In one embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In one embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms.

In one embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Methyl group; Ethyl group; Propyl group; tert-butyl group; Phenyl group; Naphthyl group; Biphenyl group; Fluorenyl group; Or a dimethylfluorenyl group.

In one embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently an ethyl group; Or a phenyl group.

In one embodiment of the present specification, A1 and A2 are ethyl groups.

In one embodiment of the present specification, x1 is an integer of 0 to 6, and when 2 or more, R1 is the same or different from each other.

In one embodiment of the present specification, x2 is an integer from 0 to 6, and when 2 or more, R2 is the same or different from each other.

In one embodiment of the present specification, x1 and x2 are the same as or different from each other, and each independently 0 or 1.

In one embodiment of the present specification, x1 and x2 are 1.

In one embodiment of the present specification, x1 and x2 are the same as each other.

In one embodiment of the present specification, x3 is an integer of 0 to 4, and when x3 is 2 or more, a plurality of R3s are the same or different from each other.

In one embodiment of the present specification, x3 is 0 or 1.

In one embodiment of the present specification, x3 is 1.

In one embodiment of the present specification, y1 and y2 are the same as or different from each other, and each independently 0 or 1.

In one embodiment of the present specification, the number of unit repeats in which the unit represented by Chemical Formula 1 is included in the polymer is n.

In one embodiment of the present specification, n is an integer of 3 or more. In one embodiment, n is an integer of 10 or more.

In one embodiment of the present specification, n is an integer of 500 or less. In one embodiment, n is an integer of 250 or less. In one embodiment, n is an integer of 100 or less.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by Chemical Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

The definitions of M, X, a, R1 to R3, x3 and * are as defined in Formula 1,

x10 and x20 are the same or different from each other, each independently an integer of 0 to 5, and R1 and R2 of 2 or more are the same or different from each other,

x11 and x21 are the same or different from each other, each independently an integer of 0 to 3, and R1 and R2 of 2 or more are the same or different from each other.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Chemical Formulas 2-1 and 2-2,

The definitions of M, X, a, R1 to R3, x3 and * are as defined in Formula 1,

x10 and x20 are the same or different from each other, each independently an integer of 0 to 5, and R1 and R2 of 2 or more are the same or different from each other,

x11 and x21 are the same or different from each other, each independently an integer of 0 to 3, and R1 and R2 of 2 or more are the same or different from each other.

In one embodiment of the present specification, x10 is 0 or 1.

In one embodiment of the present specification, x20 is 0 or 1.

In one embodiment of the present specification, x11 is 0 or 1.

In one embodiment of the present specification, x21 is 0 or 1.

In one embodiment of the present specification, x10 and x20 are the same.

In one embodiment of the present specification, x11 and x21 are the same.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any of the following Chemical Formulas, but is not limited thereto.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the polymer comprising the unit of the formula (1) is 1,000 g / mol or more; 3,000 g/mol or more; Or 6,000 g/mol or more.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the polymer comprising the unit of the formula (1) is 1,000,000 g / mol or less; Up to 500,000 g/mol; 300,000 g/mol or less; Or 200,000 g/mol or less.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the polymer containing the unit of the formula (1) is 1,000 g / mol to 500,000 g / mol.

When the polymer satisfies the weight average molecular weight range, it may have excellent heat resistance in the process of a display color filter that requires high heat resistance. In addition, the insoluble type may have excellent dye transfer characteristics that do not contaminate other color filters during the pattern production process.

In the present specification, the weight average molecular weight is a value obtained by averaging the molecular weights of the molecular weights of the components of the polymer compound having a molecular weight distribution as one of the average molecular weights in which the molecular weight is not uniform and the molecular weight of a certain polymer material is used as a standard. to be.

The weight average molecular weight can be measured through Gel Permeation Chromatography (GPC) analysis.

Further, according to an exemplary embodiment of the present specification, it is possible to provide a color material composition comprising a polymer comprising a unit represented by the formula (1).

The colorant composition may further include at least one of dyes and pigments in addition to the compound of Formula 1 above. For example, the color material composition may include only the polymer containing the unit of Formula 1, but may include the polymer and one or more dyes, or the polymer and one or more pigments, or the unit of Formula 1 It may also contain a polymer, one or more dyes and one or more pigments.

Specifically, in one embodiment, the colorant composition is a colorant composition of a mixed type of a dye containing the polymer and a dye not containing the polymer.

In another exemplary embodiment, the colorant composition is a hybrid type colorant composition comprising a dye and a pigment containing the polymer.

In another exemplary embodiment, the colorant composition is a hybrid type colorant composition including a dye containing the polymer, a dye not containing the polymer, and a pigment.

In the case of a color filter using a photosensitive resin composition containing a colorant composition for a polymer according to an exemplary embodiment of the present specification, absorption and transmission spectra suitable for a light source to be applied using various dyes and pigments can be obtained, resulting in high color reproduction. , Can achieve high brightness and high contrast ratio

According to an exemplary embodiment of the present specification, it is possible to provide a photosensitive resin composition comprising the color material composition.

According to an exemplary embodiment of the present specification, the photosensitive resin composition is a colorant composition comprising a polymer comprising a unit represented by the formula (1); Binder resin; Polyfunctional monomers; And photoinitiators.

According to an exemplary embodiment of the present specification, the photosensitive resin composition is a colorant composition comprising a polymer comprising a unit represented by the formula (1); Binder resin; Polyfunctional monomers; Photoinitiators; And solvents.

The binder resin is not particularly limited as long as it can exhibit physical properties such as strength and developability of a film made of 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 the art.

Polyfunctional monomers that impart the mechanical strength of the membrane include unsaturated carboxylic acid esters; Aromatic vinyls; Unsaturated ethers; Unsaturated imides; And acid anhydride.

Specific examples of the unsaturated carboxylic acid esters include benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and isobutyl ( Meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetra Hydrofuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl ( Meth)acrylate, acyloctyloxy-2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxy CD ethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, phenoxydiethylene glycol (meth) )Acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth) )Acrylates, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate, but only these It is not limited.

Specific examples of the aromatic vinyls include styrene, α-methylstyrene, (o,m,p)-vinyl toluene, (o,m,p)-methoxy styrene, and (o,m,p)-chloro styrene. It may be selected from the group consisting, but is not limited to these.

Specific examples of the unsaturated ethers may be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but are not limited thereto.

Specific examples of the unsaturated imides include N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide. It can be, but is not limited to these.

Examples of the acid anhydride include maleic anhydride, methyl maleic anhydride, and tetrahydro phthalic anhydride, but are not limited thereto.

The monomer that gives the alkali solubility is not particularly limited as long as it contains an acid group, for example, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono -2-((meth)acryloyloxy)ethyl phthalate, mono-2-((meth)acryloyloxy)ethyl succinate, ω-carboxy polycaprolactone mono(meth)acrylate It is preferable to use one or more, but is not limited to these.

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

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

According to an exemplary embodiment of the present specification, the binder resin is a copolymer of a monomer containing an unsaturated carboxylic acid ester and an acid group.

According to an exemplary embodiment of the present specification, the binder resin is a copolymer of benzyl methacrylate and methacrylic acid.

The polyfunctional monomer is a monomer that serves to form a photoresist phase by light, specifically, propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol di Acrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethyl 1 selected from the group consisting of propane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate It may be a species or a mixture of two or more.

The photoinitiator is not particularly limited as long as it is an initiator that generates radicals by light to trigger crosslinking, but is selected from the group consisting of, for example, acetophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds. It may be one or more.

The acetophenone-based compounds are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, benzoinmethyl ether, benzoinethyl ether, benzoinisobutyl ether, benzoin Butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butan-1-one, 2-(4-bromo-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and the like, but is not limited thereto.

The biimidazole-based compound is 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4 ,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4, 4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole, etc. , But is not limited to this.

The triazine-based compound is 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3- Hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4 -Bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6 -Yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, benzyl-2-{4-[ 2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6 -Yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionamide, 2,4-bis(trichloro Methyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s -Triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

The oxime-based compound is 1,2-octadione,-1-(4-phenylthio)phenyl,-2-(o-benzoyloxime) (Shibagai, Shijii124), ethanone,-1-(9 -Ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(O-acetyloxime) (CG 242), N-1919 (Adeka), and the like.

The solvent is 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-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2 -Ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy It may be one or more selected from the group consisting of propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, but is not limited thereto.

According to an exemplary embodiment of the present specification, based on the total weight of the solid content in the photosensitive resin composition, the content of the polymer containing the unit represented by Formula 1 is 1% to 60% by weight, the content of the binder resin Silver is 1% by weight to 80% by weight, the content of the photoinitiator is 0.1% by weight to 20% by weight, and the content of the multifunctional monomer is 0.1% by weight to 50% by weight.

According to one embodiment of the present specification, based on 100 parts by weight of the total weight of solids in the photosensitive resin composition, the content of the polymer including the unit represented by Formula 1 is 1% by weight to 60% by weight; 3% to 30% by weight; 5% to 20% by weight; Or 6% to 10% by weight.

The total weight of the solid content means the sum of the total weight of the components excluding the solvent in the resin composition. The basis of the solid content and the weight percent based on the solid content of each component can be measured by general analytical means used in the art, such as liquid chromatography or gas chromatography.

According to an exemplary embodiment of the present specification. The photosensitive resin composition may further include a surfactant.

According to an exemplary embodiment of the present specification, the photosensitive resin composition is 1 or 2 selected from the group consisting of photo-crosslinking agent, curing accelerator, adhesion promoter, surfactant, thermal polymerization inhibitor, antioxidant, ultraviolet absorber, dispersant and leveling agent The above additives are further included.

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

The photocrosslinking agent is benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl Benzophenone compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; Florenone-based compounds, such as 9-Florenone, 2-Croro-9-Prorenone, and 2-methyl-9-Florenone; Thioxanthone series such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. Acridine compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptan-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo Coumarin-based compounds such as pyrano[6,7,8-ij]-quinolinazine-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azide benzal acetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline; one or more selected from the group consisting of;

The curing accelerator is used to increase curing and mechanical strength, specifically 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3 ,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis(3-mercaptopropionate), pentaerythritol-tris(3-mercaptopropionate), penta Erythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate), and trimethylolpropane-tris (3-mercaptopropio) Nate) can be used one or more selected from the group consisting of.

As the adhesion promoter used in the present specification, methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, methacryloyloxy propyldimethoxysilane One or more of meta acryloyl silane coupling agents can be selected and used. As the alkyl trimethoxy silane, at least one of octyl trimethoxy silane, dodecyl trimethoxy silane, and octadecyl trimethoxy silane can be used. You can choose and use.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, the silicone-based surfactant is BYK-077, 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-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used. DIC is a fluorine-based surfactant (DaiNippon Ink & Chemicals) 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-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. may be used, but is not limited thereto.

The antioxidant may be at least one selected from the group consisting of hindered phenol antioxidants, amine antioxidants, thio antioxidants, and phosphine antioxidants, but is not limited thereto.

Specific examples of the antioxidant include phosphoric acid-based thermal stabilizers such as phosphoric acid, trimethylphosphate or triethylphosphate; 2,6-di-t-butyl-p-cresol, octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, tetrabis[methylene-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy Benzyl)benzene, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) or bis[3 ,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]glycol ester (Bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoicacid]glycol esters, such as hindered phenol-based primary antioxidants; Amines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine or N,N'-di-β-naphthyl-p-phenylenediamine Secondary antioxidants; Thio such as dilauryl disulfide, dilaurylthiopropionate, distearylthiopropionate, mercaptobenzothiazole or tetramethylthiuramdisulfide tetrabis[methylene-3-(laurylthio)propionate]methane Secondary antioxidants; Or triphenyl phosphite, tris(nonylphenyl)phosphite, triisodecylphosphite, bis(2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4-ditbutylphenyl)Pentaerythritol Diphosphite or (1, 1'-biphenyl)-4,4'-diylbisphosphonoic acid tetrakis [2,4-bis(1,1-dimethylethyl)phenyl]ester ((1,1'-Biphenyl)-4,4' And phosphite-based secondary antioxidants such as -Diylbisphosphonous acid tetrakis[2,4-bis(1,1-dimethylethyl)phenyl] ester).

As the ultraviolet absorber, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole, alkoxy benzophenone, etc. may be used, but is not limited thereto, and in the art Anything commonly used can be used.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, and N-nitrosophenylhydroxy Amine aluminum salt, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, benzoquinone, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2- Methylene bis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole, and phenothiazine (phenothiazine) may include one or more selected from the group consisting of, but are not limited to these, and the sugar technology These may include those commonly known in the art.

The dispersant may be used as a method of internally adding the pigment to the pigment in the form of surface treatment in advance, or a method of externally adding to the pigment. As the dispersing agent, a compound type, nonionic, anionic or cationic dispersing agent may be used, and examples thereof include fluorine-based, ester-based, cationic-based, anionic-based, non-ionic and amphoteric surfactants. These may be used individually or in combination of two or more.

Specifically, the dispersant is polyalkylene glycol and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, There is at least one selected from the group consisting of alkylamide alkylene oxide adducts and alkylamines, but is not limited thereto.

The leveling agent may be polymeric or non-polymeric. Specific examples of the polymeric leveling agent include polyethyleneimine, polyamideamine, amine and epoxide reaction products, and specific examples of the non-polymeric leveling agent include non-polymeric sulfur-containing and non-polymeric nitrogen-containing Compounds include, but are not limited to, any of those commonly used in the art may be used.

According to an exemplary embodiment of the present specification, to provide a photosensitive material comprising the photosensitive resin composition or a cured product thereof.

More specifically, the resin composition of the present specification is applied on a substrate in an appropriate manner and cured to form a thin film or patterned photosensitive material.

Although the coating method is not particularly limited, a spray method, a roll coating method, a spin coating method, or the like can be used, and the spin coating method is generally widely used. In addition, after forming the coating film, in some cases, the residual solvent may be partially removed under reduced pressure.

As a light source for curing the resin composition according to the present specification, for example, there is a mercury vapor arc (arc), carbon arc, Xe arc, etc. that emits light having a wavelength of 250 nm to 450 nm, but is not limited thereto.

The resin composition according to the present specification is a thin film transistor type liquid crystal display (TFT LCD) pigment dispersion type photosensitive material for manufacturing a color filter, a thin film transistor liquid crystal display device (TFT LCD) or a photosensitive material for forming a black matrix of an organic light emitting diode, It can be used for photoresist for overcoat layer formation, column spacer photoresist, photocurable paint, photocurable ink, photocurable adhesive, printing plate, photosensitive material for printed wiring board, photosensitive material for plasma display panel (PDP), etc. It is not specially placed.

According to one embodiment of the present specification, a color filter including the photosensitive material is provided.

The color filter may be prepared by using a photosensitive resin composition comprising a color material composition comprising a polymer comprising a unit represented by Formula 1. A color filter may be formed by applying the photosensitive resin composition on a substrate to form a coating film, and exposing, developing, and curing the coating film.

The resin composition according to an exemplary embodiment of the present specification is excellent in heat resistance, and the color change due to heat treatment is small, and thus a color filter having high color reproducibility and excellent sensitivity can be provided even by a curing process in the production of a color filter.

The substrate may be a glass plate, a silicon wafer, and a plastic-based plate such as polyethersulfone (PES) or polycarbonate (PC), and the type 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 exemplary embodiment, the color filter may further include an overcoat layer.

A black pattern on a grid called a black matrix may be disposed between color pixels of the color filter for the purpose of improving contrast. Chrome can be used as the material of the black matrix. In this case, a method of depositing chromium on the entire glass substrate and forming a pattern by etching may be used. However, considering the high cost in the process, high reflectance of chromium, and environmental pollution by chromium waste liquid, a resin black matrix by a pigment dispersion method capable of fine processing can be used.

The black matrix according to one embodiment of the present specification may use a black pigment or black dye as a color material. For example, carbon black may be used alone, or a mixture of carbon black and a coloring pigment may be used. In this case, since the coloring pigment having insufficient light-shielding property is mixed, the strength of the film or the adhesion to the substrate decreases even when the amount of the coloring material is relatively increased. It has the advantage of not being.

According to one embodiment of the present specification, a display device including the color filter is provided.

The display device includes a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), a thin film transistor It may be any one of a liquid crystal display (Thin FIlm Transistor-Liquid Crystal Display, LCD-TFT) and a cathode ray tube (CRT).

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

<Production Example>

Preparation Example 1 Synthesis of Polymer A

1. Synthesis of Compound A-1

5-bromo-2-hydroxybenzaldehyde (5.0 g, 25.0 mmol) and bis(pinacolato)diborane (9.5 g, 37.5 mmol), potassium acetic acid (7.4 g, 75 mmol), Pd(dba) ₂ (0.14 g, 0.25 mmol), PCy ₃ (0.14 g, 0.50 mmol) and 1,4-dioxane (400 ml) were added and stirred at reflux for about 4 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure, and then recrystallized with ethyl acetate/hexane to obtain compound A-1 (4.5 g, 72%).: MS[M] = 248.1

2. Synthesis of Compound A-2

Compound A-1 (5 g, 20.2 mmol) and 5-bromo-2-hydroxybenzaldehyde (3.37 g, 16.8 mmol) and Pd(t-Bu ₃ P) ₂ (0.017 g, 0.03 mmol) in 2M K ₂ CO ₃ Aqueous solution (30 mL) and tetrahydrofuran (THF) (200 mL) were added and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure, and recrystallized with ethyl acetate/hexane to obtain Compound A-2 (3.38 g, 83%): MS [M] = 242.1

3. Synthesis of Polymer A

Compound A-2 (5.0 g, 20.66 mmol), benzene-1,2-diamine (2.23 g, 20.66 mmol), zinc acetate dihydrate (4.8 g, 21.69 mmol) and ethanol (100 ml) were added to about 60 It was stirred at ℃ for 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The filtrate was collected, placed in distilled water (50 ml), stirred at room temperature for 30 minutes, and then filtered again. The filtrate was dried to obtain Polymer A (4.53 g, 54%).: Weight average molecular weight: 11,300 g/mol

Preparation Example 2: Synthesis of Polymer B

1. Synthesis of Compound B-1

5-bromo-3-(tert-butyl)-2-hydroxybenzaldehyde (5.0 g, 19.53 mmol) and bis(pinacolato)diborane (7.45 g, 29.3 mmol), potassium acetic acid (5.6 g, 58.58 mmol), Pd(dba) ₂ (0.22 g, 0.39 mmol), PCy ₃ (0.22 g, 0.78 mmol) and 1,4-dioxane (400 ml) were added and stirred at reflux for about 4 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, the organic layer was distilled under reduced pressure, and then recrystallized with ethyl acetate/hexane to obtain compound B-1 (4.52 g, 76%).: MS[M] = 304.19

2. Synthesis of Compound B-2

Compound B-1 (5.0 g, 16.4 mmol) and 5-bromo-3-(tert-butyl)-2-hydroxybenzaldehyde (4.85 g, 13.70 mmol) and Pd(t-Bu ₃ P) ₂ (0.025 g, 0.05 mmol) was added to a 2M K ₂ CO ₃ aqueous solution (30 mL) and tetrahydrofuran (THF) (200 mL) and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure, and recrystallized with ethyl acetate/hexane to obtain compound B-2 (4.76 g, 82%): MS [M] = 354.18

3. Synthesis of Polymer B

Compound B-2 (5.0 g, 14.1 mmol), benzene-1,2-diamine (1.53 g, 14.1 mmol) and aluminum chloride (2.0 g, 14.8 mmol) and ethanol (100 ml) were added and 12 at about 60°C. Stir for hours. After the reaction was completed, it was cooled to room temperature and filtered. The filtrate was collected, placed in distilled water (50 ml), stirred at room temperature for 30 minutes, and then filtered again. The filtrate was dried to obtain polymer B (4.3 g, 59%).: Weight average molecular weight: 8,470 g/mol

Preparation Example 3: Synthesis of Polymer C

1. Synthesis of Compound C-1

6-bromo-2-hydroxy-1-naphthalaldehyde (5.0 g, 20.0 mmol) and bis(pinacolato)diborane (7.62 g, 30.0 mmol), potassium acetic acid (5.76 g, 60.0 mmol), Pd (dba) ₂ (0.22 g, 0.8 mmol), PCy ₃ (0.22 g, 0.8 mmol) and 1,4-dioxane (400 ml) were added and stirred at reflux for about 4 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure, and then recrystallized with ethyl acetate/hexane to obtain compound C-1 (4.95 g, 83%). MS [M] = 298.14

2. Synthesis of Compound C-2

Compound C-1 (5.0 g, 16.78 mmol) and 6-bromo-2-hydroxy-1-naphthalaldehyde (3.49 g, 13.98 mmol) and Pd(t-Bu ₃ P) ₂ (0.026 g, 0.05 mmol) ) In 2M K ₂ CO ₃ aqueous solution (30 mL) and tetrahydrofuran (THF) (200 mL), and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from ethyl acetate/hexane to obtain compound C-2 (4.65 g, 81%): MS [M] = 342.09

3. Synthesis of Polymer C

Compound C-2 (5.0 g, 14.62 mmol), benzene-1,2-diamine (1.58 g, 14.62 mmol) and cobalt(II) acetate tetrahydrate (3.82 g, 15.35 mmol) and ethanol (100 ml) were added. The mixture was stirred at about 60°C for 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The filtrate was collected, placed in distilled water (50 ml), stirred at room temperature for 30 minutes, and then filtered again. The filtrate was dried to give polymer C (3.96 g, 54%).: Weight average molecular weight: 6,920 g/mol

The weight average molecular weight, maximum molecular weight and minimum molecular weight of the polymers A to C were measured through GPC (Gel Permeation Chromatography), and the results are shown in Table 1 below.

Average molecular weight
(Mw) (g/mol) Maximum molecular weight
(Mw) (g/mol) Minimum molecular weight
(Mw) (g/mol) Average molecular weight
/ Minimum molecular weight Polymer A 11,293 21,710 5,025 2.25 Polymer B 8,467 14,647 4,140 2.05 Polymer C 6,920 11,410 3,870 1.79

<Product composition>

Example 1

Colorant composition containing 3.000 g of polymer A, 29.480 g of binder resin, 2.000 g of photoinitiator (Igacure-369), multifunctional monomer (photopolymerizable compound, DPHA (Japanese Chemicals)) 7.370 g, solvent (propylene glycol monomethyl ether acetate) (PGMEA)) A photosensitive resin composition was prepared by mixing 17.650 g and 40.000 g of DMF (dimethylformamide) and 1.016 g of an additive (surfactant, F-475 manufactured by DIC).

The binder resin is a copolymer of benzyl methacrylate and methacrylic acid, the molar ratio of benzyl methacrylate and methacrylic acid is 70:30, and the acid value is 80 KOH mg/g. The weight average molecular weight measured by GPC is 12,000, and the molecular weight distribution (PDI) is 2.0 g. Propylene glycol monomethyl ether acetate (PGMEA) was used in 25 parts by weight of solids (S.C.).

Examples 2 and 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that Polymer B or C was used instead of Polymer A in Example 1.

Comparative Examples 1 and 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that Compound K1 or K2 described below was used instead of Compound A in Example 1.

<Experimental Example>

Substrate production

The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were used for substrate production, respectively. Specifically, the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were spin coated on glass (5 X 5 cm), and subjected to a prebake (PrB) at 100° C. for 100 seconds. A film was formed.

The distance between the substrate on which the film was formed and the photomask was set to 300 μm, and an exposure dose of 40 mJ/cm ² was investigated on the entire surface of the substrate using an exposure machine. The photomask is made of quartz.

Thereafter, the exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds. Thereafter, the L, a, and b values were measured using a spectrophotometer as a C light source and a 2-degree viewing angle.

After measurement, the substrate was post-heated at 230°C for 20 minutes (postbake; PB), and the L, a, and b values were measured using a spectrophotometer with a C light source and a 2 degree viewing angle.

In addition, after the measurement, post-heat treatment was performed at 230°C for 360 minutes (postbake; PB360), and the L, a, and b values were measured using a spectrophotometer with a C light source and a 2 degree viewing angle.

Heat resistance evaluation

The color difference was obtained using the measured value and the following equation. The smaller the color difference, the smaller the change in color, which means that it has excellent heat resistance.

Chrominance-1(ΔE _ab = [(L value of PB-L value of PrB) ² + (a value of PB-a value of PrB) ² + (b value of PB-b value of PrB) ² ] ^1/2

Chrominance-2(ΔE _ab = [(L value of PB360-L value of PB) ² + (a value of PB360-a value of PB) ² + (b value of PB360-b value of PB) ² ] ^1/2

The values of color difference-1 and color difference-2 of Comparative Examples 1 and 2 and Examples 1 to 3 are shown in Table 2 below.

Chrominance-1 (ΔE _ab ) Chrominance-2 (ΔE _ab ) Comparative Example 1 16.4 22.3 Comparative Example 2 12.3 18.8 Example 1 9.8 12.5 Example 2 10.3 14.5 Example 3 11.5 16.2

Comparative Examples 1 and 2 used a colorant composition comprising the unit of Formula 1 as a compound, and Examples 1 to 3 used a colorant composition of a polymer comprising the unit of Formula 1 above. According to Table 1, the color difference of Examples 1 to 3 according to an exemplary embodiment of the present invention is smaller than Comparative Examples 1 and 2. In particular, in Example 1, the color difference-1 was reduced by 40.2% compared to the color difference-1 of Comparative Example 1, and the color difference-2 of Example 1 was decreased by 43.9% compared to the color difference-2 of Comparative Example 1.

Therefore, it was found that the color material composition of the present invention was excellent in heat resistance.

Claims (13)

Color material composition comprising a polymer comprising a unit represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
M is a transition metal or a metal after transition,
X is a halogen group; Nitrile group; O(C=O)CH ₃ ; ONO ₂ ; Or OSO ₂ ,
a is 0 or 1,
R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring,
x1 is an integer from 0 to 5, and when 2 or more, R1 is the same or different from each other,
x2 is an integer from 0 to 5, and when 2 or more, R2 is the same or different from each other,
x3 is an integer from 0 to 4, and when 2 or more, R3 is the same or different from each other,
y1 and y2 are the same as or different from each other, and each independently 0 or 1,
A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
* Is a site bonded to the polymer chain. The method according to claim 1, wherein the formula 1 is a colorant composition represented by the following formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,
The definitions of M, X, a, R1 to R3, x3 and * are as defined in Formula 1,
x10 and x20 are the same or different from each other, each independently an integer of 0 to 5, and R1 and R2 of 2 or more are the same or different from each other,
x11 and x21 are the same or different from each other, each independently an integer of 0 to 3, and R1 and R2 of 2 or more are the same or different from each other. The method according to claim 1, wherein the formula 1 is a colorant composition represented by the following formula 2-1 or 2-2:
[Formula 2-1]

[Formula 2-2]

In Chemical Formulas 2-1 and 2-2,
The definitions of M, X, a, R1 to R3, x3 and * are as defined in Formula 1,
x10 and x20 are the same or different from each other, each independently an integer of 0 to 5, and R1 and R2 of 2 or more are the same or different from each other,
x11 and x21 are the same or different from each other, each independently an integer of 0 to 3, and R1 and R2 of 2 or more are the same or different from each other. The method according to claim 1,
R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitro group; Halogen group; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or N(A1)(A2), or adjacent substituents combine with each other to form a substituted or unsubstituted ring,
A1 and A2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms. The method according to claim 1,
M is Zn, Co, Cu, Fe, Mn, Cr, Al, In or Ga colorant composition. The method according to claim 1,
The color material composition of the polymer having a weight average molecular weight of 1,000 g/mol to 500,000 g/mol. The method according to claim 1, The unit represented by the formula (1) is a colorant composition represented by any one of the following formula:

. The color material composition of any one of claims 1 to 7; Binder resin; Polyfunctional monomers; And a photoinitiator. The method according to claim 8,
Based on the total weight of solids in the photosensitive resin composition
The content of the polymer containing the unit represented by Formula 1 is 1% to 60% by weight,
The content of the binder resin is 1% by weight to 80% by weight,
The content of the photoinitiator is 0.1% to 20% by weight,
The content of the polyfunctional monomer is 0.1 to 50% by weight of the photosensitive resin composition. The photosensitive resin composition of claim 8, further comprising a solvent. A photosensitive material comprising the photosensitive resin composition according to claim 8 or a cured product thereof. Color filter comprising a photosensitive material according to claim 11. A display device comprising the color filter according to claim 12.