Colorant composition, photosensitive resin composition, photoresist, color filter, and liquid crystal display device

Abstract

The present invention relates to a colorant composition comprising a first color material and a second color material, wherein the first color material and the second color material each have a transmittance of 60% or less at a wavelength of 490 nm or more and 605 nm or less, a transmittance of 90% or more at a wavelength of 470 nm or less, and a transmittance of 98% or more at a wavelength of 620 nm or more.

Description

Technical Field

[0001] This application claims priority and benefit to Korean Patent Application No. 10-2019-0158334, filed with the Korean Intellectual Property Office on December 2, 2019, the entire contents of which are incorporated herein by reference.

[0002] This invention relates to colorant compositions, photosensitive resin compositions, photoresists, color filters, and liquid crystal display devices. Background Technology

[0003] A smooth coating film can be obtained by spin-coating a photosensitive resin composition onto a substrate and then heating and drying the photosensitive resin composition to remove the solvent.

[0004] After the resulting coating is cured by irradiating the exposed portion with ultraviolet light through a negative mask used to form the desired image, the coating is developed by dissolving the unexposed portion in a developing solution.

[0005] By repeating the above process in the same manner using a photosensitive resin composition, a coating film prepared using photosensitive resin compositions of various colors as target pixels (patterns) can be formed.

[0006] The problem is that when the same process needs to be repeated three times to form a color filter using the above method, the process cost increases, and because the heat treatment process needs to be repeated, dyes with high transparency but heat susceptibility cannot be used. Summary of the Invention

[0007] Technical issues

[0008] This specification provides colorant compositions, photosensitive resin compositions, photoresists, color filters, and liquid crystal display devices.

[0009] Technical solution

[0010] An exemplary embodiment of this specification provides a colorant composition comprising a first color material and a second color material, wherein the first color material and the second color material each have a transmittance of 60% or less at wavelengths of 490 nm or greater and 605 nm or less, a transmittance of 90% or greater at wavelengths of 470 nm or less, and a transmittance of 98% or greater at wavelengths of 620 nm or greater.

[0011] An exemplary embodiment of this specification provides a photosensitive resin composition comprising the colorant composition.

[0012] An exemplary embodiment of this specification provides a photoresist formed using the photosensitive resin composition.

[0013] An exemplary embodiment of this specification provides a color filter manufactured using the photoresist described herein.

[0014] An exemplary embodiment of this specification provides a liquid crystal display device including the color filter.

[0015] Beneficial effects

[0016] When color filters are prepared using the colorant composition according to this specification and the photosensitive resin composition containing therein, there is an effect of excellent transmittance and reduced process costs.

[0017] Furthermore, when color filters are prepared using a colorant composition and a photosensitive resin composition containing the colorant, both red and blue can be achieved with a single color filter. Detailed Implementation

[0018] An exemplary embodiment of the present invention provides a colorant composition comprising a first color material and a second color material, wherein the first color material and the second color material each have a transmittance of 60% or less at wavelengths of 490 nm or greater and 605 nm or less, a transmittance of 90% or greater at wavelengths of 470 nm or less, and a transmittance of 98% or greater at wavelengths of 620 nm or greater.

[0019] When the first color material and the second color material satisfy the above wavelength range and transmittance range, the matching range with the range of the light source of the emitted light is high, resulting in an effect of improving transmittance.

[0020] In one exemplary embodiment of this specification, the first color material and the second color material are pigments or dyes.

[0021] There are no particular restrictions on the type of pigment or dye, as long as the pigment or dye meets the wavelength range and transmittance range specified in this specification.

[0022] In this specification, pigments or dyes may be referred to as "compounds".

[0023] In one exemplary embodiment of this specification, the maximum absorption wavelength of the first color material is in the range of 550 nm to 580 nm.

[0024] In one exemplary embodiment of this specification, the first color material has a transmittance of 85% or greater at wavelengths of 480 nm or less and 610 nm or greater.

[0025] Specifically, the first color material exhibits maximum transmittance at 680 nm or greater.

[0026] In one exemplary embodiment of this specification, the maximum absorption wavelength of the second color material is in the range of 530 nm to 560 nm.

[0027] In one exemplary embodiment of this specification, the second color material has a transmittance of 85% or greater at wavelengths of 470 nm or less and 580 nm or greater.

[0028] Specifically, the second color material exhibits maximum transmittance at 470 nm or smaller.

[0029] In one exemplary embodiment of this specification, the first color material and the second color material are zeta-based color materials.

[0030] In one exemplary embodiment of this specification, the first color material and the second color material each have a transmittance of 60% or less at wavelengths of 490 nm or greater and 606 nm or less. Specifically, the first color material and the second color material each have a transmittance of 60% or less at wavelengths of 501 nm or greater and 601 nm or less. More specifically, the first color material and the second color material each have a transmittance of 60% or less at wavelengths of 516 nm or greater and 574 nm or less.

[0031] The first and second color materials can be used without restriction, as long as the first and second color materials meet the above wavelength range and the above transmittance range.

[0032] In one exemplary embodiment of this specification, the transmittance is a value obtained by spin-coating a first color material, a second color material, or a colorant composition onto a substrate; heat-treating the substrate to form a color substrate; and then measuring the formed color substrate using a spectrometer (MCPD, manufactured by Otsuka Electronics Co., Ltd.).

[0033] In one exemplary embodiment of this specification, a substrate can be used without limitation, as long as the substrate serves as a support. For example, the substrate can be glass.

[0034] In one exemplary embodiment of this specification, the weight ratio of the first color material to the second color material is 1:9 to 9:1. Specifically, the weight ratio of the first color material to the second color material is 3:7 to 6:4.

[0035] When the colorant composition meets the stated weight ratio range, a color filter layer capable of achieving both red and blue can be formed by a single coating.

[0036] In one exemplary embodiment of this specification, in addition to the first and second color materials, the colorant composition also contains other color materials. That is, the colorant composition contains two or more color materials.

[0037] In one exemplary embodiment of this specification, other color materials may be used without limitation, as long as the other color materials are color materials used in the art.

[0038] In one exemplary embodiment of this specification, the colorant composition may further comprise one or more of the following: a binder resin; a leveling agent; an adhesive aid; an initiator; and a solvent.

[0039] In this specification, when the colorant composition further comprises one or more materials, the colorant composition may be referred to as a photosensitive resin composition. That is, when the colorant composition further comprises one or more materials, the terms "colorant composition" and "photosensitive resin composition" may be used interchangeably.

[0040] In one exemplary embodiment of this specification, the colorant composition further comprises: a binder resin; a leveling agent; and a solvent.

[0041] An exemplary embodiment of this specification provides a photosensitive resin composition comprising the above-described colorant composition.

[0042] In one exemplary embodiment of this specification, the photosensitive resin composition further comprises one or more of the following: an adhesive resin; a leveling agent; an adhesive aid; an initiator; and a solvent.

[0043] In one exemplary embodiment of this specification, the photosensitive resin composition further comprises: an adhesive resin; a leveling agent; and a solvent.

[0044] In one exemplary embodiment, the photosensitive resin composition may also contain a photoinitiator.

[0045] There are no particular restrictions on the binder resin, as long as the binder resin can exhibit the physical properties of the film made by using the resin composition, such as strength and developability.

[0046] The adhesive resin may be a copolymer resin of a multifunctional monomer that imparts mechanical strength and a monomer that imparts alkali solubility, and may also include adhesives commonly used in the art.

[0047] The multifunctional monomers that impart mechanical strength to the membrane can be any or more of the following: unsaturated carboxylic acid esters; aromatic vinyl groups; unsaturated ethers; unsaturated imides; and acid anhydrides.

[0048] Specific examples of unsaturated carboxylic acid esters may be selected from benzyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acyloctyl-2-hydroxypropyl (meth)acrylate, glyceryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and (meth)acrylate. 3-Methoxybutyl acrylate, ethoxydiethylene 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 methacrylate, tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, tribromophenyl methacrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, and butyl α-hydroxymethyl acrylate, but not limited thereto.

[0049] Specific examples of aromatic vinyl groups may be selected from, but are not limited to, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene.

[0050] Specific examples of unsaturated ethers may be selected from, but are not limited to, vinyl methyl ethers, vinyl ethyl ethers, and allyl glycidyl ethers.

[0051] Specific examples of unsaturated imides may be selected from, but are not limited to, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide.

[0052] Examples of acid anhydrides include maleic anhydride, methylmaleic anhydride, tetrahydrophthalic anhydride, etc., but are not limited to these.

[0053] There are no particular limitations on the monomers that impart alkali solubility, as long as the monomer contains an acid group, and preferably one or more of the following are used: for example, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, 5-norbornene-2-carboxylic acid, phthalic acid mono-2-((meth)acryloyloxy)ethyl ester, succinic acid mono-2-((meth)acryloyloxy)ethyl ester, and ω-carboxylated polycaprolactone mono(meth)acrylate, but the monomers are not limited to these.

[0054] According to an exemplary embodiment of this specification, the adhesive resin has an acid value of 50 KOH mg / g to 130 KOH mg / g and a weight-average molecular weight of 1000 g / mol to 50000 g / mol.

[0055] Leveling agents can be polymeric or non-polymeric. Specific examples of polymeric leveling agents include polyethyleneimine, polyamide amine, and reaction products of amines and epoxides, while specific examples of non-polymeric leveling agents include non-polymeric sulfur-containing compounds and non-polymeric nitrogen-containing compounds, but are not limited to these examples, and those commonly used in the art can also be used.

[0056] There are no particular limitations on the adhesive additives, and adhesive additives commonly used in the art can be used.

[0057] The photosensitive resin compositions according to this specification may additionally contain a photoinitiator.

[0058] As a photoinitiator, one or more compounds selected from the following can be used: 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2,4-trichloromethyl-(fipronil)-6-triazine, 1-hydroxycyclohexylphenyl ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy)propyl ketone, benzophenone, 2,4,6-trimethylaminobenzophenone, etc., but the photoinitiator is not limited to these.

[0059] Based on the total weight of the photosensitive resin composition, the content of the photoinitiator is preferably from 0.1% to 5% by weight, but is not limited thereto.

[0060] In the photosensitive resin composition according to this specification, one or more compounds selected from the following can be used as solvents: methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether, etc., but the solvent is not limited to these.

[0061] Based on the total weight of the photosensitive resin composition, the solvent content is preferably from 45% to 95% by weight, but is not limited thereto.

[0062] In addition, the photosensitive resin composition according to this specification may further include one or more additives selected from the following, depending on the application: curing accelerator, thermal polymerization inhibitor, surfactant, photoresist, plasticizer, adhesion promoter, and filler.

[0063] Examples of curing accelerators include one or more of the following: 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzo[] The range includes, but is not limited to, azoles, 2,5-dimercapto-1,3,4-thiadiazoles, 2-mercapto-4,6-dimethylaminopyridines, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tri(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tri(2-mercaptoacetate), trimethylolpropane tri(2-mercaptoacetate), trimethylolethane tri(2-mercaptoacetate), and trimethylolethane tri(3-mercaptopropionate), and may include those commonly known in the art.

[0064] Examples of thermal polymerization inhibitors include, but are not limited to, one or more of the following: p-anisole, hydroquinone, catechol, tert-butylcatechol, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, and phenothiazines, and may include those commonly known in the art.

[0065] As surfactants, photoresists, plasticizers, adhesion promoters, fillers, etc., all compounds that can be included in photosensitive resin compositions in related fields can be used.

[0066] Based on the total weight of the photosensitive resin composition, the content of each additive is preferably from 0.01% to 5% by weight, but is not limited thereto.

[0067] Simultaneously, the photosensitive resin composition according to this specification can be applied to supports such as metal, paper, and glass / plastic substrates using roller coaters, curtain coaters, spin coaters, stencil coaters, various printing methods, deposition methods, etc. Furthermore, the photosensitive resin composition can be applied to a support such as a film and then transferred to another support, or applied to a first support and then transferred to a rubber blanket, etc., and then transferred to a second support; the application method is not particularly limited.

[0068] The photosensitive resin composition is preferably used to manufacture pigment-dispersed photoresist for TFT LCD color filters, photoresist for forming black matrices of TFT LCDs or organic light-emitting diodes, photoresist for forming outer coatings, and photoresist for columnar spacers. However, it can also be used to manufacture photocurable coatings, photocurable inks, photocurable adhesives, photoresist for printing plates and printed circuit boards, other transparent photoresist, PDPs, etc., and its use is not particularly limited.

[0069] An exemplary embodiment of this specification provides a photoresist formed using a photosensitive resin composition.

[0070] An exemplary embodiment of this specification provides a color filter manufactured using a photosensitive resin composition.

[0071] An exemplary embodiment of this specification provides a color filter manufactured using a photoresist.

[0072] The color filter can be manufactured by methods known in the art, except that it uses a photosensitive resin composition according to this specification.

[0073] An exemplary embodiment of this specification provides a color substrate including a color filter.

[0074] In one exemplary embodiment of this specification, the color substrate includes: a substrate; and a color filter.

[0075] In one exemplary embodiment of this specification, the color filter may be manufactured in the form of a membrane.

[0076] An exemplary embodiment of this specification provides a liquid crystal display device including a color filter.

[0077] The liquid crystal display device according to this specification can be manufactured using techniques in the art, except that it uses the photosensitive resin composition of the present invention.

[0078] For example, after a metal film (e.g., Cr) or a black resin film is applied to a transparent substrate, a partition wall (black matrix) is formed as a boundary other than the pixel areas in which color filters are patterned by photolithography.

[0079] Red, green, and blue color filters can be formed by injecting a color filter ink composition containing red, green, and blue into a pixel area defined by a transparent opening between separator walls and then curing the ink composition. In this case, the aforementioned photosensitive resin composition can be used as the color filter ink composition.

[0080] In one exemplary embodiment of this specification, the liquid crystal display device includes a color filter and a liquid crystal panel disposed thereon, wherein the color filter comprises a first color material and a second color material, and the first color material and the second color material each have a transmittance of 60% or less at a wavelength of 490 nm or greater and 605 nm or less, a transmittance of 90% or greater at a wavelength of 470 nm or less, and a transmittance of 98% or greater at a wavelength of 620 nm or greater.

[0081] Invention Embodiments

[0082] Preferred embodiments of the invention will be presented below to aid in understanding the invention. However, these embodiments are provided to illustrate the application, and the scope of this specification is not limited thereto.

[0083] <Preparation Example>

[0084] Preparation of compounds A to G

[0085] In Table 1, compounds A and B were obtained by synthesis in the same manner as compounds 1 to 32 and compound Ay in Synthesis Example 2 of patent JP 2016-170282.

[0086] Compounds C and D were obtained by synthesis in the same manner as chemical formulas 3 and 5 in patent KR 2015-0055895.

[0087] Compound E was obtained by synthesis in the same manner as compound 3 in patent JP 2014-056214.

[0088] Compounds F and G were obtained by synthesis in the same manner as compounds A-1 and A-2 in patent WO 2019-082593.

[0089] Preparation of compound compositions

[0090] Compound Composition 1

[0091] Based on the total weight of 100 parts by weight of the compound composition, compound composition 1 was prepared by mixing 0.4 parts by weight of compound A, 79.95 parts by weight of adhesive resin A, 0.68 parts by weight of leveling agent F-554, and 18.97 parts by weight of propylene glycol methyl ether acetate.

[0092] The adhesive resin A is a copolymer having a mass ratio of benzyl methacrylate: N-phenylmaleimide: styrene: methacrylic acid = 55:9:11:25.

[0093] Compound compositions 2 to 9

[0094] Compound compositions 2 to 9 were prepared in the same manner as in the preparation of compound composition 1, except that in the preparation of compound composition 1, compounds listed in Table 1 below were used instead of compound A.

[0095] The structures of compounds A to G, R177 and B15:6 described in Table 1 are as follows.

[0096]

[0097] Substrate manufacturing

[0098] The prepared compound compositions 1 to 9 were spin-coated onto glass (5cm × 5cm) and preheated at 100°C for 100 seconds to manufacture a substrate.

[0099] Transmittance assessment

[0100] The absorption spectra of the fabricated substrate in the wavelength range of 380 nm to 780 nm were measured using a spectrometer (MCPD, manufactured by Otsuka Electronics Co., Ltd.) and are shown in Table 1 below.

[0101] [Table 1]

[0102]

[0103] In Table 1, "Applicable" means that the compound composition can be used as the red and blue color filter intended in this specification, and "Not Applicable" means that the compound composition cannot be used as the red and blue color filter intended in this specification.

[0104] In Table 1, λ*@T=60% means the wavelength of the left slope at 60% transmittance (the shorter wavelength value among the wavelengths at 60% transmittance).

[0105] λ**@T=60% means the wavelength with the right slope at 60% transmittance (the value of the longer wavelength at 60% transmittance).

[0106] T@λ=470nm means the transmittance at a wavelength of 470nm, and

[0107] T@λ = 620nm means the transmittance at a wavelength of 620nm.

[0108] In Table 1, all wavelengths between λ*@T=60% and λ**@T=60% show a transmittance of 60% or less.

[0109] Preparation of colorant compositions

[0110] Example 1

[0111] The colorant composition of Example 1 was prepared by mixing 33 parts by weight of compound composition 1 and 67 parts by weight of compound composition 3, based on the total weight of 100 parts by weight of the colorant composition.

[0112] Examples 2 and 3 and Comparative Examples 1 to 5

[0113] The colorant compositions of Examples 2 and 3 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that in Example 1, the compound compositions in Table 2 below were used instead of compound compositions 1 and 3.

[0114] [Table 2]

[0115]

[0116] Color filter manufacturing

[0117] The prepared colorant composition was spin-coated onto glass (5cm×5cm), preheated at 100°C for 100 seconds, and then postheated at 230°C for 20 minutes to manufacture the substrate.

[0118] Transmittance assessment

[0119] The absorption spectra of the substrates after post-heat treatment (one post-baking) were measured in the wavelength range of 380 nm to 780 nm using a spectrometer (MCPD, manufactured by Otsuka Electronics Co., Ltd.), and are shown in Table 3 below.

[0120] In Table 3 below, for transmittance, each transmittance value is shown based on the value obtained by converting the transmittance of Example 3 to 100 after measuring each transmittance as a reference when light with wavelengths from 380 nm to 780 nm passes through 100%.

[0121] [Table 3]

[0122]

[0123] In Table 3, a higher transmittance value indicates a higher transmittance. Table 3 shows that Examples 1 to 3 have higher transmittance compared to Comparative Examples 1 to 5. Furthermore, it can be determined that Comparative Example 1 cannot produce a blue-colored material, and Comparative Example 2 cannot produce a red-colored material.

[0124] Therefore, it can be determined that since the colorant composition according to this specification and the photosensitive resin composition containing it can simultaneously exhibit both red and blue color materials while having excellent transmittance, the cost of manufacturing color filters can be reduced.

Claims

1. A colorant composition comprising a first color material and a second color material, The first color material and the second color material each have a transmittance of 60% or less at wavelengths of 516 nm or greater and 574 nm or less, a transmittance of 90% or greater at wavelengths of 470 nm or less, and a transmittance of 98% or greater at wavelengths of 620 nm or greater. The transmittance is measured as follows: a colorant composition containing only the first or second color material is spin-coated onto a substrate; the substrate is preheated at 100°C for 100 seconds to form a color substrate; and then the absorption spectrum of the formed color substrate in the wavelength range of 380 nm to 780 nm is measured using a spectrometer. The weight ratio of the first color material to the second color material is 3:7 to 6:

4. The first color material comprises: And said second color material comprises at least one of the following:

2. The colorant composition according to claim 1, wherein the first color material and the second color material are pigments or dyes.

3. The colorant composition according to claim 1, wherein the maximum absorption wavelength of the first color material is in the range of 550 nm to 580 nm.

4. The colorant composition according to claim 1, wherein the maximum absorption wavelength of the second color material is in the range of 530 nm to 560 nm.

5. The colorant composition according to claim 1, wherein the first color material and the second color material are thallium-based color materials.

6. A photosensitive resin composition comprising a colorant composition according to any one of claims 1 to 5.

7. The photosensitive resin composition according to claim 6, further comprising one or more of the following: Adhesive resin; Leveling agent; Adhesive additives; Initiator; and Solvent.

8. A photoresist formed using the photosensitive resin composition according to claim 6.

9. A color filter manufactured using the photoresist according to claim 8.

10. A liquid crystal display device comprising the color filter according to claim 9.

Images