Photosensitive resin composition, photosensitive resin film using same, color filter, and display device

Abstract

(D) a colorant including a blue pigment; (E) a solvent; (F) a thiol-based compound; and (G) a silane coupling agent; wherein the thiol-based compound and the silane coupling agent are each independently contained in an amount of 0.1% by weight or more and less than 0.3% by weight based on the total amount of the photosensitive resin composition; a photosensitive resin film produced using the photosensitive resin composition; a color filter including the photosensitive resin film; and a display device including the color filter.

Description

Technical Field

[0001] This description relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, a color filter including the photosensitive resin film, and a display device including the color filter.

Background Art

[0002] A liquid crystal display device, which is one type of display device, has advantages such as weight reduction, thinning, low cost, low power consumption drive, and excellent bonding properties with integrated circuits, and its range of use has been expanded for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a color filter in which unit pixels in which sub-pixels of red (R), green (G), and blue (B) corresponding to the three primary colors of light are assembled are repeatedly formed. When color signals are applied to the respective sub-pixels in a state where the sub-pixels are arranged adjacent to each other to control the brightness, a specific color is displayed in the unit pixel by the synthesis of the three primary colors.

[0003] Color filters are manufactured from dyes or pigments of red (R), green (G), and blue (B), and such dye materials serve to change the white light of the backlight unit into the corresponding colors. The color characteristics are improved as long as the spectrum of the dye material has no unnecessary wavelengths other than the required absorption wavelengths and has a narrow absorption band. Also, it must have excellent heat resistance, light resistance, and chemical resistance so as not to fade or discolor under ultraviolet rays, acids, and bases exposed during the etching process of the color resist.

[0004] However, ensuring the stability of the photoresist against moisture has emerged as a new problem due to the strengthening of the requirements of panel manufacturers for maintaining the adhesion to the substrate and preventing the generation of sublimable foreign substances in a harsh environment of high temperature and high humidity.

Summary of the Invention

Problems to be Solved by the Invention

[0005] One embodiment is for providing a photosensitive resin composition that can suppress the generation of sublimable foreign substances, minimize peeling problems, and ensure patternability even in a harsh environment of high temperature and high humidity.

[0006] Another embodiment is for providing a photosensitive resin film manufactured using the photosensitive resin composition.

[0007] Still another embodiment is for providing a color filter including the photosensitive resin film.

[0008] Still another embodiment is for providing a display device including the color filter.

Means for Solving the Problems

[0009] One embodiment of the present invention includes (A) a binder resin; (B) a photopolymerizable compound; (C) a photoinitiator; (D) a colorant including a blue pigment; (E) a solvent; (F) a thiol-based compound; and (G) a silane coupling agent, and provides a photosensitive resin composition in which the thiol-based compound and the silane coupling agent are each independently contained in an amount of 0.1% by weight or more and less than 0.3% by weight based on the total amount of the photosensitive resin composition.

[0010] The thiol-based compound and the silane coupling agent may be contained in a weight ratio of 1:1 to 2:1.

[0011] The thiol-based compound can contain at least two or more functional groups represented by the following Chemical Formula 1 at its terminals.

[0012]

Chemical Formula

[0013] In the above Chemical Formula 1, L 1 and L 2Each is independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

[0014] The thiol compound can be represented by the following Chemical Formula 1-1.

[0015]

Chem.

[0016] In the above Chemical Formula 1-1, L 1 and L 2 Each is independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, u1 and u2 are each independently an integer of 0 or 1.

[0017] The silane coupling agent may be an amino-based silane coupling agent.

[0018] The amino-based silane coupling agent can be represented by the following Chemical Formula 2.

[0019]

Chem.

[0020] In the above Chemical Formula 2, R 1 ~R 3 Each is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, R 4 and R 5is, independently of each other, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L 3 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0021] The binder resin can include an acrylic binder resin, a cardo binder resin, or a combination thereof.

[0022] The binder resin is an acrylic binder resin, and the acrylic binder resin can have a weight average molecular weight of 5000 g / mol to 15000 g / mol.

[0023] The binder resin is an acrylic binder resin, and the acrylic binder resin can have an acid value of 80 mgKOH / g to 130 mgKOH / g.

[0024] The photosensitive resin composition can include, based on the total amount of the photosensitive resin composition, 5% to 20% by weight of the binder resin; 1% to 10% by weight of the photopolymerizable compound; 0.1% to 10% by weight of the photoinitiator; 5% to 50% by weight of the colorant; 30% to 70% by weight of the solvent; 0.1% to 0.29% by weight of the thiol-based compound; and 0.1% to 0.29% by weight of the silane coupling agent.

[0025] The photosensitive resin composition can further include malonic acid; 3-amino-1,2-propanediol; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0026] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0027] Still another embodiment provides a color filter including the photosensitive resin film.

[0028] Another embodiment provides a display device including the color filter.

[0029] Specific matters of other aspects of the present invention are included in the following detailed description.

Advantages of the Invention

[0030] The photosensitive resin composition according to one embodiment can suppress the generation of sublimation foreign matters in a high-temperature and high-humidity environment and simultaneously ensure patterning.

Brief Description of the Drawings

[0031] [Fig. 1] It is a pattern photograph produced from the photosensitive resin composition according to Example 1. [Fig. 2] It is a pattern photograph produced from the photosensitive resin composition according to Example 2. [Fig. 3] It is a pattern photograph produced from the photosensitive resin composition according to Comparative Example 10.

Modes for Carrying Out the Invention

[0032] Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example and the present invention is not limited thereby. The present invention is defined only by the scope of the claims described later.

[0033] Unless otherwise specifically mentioned in this specification, "substituted" or "substitution" means that one or more hydrogen atoms in the functional group of the present invention are halogen atoms (F, Br, Cl or I), hydroxy groups, nitro groups, cyano groups, amino groups (NH 2 , NH(R 200 ) or N(R 201 )(R 202 ), where R 200 , R 201 and R 202are the same or different from each other and are each independently an alkyl group having 1 to 10 carbon atoms), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, which means being substituted with one or more substituents selected from the group consisting of

[0034] Unless otherwise specifically mentioned in this specification, "alkyl group" means an alkyl group having 1 to 20 carbon atoms, specifically an alkyl group having 1 to 15 carbon atoms, "cycloalkyl group" means a cycloalkyl group having 3 to 20 carbon atoms, specifically a cycloalkyl group having 3 to 18 carbon atoms, "alkoxy group" means an alkoxy group having 1 to 20 carbon atoms, specifically an alkoxy group having 1 to 18 carbon atoms, "aryl group" means an aryl group having 6 to 20 carbon atoms, specifically an aryl group having 6 to 18 carbon atoms, "alkenyl group" means an alkenyl group having 2 to 20 carbon atoms, specifically an alkenyl group having 2 to 18 carbon atoms, "alkylene group" means an alkylene group having 1 to 20 carbon atoms, specifically an alkylene group having 1 to 18 carbon atoms, "arylene group" means an arylene group having 6 to 20 carbon atoms, specifically an arylene group having 6 to 16 carbon atoms.

[0035] Unless otherwise specifically mentioned in this specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means that both "acrylic acid" and "methacrylic acid" are possible.

[0036] Unless otherwise defined in this specification, "combination" means mixing or copolymerization. Also, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

[0037] Unless otherwise defined within the chemical formulas in this specification, if a chemical bond is not drawn at a position where a chemical bond must be drawn, it means that a hydrogen atom is bonded to that position.

[0038] As used herein, the cardo resin means a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 3-1 to 3-11 are included in the main backbone of the resin.

[0039] Also, unless otherwise defined in this specification, "*" means a portion that is linked to the same or different atoms or chemical formulas.

[0040] One embodiment provides a photosensitive resin composition comprising (A) a binder resin; (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant containing a blue pigment; (E) a solvent; (F) a thiol-based compound; and (G) a silane coupling agent, wherein the thiol-based compound and the silane coupling agent are each independently contained in an amount of 0.1% by weight or more and less than 0.3% by weight based on the total amount of the photosensitive resin composition.

[0041] In order to prevent the formation of sublimable foreign substances under high temperature and high humidity conditions, conventionally, methods such as changing the surface treatment of the pigment or changing the dispersant to ensure the dispersion stability in the pigment dispersion liquid have been used. To improve the photoresist peeling characteristics on the substrate, a silane coupling agent has been introduced, and an initiator for enhancing the lower curing degree has been applied, or a specific photopolymerizable monomer or binder resin having good adhesion to glass has been applied to increase the adhesion to the substrate.

[0042] The factors of sublimable foreign substances under high temperature and high humidity conditions are mainly the dispersant or pigment applied in the pigment dispersion liquid in many cases, which is due to the decrease in the stability of the pigment dispersion liquid. In the case of methods for changing the pigment or the dispersant to ensure the stability of the pigment dispersion liquid (conventional methods), there is a problem that it is difficult to select a material that satisfies all the characteristics within a short period because it affects the color characteristics. Also, in the case of a general silane coupling agent, although there is an effect of enhancing the adhesion to the substrate, it has a limit in that it does not show an effect of controlling sublimable foreign substances.

[0043] Therefore, the inventors clearly recognized the limitations of the conventional methods as described above. After numerous trials and errors, an appropriate amount of an amino-based silane coupling agent was introduced. The *-NH groups in the structure of the amino-based silane coupling agent ensured the stability of the dispersion degree in the pigment dispersion liquid. Additionally, since the silane groups strengthened the adhesive force between glass and the binder resin in the photoresist, the peeling characteristics could also be satisfied simultaneously.

[0044] However, it was difficult to overcome the decrease in sensitivity of the amino-based silane coupling agent only by increasing the content of the photoinitiator. Therefore, after conducting numerous studies, the inventors confirmed that the application of an amplifier was essential to overcome the sensitivity decrease problem. However, it was also confirmed that the problem of stronger non-uniformity at the edge of the pattern occurred as the content of the amplifier increased. After again going through numerous trials and errors, the inventors finally overcame the sensitivity decrease problem by controlling the contents of the amplifier and the amino-based silane coupling agent within a specific range.

[0045] Hereinafter, each component will be specifically described.

[0046] (G) Silane coupling agent The photosensitive resin composition according to one embodiment contains a silane coupling agent. At this time, by containing the silane coupling agent in an amount of 0.1 wt% or more and less than 0.3 wt% based on the total amount of the photosensitive resin composition, the generation of sublimable foreign substances and the peeling problem in a high-temperature and high-humidity environment can be solved. When the silane coupling agent is contained in an amount of 0.3 wt% or more based on the total amount of the photosensitive resin composition, it is impossible to ensure CD sensitivity. When the silane coupling agent is contained in an amount of less than 0.1 wt% based on the total amount of the photosensitive resin composition, its content may be excessively small and it may be impossible to achieve the effects intended by adding the silane coupling agent. For example, the silane coupling agent may be contained in an amount of 0.1 wt% to 0.29 wt% based on the total amount of the photosensitive resin composition.

[0047] For example, the silane coupling agent may be an amino-based silane coupling agent. When the silane coupling agent is not an amino-based silane coupling agent, it may not be possible to suppress the generation of sublimable foreign substances in a high-temperature and high-humidity environment or it may be difficult to solve the peeling problem.

[0048] Specifically, the amino-based silane coupling agent can mean a silane coupling agent containing a *-NR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) group, and can be represented by, for example, the following Chemical Formula 2.

[0049]

Chemical formula

[0050] In the above Chemical Formula 2, R 1 ~R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, R 4 and R 5 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L 3 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0051] For example, in the above Chemical Formula 2, at least one of R 4 and R 5 may be a hydrogen atom.

[0052] When the amino-based silane coupling agent also has a structure different from that of Chemical Formula 2, it may not be effective in suppressing the generation of sublimable foreign substances and the peeling phenomenon in a high-temperature and high-humidity environment.

[0053] Through the application of the silane coupling agent, specifically the amino-based silane coupling agent represented by the chemical formula 2, the problems of sublimable foreign substances and peeling in a high-temperature and high-humidity environment can be solved. However, there are side effects such as a decrease in CD sensitivity and a reduction in chemical resistance. Therefore, the thiol-based compound described below must be used as an amplifier.

[0054] (F) Thiol compound The photosensitive resin composition according to one embodiment contains a thiol-based compound in an amount of 0.1% by weight or more and less than 0.3% by weight based on the total amount of the photosensitive resin composition. Thereby, side effects caused by the use of the silane coupling agent, namely, side effects such as a decrease in CD sensitivity, can be improved. Furthermore, by controlling the content of the thiol-based compound within the above range, the uniformity of the pattern edge portion can be ensured. Also, through the use of the thiol-based compound, while significantly reducing the curing shrinkage rate, a great effect can be obtained in preventing a decrease in luminance at the same time. When the thiol-based compound is contained in an amount of 0.3% by weight or more based on the total amount of the photosensitive resin composition, it is impossible to ensure pattern uniformity. When the thiol-based compound is contained in an amount of less than 0.1% by weight based on the total amount of the photosensitive resin composition, the content may be excessively minute and it may be impossible to realize the effects to be obtained by adding the thiol-based compound. For example, the thiol-based compound may be contained in an amount of 0.1% by weight to 0.29% by weight based on the total amount of the photosensitive resin composition.

[0055] The thiol-based compound can have 2 to 10, for example, 2 to 4 thiol groups (-SH) at its terminals depending on its structure.

[0056] For example, the thiol-based compound can contain at least 2 or more functional groups represented by the following chemical formula 1 at its terminals.

[0057]

Chemical formula

[0058] In the above chemical formula 1, L 1and L 2 is, independently of one another, a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

[0059] For example, the thiol compound can be represented by the following Chemical Formula 1-1.

[0060] [Chemical formula]

[0061] In Chemical Formula 1-1 above, L 1 and L 2 are, independently of one another, a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, u1 and u2 are, independently of each other, an integer of 0 or 1.

[0062] For example, in Chemical Formula 1 and Chemical Formula 1-1 above, the L 1 and L 2 may each independently be a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

[0063] Specific examples of the sulfur-containing compound include pentaerythritol tetrakis(3-mercaptopropionate) represented by the following chemical formula 1a, trimethylolpropane tris(3-mercaptopropionate) represented by the following chemical formula 1b, pentaerythritol tetrakis(mercaptoacetate) represented by the following chemical formula 1c, trimethylolpropane tris(2-mercaptoacetate) represented by the following chemical formula 1d, glycol di-3-mercaptopropionate represented by the following chemical formula 1e, and any one selected from the group consisting of combinations thereof.

[0064]

Chemical formula

[0065] The thiol compound and the silane coupling agent may be contained in a weight ratio of 1:1 to 2:1. When the thiol compound and the silane coupling agent are each contained in an amount of 0.1% by weight to 0.3% by weight based on the total amount of the photosensitive resin composition according to one embodiment and at the same time in a weight ratio of 1:1 to 1:2, the effects of suppressing the generation of sublimable foreign substances, suppressing peeling, minimizing the reduction of CD sensitivity, improving chemical resistance, and improving patternability in a high-temperature and high-humidity environment can be achieved simultaneously.

[0066] (A) Binder resin The binder resin can include an acrylic binder resin, a cardo binder resin, or a combination thereof.

[0067] The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.

[0068] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

[0069] The first ethylenically unsaturated monomer may be contained in an amount of 5% to 50% by weight, for example, 10% to 40% by weight based on the total amount of the acrylic binder resin.

[0070] The second ethylenically unsaturated monomer includes aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; etc. These can be used alone or in combination of two or more.

[0071] Specific examples of the acrylic binder resin include, but are not limited to, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. These can be used alone or in combination of two or more.

[0072] For example, the photosensitive resin composition according to the above embodiment can contain an acrylic binder resin.

[0073] The weight average molecular weight of the acrylic binder resin may be 5,000 g / mol to 15,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate during color filter manufacturing.

[0074] The acid value of the acrylic binder resin may be 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

[0075] For example, the photosensitive resin composition according to the above embodiment may be a cardo binder resin or a mixture of the acrylic binder resin and the cardo binder resin.

[0076] The cardo binder resin can be represented by the following Chemical Formula 3.

[0077]

Chemical Formula

[0078] In the above Chemical Formula 3, R 101 and R 102is independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group, R 103 and R 104 are independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Z 1 is a single bond, O, CO, SO 2 , CR 107 R 108 , SiR 109 R 110 (wherein R 107 to R 110 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) or any one of linking groups represented by the following Chemical Formulas 3-1 to 3-11,

[0079]

Chemical formula

[0080] (in the above Chemical Formula 3-5, R z is a hydrogen atom, an ethyl group, C 2 H 4 Cl, C 2 H 4 OH, CH 2 CH=CH 2 or a phenyl group.).

[0081]

Chemical formula

[0082] Z 2 is an acid anhydride residue or an acid dianhydride residue, z1 and z2 are each independently an integer of 0 to 4.

[0083] The weight average molecular weight of the caldo-based binder resin may be from 500 g / mol to 50,000 g / mol, for example, from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the caldo-based binder resin is within the above range, during the production of the light-shielding layer, pattern formation can be well performed without residue, and during development, there is no loss in the film thickness, and a good pattern can be obtained.

[0084] The caldo-based binder resin may contain a functional group represented by the following chemical formula 4 at at least one of both ends.

[0085]

Chemical formula

[0086] In the above chemical formula 4, Z 3 can be represented by the following chemical formulas 4-1 to 4-7.

[0087]

Chemical formula

[0088] (In the above chemical formula 4-1, R h and R i are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an ester group or an ether group.)

[0089]

Chemical formula

[0090] (In the above chemical formula 4-5, R j is O, S, NH, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an alkylamine group having 1 to 20 carbon atoms or an alkenylamine group having 2 to 20 carbon atoms.)

[0091]

Chemical formula

[0092] The calix-based binder resin can be produced by mixing two or more of, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds such as benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol, polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate, N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride.

[0093] When the binder resin contains a calix-based binder resin, the photosensitive resin composition has excellent developability, good sensitivity during photocuring, and excellent fine pattern forming properties.

[0094] The binder resin may be contained in an amount of 5% by weight to 20% by weight, for example, 7% by weight to 15% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, the photosensitive resin composition has excellent developability during color filter production, improved crosslinkability, and can obtain excellent surface smoothness.

[0095] (B) Photopolymerizable compound As the photopolymerizable compound, a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond can be used.

[0096] By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern excellent in heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

[0097] Specific examples of the photopolymerizable compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

[0098] Examples of commercially available products of the photopolymerizable compound are as follows. Examples of the monofunctional ester of the (meth)acrylic acid include Aronix M-101 (registered trademark), M-111 (registered trademark), M-114 (registered trademark), etc. of Toagosei Co., Ltd.; KAYARAD TC-110S (registered trademark), TC-120S (registered trademark), etc. of Nippon Kayaku Co., Ltd.; V-158 (registered trademark), V-2311 (registered trademark), etc. of Osaka Organic Chemical Industry Co., Ltd. Examples of the difunctional ester of the (meth)acrylic acid include Aronix M-210 (registered trademark), M-240 (registered trademark), M-6200 (registered trademark), etc. of Toagosei Co., Ltd.; KAYARAD HDDA (registered trademark), HX-220 (registered trademark), R-604 (registered trademark), etc. of Nippon Kayaku Co., Ltd.; V-260 (registered trademark), V-312 (registered trademark), V-335HP (registered trademark), etc. of Osaka Organic Chemical Industry Co., Ltd. Examples of the trifunctional ester of the (meth)acrylic acid include Aronix M-309 (registered trademark), M-400 (registered trademark), M-405 (registered trademark), M-450 (registered trademark), M-710 (registered trademark), M-8030 (registered trademark), M-8060 (registered trademark), etc. of Toagosei Co., Ltd.; KAYARAD TMPTA (registered trademark), DPCA-20 (registered trademark), -30 (registered trademark), -60 (registered trademark), -120 (registered trademark), etc. of Nippon Kayaku Co., Ltd.; V-295 (registered trademark), -300 (registered trademark), -360 (registered trademark), -GPT (registered trademark), -3PA (registered trademark), -400 (registered trademark), etc. of Osaka Organic Chemical Industry Co., Ltd. These products can be used alone or in combination of two or more.

[0099] The photopolymerizable compound can also be used after being treated with an acid anhydride to impart better developability.

[0100] The photopolymerizable compound may be contained in an amount of 1% by weight to 10% by weight, for example, 3% by weight to 8% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above range, curing during exposure occurs sufficiently in the pattern forming process, resulting in excellent reliability and excellent developability in an alkaline developer.

[0101] (C) Photoinitiator The photoinitiator is an initiator generally used in the photosensitive resin composition, and for example, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, or combinations thereof can be used.

[0102] Examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0103] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0104] Examples of the thioxanthone-based compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0105] Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like.

[0106] Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3’,4’-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4’-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

[0107] Examples of the oxime-based compounds include O-acyl oxime-based compounds, 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyl oxime-based compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione 2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate, and the like.

[0108] In addition to the above compounds, the photopolymerization initiator may be a carbazole-based compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene-based compound, or the like.

[0109] The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and becoming excited and then transferring its energy.

[0110] Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0111] The photoinitiator may be contained in an amount of 0.1% by weight to 10% by weight, for example, 0.1% by weight to 5% by weight, based on the total amount of the photosensitive resin composition. When the photoinitiator is contained within the above range, sufficient curing occurs during exposure in the pattern forming process, and excellent reliability can be obtained. The pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion, and it is possible to prevent a decrease in transmittance due to unreacted initiator.

[0112] (D) Colorant The photosensitive resin composition according to one embodiment contains a colorant, and the colorant contains a blue pigment.

[0113] For example, the blue pigment may include an epsilon blue pigment. For example, the blue pigment may include all of the "epsilon blue pigment" and a "blue-hybrid pigment of 'epsilon blue pigment' and 'Xanthene-based violet dye'". In this case, it is helpful for improving the luminance compared to the case where the Xanthene-based violet dye is used alone. Also, containing the epsilon blue pigment is advantageous for maintaining a low transmittance in the wavelength range of 400 nm to 450 nm. That is, in this specification, the Blue-Hybrid blue pigment dispersion can mean a blue pigment dispersion in which the Xanthene-based violet dye is mixed in a blue pigment dispersion in which the epsilon blue pigment is dispersed.

[0114] For example, the epsilon blue pigment may be C.I.Pigment Blue15:6 or the like.

[0115] For example, the blue pigment may be a derivative bonded to an organic polymer.

[0116] For example, the blue pigment may be contained in the photosensitive resin composition in the form of a pigment dispersion.

[0117] The pigment dispersion can include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment in the solvent.

[0118] The solid pigment may be contained in an amount of 1 wt% to 20 wt%, for example 8 wt% to 20 wt%, for example 8 wt% to 15 wt%, for example 10 wt% to 20 wt%, for example 10 wt% to 15 wt% based on the total amount of the pigment dispersion.

[0119] As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. can be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines, etc. These can be used alone or in combination of two or more.

[0120] Taking commercially available products of the dispersant as examples, there are DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc. of BYK; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemicals; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc. of Zeneka; or PB711, PB821, etc. of Ajinomoto.

[0121] The dispersant may be contained in an amount of 1% to 20% by weight based on the total amount of the pigment dispersion liquid. When the dispersant is contained within the above range, an appropriate viscosity can be maintained, the dispersibility of the photosensitive resin composition is excellent, and thus the optical, physical, and chemical qualities during product application can be maintained.

[0122] As the solvent for forming the pigment dispersion liquid, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used.

[0123] The colorant containing the cyan pigment may be contained in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 45% by weight, for example, 15% by weight to 40% by weight based on the total amount of the photosensitive resin composition. When the colorant is contained within the above range, it is advantageous for securing a process margin, and the color reproducibility and the contrast ratio will be excellent.

[0124] On the other hand, in addition to the cyan pigment, the colorant may further contain a dye represented by the following Chemical Formula 5.

[0125] The dye represented by the following Chemical Formula 5 has spectroscopic characteristics of strongly absorbing light in a very narrow region of 400 nm to 450 nm and has high solubility in an organic solvent. When a photosensitive resin composition containing this as a colorant is used, a color filter excellent in color reproducibility can be manufactured. The very narrow region of 400 nm to 450 nm is a blue light hazard area. The higher the transmittance in the wavelength region of 400 nm to 450 nm, the more difficult it is to realize a high color coordinate (lowering Bx). The lower the transmittance in the wavelength region of 400 nm to 450 nm, the easier it is to realize a high color coordinate (lowering Bx). Since the transmittance in the wavelength region of 400 nm to 450 nm is proportional to the area of the lower part of the transmittance graph, it is possible to easily confirm whether the transmittance is high or low by checking the transmittance spectrum. Furthermore, the photosensitive resin film produced using the composition containing the dye represented by the following Chemical Formula 5 as a colorant has high color reproducibility and low reflectance.

[0126]

Chemical Formula

[0127] In the above Chemical Formula 5, M is Cu, Co, VO, Zn, Pt or In, L 4 ~L 7 are each independently *-C(=O)O-* or *-S(=O) 2 NH-*, R 14~R 17 is, independently of one another, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 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, R 6 ~R 13 is, independently of one another, a hydrogen atom or a halogen atom.

[0128] In the chemical formula 5, the substitution positions of the substituents (*-L 4 -R 14 , *-L 5 -R 15 , *-L 6 -R 16 , and *-L 7 -R 17 ) are advantageously located at the para position among ortho, meta, and para positions in order to increase the absorbance in a narrow wavelength range of 400 nm to 450 nm. For example, the dye represented by the chemical formula 1 in which the substitution position of the substituent is para exhibits a very strong absorbance at 400 nm to 450 nm, for example, 400 nm to 435 nm. Therefore, a composition containing this as a colorant is excellent in color reproducibility, color stability, light resistance, etc. while having a low Bx.

[0129] For example, in the chemical formula 5, the L 4 ~L 7 may each independently be *-C(=O)O-*, and the R 14 ~R 17 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. In this case, the compatibility with the phthalocyanine-based dye is most excellent, and it is possible to maintain excellent durability while having a low transmittance in the wavelength range of 400 nm to 450 nm and maintaining a low Bx.

[0130] For example, the dye represented by the chemical formula 5 can have maximum light absorption in the wavelength range of 400 nm to 435 nm.

[0131] For example, the compound represented by the above Chemical Formula 5 can be represented by any one of the following Chemical Formula 5-1 to Chemical Formula 5-14, but is not necessarily limited thereto.

[0132]

Chem.

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

[0136]

Chem.

[0137]

Chem.

[0138] In the above Chemical Formula 5-1 or Chemical Formula 5-14, M is Cu, Co, VO, Zn, Pt or In.

[0139] For example, the dye represented by the above Chemical Formula 5 may be contained in a content lower than that of the phthalocyanine-based dye described later. For example, the dye represented by the above Chemical Formula 5 and the phthalocyanine-based dye may be contained in a weight ratio of 1:1.1 to 1:2. The fact that the dye represented by the above Chemical Formula 5 is contained in a content lower than that of the phthalocyanine-based dye, specifically contained in the above weight ratio, is advantageous for improving durability such as heat resistance and chemical resistance (while maintaining a low Bx).

[0140] The dye represented by the above chemical formula 5 may be contained in an amount of 1% by weight to 10% by weight, for example, 5% by weight to 10% by weight, based on the total amount of the photosensitive resin composition according to one embodiment.

[0141] In addition to the blue pigment and the dye represented by the chemical formula 5, the photosensitive resin composition according to one embodiment may further contain a phthalocyanine-based dye represented by the following chemical formula 6.

[0142]

Chemical formula

[0143] In the above chemical formula 6, R 17 ~R 32 are each independently a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0144] For example, in the chemical formula 6, at least one of R 17 ~R 20 and at least one of R 25 ~R 28 may be an aryloxy group having 6 to 20 carbon atoms substituted with a halogen atom, and at least one of R 21 ~R 24 and at least one of R 29 ~R 32 may be an aryloxy group having 6 to 20 carbon atoms substituted with an aryl group having 6 to 10 carbon atoms. Specifically, in the chemical formula 6, any one of R 18 and R 19 and any one of R 26 and R 27 may be an aryloxy group having 6 to 20 carbon atoms substituted with a halogen atom, and any one of R 22 and R 23 and any one of R 30 and R 31Any one of them may be an aryloxy group having 6 to 20 carbon atoms which may be substituted with an aryl group having 6 to 10 carbon atoms. When the phthalocyanine-based dye represented by the chemical formula 6 is like this, the compatibility with the dye represented by the chemical formula 5 described above is the most excellent, and (while maintaining a low Bx), durability improvements such as heat resistance and chemical resistance can be effectively achieved.

[0145] The phthalocyanine-based dye may be contained in an amount of 5% by weight to 20% by weight, for example, 5% by weight to 15% by weight, based on the total amount of the photosensitive resin composition according to one embodiment. When contained within the above range, a high color coordinate having a low transmittance in the wavelength region of 400 nm to 450 nm can be easily achieved.

[0146] (E) Solvent As the solvent, a substance that has compatibility with the thiol-based compound, the silane coupling agent, the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator but does not react can be used.

[0147] Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate; ketone esters such as ethyl pyruvate, etc. There are also high-boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. ;

[0148] Among these, considering compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

[0149] The solvent may be contained in the balance amount, for example, 30% by weight to 70% by weight, for example 30% by weight to 60% by weight, for example 40% by weight to 70% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus is excellent in processability during the production of a color filter.

[0150] (H) Other additives The photosensitive resin composition according to one embodiment may further contain malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl group or a (meth)acryloxy group; a leveling agent; a fluorine-based surfactant; or a combination thereof.

[0151] For example, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc. in order to improve the adhesion to a substrate and the like.

[0152] Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, (β-epoxycyclohexyl)ethyltrimethoxysilane, etc. These can be used alone or in admixture of two or more.

[0153] The silane coupling agent may be contained in an amount of 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, it is excellent in adhesion, storage stability, etc.

[0154] In addition, the photosensitive resin composition may further contain a surfactant, for example, a fluorine-based surfactant, if necessary, for the purpose of improving coating properties and preventing defect generation.

[0155] Examples of the fluorosurfactant include BM-1000 (registered trademark), BM-1100 (registered trademark), etc. of BM Chemie; Megafac F 142D (registered trademark), Megafac F 172 (registered trademark), Megafac F 173 (registered trademark), Megafac F 183 (registered trademark), etc. of Dainippon Ink and Chemicals, Incorporated; Fluorad FC-135 (registered trademark), Fluorad FC-170C (registered trademark), Fluorad FC-430 (registered trademark), Fluorad FC-431 (registered trademark), etc. of Sumitomo 3M Limited; Surfynol S-112 (registered trademark), Surfynol S-113 (registered trademark), Surfynol S-131 (registered trademark), Surfynol S-141 (registered trademark), Surfynol S-145 (registered trademark), etc. of Asahi Glass Co., Ltd.; SH-28PA (registered trademark), SH-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc. of Toray Silicone Co., Ltd.; and fluorosurfactants commercially available under the names such as F-482, F-484, F-478, F-554 of DIC Corporation can be used.

[0156] The fluorosurfactant can be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the fluorosurfactant is contained within the above range, coating uniformity is ensured, bleeding does not occur, and wettability to the glass substrate is excellent.

[0157] In addition, other additives such as antioxidants and stabilizers may be further added in a certain amount within a range that does not inhibit the physical properties of the photosensitive resin composition.

[0158] According to another embodiment, there is provided a photosensitive resin film produced using the photosensitive resin composition according to the above embodiment.

[0159] The process for forming a pattern in the photosensitive resin film is as follows.

[0160] A step of applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing, or the like; a step of drying the applied photosensitive resin composition to form a photosensitive resin composition film; a step of exposing the photosensitive resin composition film; a step of developing the exposed photosensitive resin composition film with an aqueous alkali solution to produce a photosensitive resin film; and a step of heat-treating the photosensitive resin film. Since matters such as the conditions in the above steps are widely known in the art, detailed description in this specification is omitted.

[0161] According to another embodiment, a color filter including the photosensitive resin film is provided.

[0162] According to another embodiment, a display device including the color filter is provided.

[0163] Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are merely preferred examples of the present invention, and the present invention is not limited to the following examples.

Examples

[0164] (Example) (Synthesis of photosensitive resin composition) Examples 1 to 6 and Comparative Examples 1 to 13 The components mentioned below were mixed in the compositions shown in Table 1 below to produce photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 13.

[0165] Specifically, after dissolving a photopolymerization initiator in a solvent and stirring at room temperature for 2 hours, a binder resin and a photopolymerizable compound were added thereto and stirred at room temperature for 2 hours. Next, a colorant, a thiol-based compound, a silane coupling agent, and other additives were added to the obtained reactant and stirred at room temperature for 2 hours. Next, the product was filtered three times to remove impurities, thereby producing a photosensitive resin composition.

[0166]

Table 1

[0167] (A) Binder resin Acrylic binder resin (SP-RY-25, Showadenko) (B) Photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.) (C) Photoinitiator Oxime-based initiator (Sanyo Chemical Industries, Ltd.; SPI03) (D) Colorant (A-1) C.I. Pigment Blue15:6 dispersion (Iridos Co., Ltd.; pigment solid content 10%) (A-2) Blue-Hybrid blue pigment dispersion (Iridos Co., Ltd.; epsilon blue pigment + xanthene-based violet dye) (E) Solvent PGMEA (Kyowa Chemical Industry Co., Ltd.) (F) Thiol compound Pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-20P, SC Organic Chemical Co., Ltd.) (G) Silane coupling agent (G-1) Amino-based silane coupling agent (KBM573, Shin-Etsu Chemical Co., Ltd.)

[0168]

Chem.

[0169] (G-2) Non-amino-based silane coupling agent (S510, Chisso Corporation)

[0170]

Chem.

[0171] (G-3) Non-amino-based silane coupling agent (KBM403, Shin-Etsu Chemical Co., Ltd.)

[0172]

Chem.

[0173] (G-4) Non-amino silane coupling agent (KBM503, Shin-etsu)

[0174]

Chem.

[0175] (G-5) Non-amino silane coupling agent (KBM803, Shin-etsu)

[0176]

Chem.

[0177] (H) Additive Fluorine-based surfactant (F-554, DIC Corporation) (Evaluation) 1. Pattern characteristics The photosensitive resin compositions produced in Examples 1 to 6 and Comparative Examples 1 to 13 were applied at a thickness of 1 μm to 3 μm on a degreased and cleaned glass substrate with a thickness of 1 mm under the conditions of 250 rpm to 350 rpm, and dried on a hot plate at 90 °C for 2 minutes to obtain a coating film. Subsequently, after performing overall exposure on the coating film using a high-pressure mercury lamp having a main wavelength of 365 nm under the condition of 40 mJ / cm 2 , it was developed using a developer (diluted and used CD821 solution from Daxin Co., Ltd.) in a developing machine, and dried in a hot air circulation drying furnace at 240 °C for 20 minutes to complete pattern formation.

[0178] The completed pattern was magnified 500 times through an optical microscope to measure the size of the wide 100-μm pattern. At this time, the wide size of the pattern was targeted at the level of 104 to 105 μm.

[0179] 2. Sublimation Characteristics After the pattern was formed, it was processed in a PCT equipment at 120 °C and 100% humidity for 1 hour. Then, through an optical microscope, the presence or absence of foreign substances around the pattern was confirmed at 50 times zoom.

[0180] (Evaluation Result Display Method) O: No sublimable foreign substances △: Sublimable foreign substances are faintly shown around the pattern X: Sublimable foreign substances are widely shown around the pattern.

[0181] 3. Peeling Characteristics After cutting the specimen with the formed pattern into 4*4 size, a 3M tape was attached, and then it was put into a sus tray filled with water. After the tray with the specimen was processed in a PCT equipment at 115 °C and 100% humidity for 30 minutes, the specimen was taken out of the water and the tape was removed, and then the presence or absence of peeling between the substrate and the film was confirmed.

[0182] (Evaluation Result Display Method) O: No peeling △: Partial peeling confirmed X: All peeling confirmed.

[0183] 4. Chemical Resistance After dropping 3 - 4 drops of NMP solution onto the pattern, it was left at room temperature for 10 minutes. Before and after the solution treatment, the color coordinates and luminance were measured using an LCF equipment, and the del(E*) value was calculated based on the color change numerical value to confirm the chemical resistance characteristics.

[0184] The above evaluation results are shown in Table 2 and Figures 1 - 3 below.

[0185]

Table 2

[0186] From Table 2 and FIGS. 1 to 3 above, it can be seen that the photosensitive resin composition according to one embodiment can solve the problems of sublimable foreign matters and peeling problems in a high-temperature and high-humidity environment by containing an amino-based silane coupling agent. By controlling the content of the amino-based silane coupling agent and simultaneously using a thiol-based compound as an amplifier, the problem of CD sensitivity reduction, which is a problem caused by the use of the amino-based silane coupling agent, and the problem of inferior chemical resistance can be improved. It can also be confirmed that the uniformity (patternability) of the pattern edge portion can be ensured through the control of the content of the thiol-based compound.

[0187] As described above, the preferred embodiments of the present invention have been described. However, the present invention is not limited thereto, and various modifications can be made and implemented within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It is natural that these also belong to the scope of the present invention.

Claims

1. With respect to the total amount of the photosensitive resin composition, (A) binder resin: 5% by weight to 20% by weight; (B) Photopolymerizable compound 1% to 10% by weight; (C) photopolymerization initiator 0.1% by weight to 10% by weight; (D) colorant including a blue pigment, 5% to 50% by weight; (E) solvent 30% by weight to 70% by weight; (F) 0.1% by weight to 0.29% by weight of a thiol compound; and (G) silane coupling agent 0.1% by weight to 0.29% by weight; A photosensitive resin composition comprising: The thiol-based compound is represented by the following formulas 1a to 1e: 【Chemistry 1】 The silane coupling agent is an amino-based silane coupling agent represented by the following chemical formula 2: 【Chemistry 2】 In the above chemical formula 2, R １ ~R ３ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, R ４ and R ５ each independently represents a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, L ３ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein the thiol compound and the silane coupling agent are contained in a weight ratio of 1:1 to 2:

1.

3. The photosensitive resin composition of claim 1 , wherein the binder resin comprises an acrylic binder resin, a cardo binder resin, or a combination thereof.

4. 4. The photosensitive resin composition according to claim 3, wherein the binder resin is an acrylic binder resin, and the acrylic binder resin has a weight average molecular weight of 5000 g / mol to 15000 g / mol.

5. 4. The photosensitive resin composition according to claim 3, wherein the binder resin is an acrylic binder resin, and the acrylic binder resin has an acid value of 80 mg KOH / g to 130 mg KOH / g.

6. The photosensitive resin composition of claim 1, further comprising: malonic acid; 3-amino-1,2-propanediol; a leveling agent; a fluorosurfactant; or a combination thereof.

7. A photosensitive resin film produced by using the photosensitive resin composition according to any one of claims 1 to 6.

8. A color filter comprising the photosensitive resin film of claim 7.

9. A display device comprising the color filter of claim 8.

Images