TW202124459A - Colored photosensitive resin composition and black matrix prepared therefrom - Google Patents

Abstract

The colored photosensitive resin composition of the present invention comprises a multifunctional thiol compound and/or a compound containing a double bond and a hydroxyl group, whereby it can sufficiently form a cured film even at low temperatures. In addition, the photosensitive resin composition of the present invention has a fast development speed and excellent resolution and chemical resistance.

Description

Colored photosensitive resin composition and black matrix prepared therefrom

The present invention relates to a photosensitive resin composition capable of forming a colored cured film with excellent developability and resolution even at low temperatures, and a black matrix prepared therefrom.

Colored photosensitive resin compositions are widely used in LCD, OLED and quantum dot (QD)-based display devices.

The LCD includes an upper substrate, a lower substrate, and liquid crystals between the substrates. If necessary, a touch screen panel (TSP), etc. can be connected to the upper substrate. Generally, the TSP is manufactured after the assembly step in which the color filter and the thin film transistor (TFT) are combined. In order to minimize the influence on the already manufactured color filter, the composition must be cured at a low temperature to prepare a cured film. However, there are problems in that the composition is not sufficiently crosslinked when cured at a low temperature, a cured film cannot be formed, or its strength is insufficient. Therefore, there is a demand for compositions that can be cured at low temperatures. In addition, OLEDs and quantum dot (QD)-based display devices require compositions suitable for curing at low temperatures because they are manufactured at low temperatures.

Meanwhile, the technology of preparing a cured film by curing a composition containing an acrylate-based resin as a binder at a low temperature has been known in the related field (see Korean Laid-open Patent Publication No. 2010-0029479). However, it is not sufficient to satisfy chemical resistance.

Conventional coloring compositions that are curable at low temperatures use excessive heat curing agents (such as epoxy compounds) or additives for reducing reaction energy to increase the degree of curing at low temperatures. However, these materials have problems in storage stability, which can cause problems such as peeling, pattern tearing, and insufficient resolution during the process of preparing the cured film.

DETAILED DESCRIPTION Technical Problem Therefore, the object of the present invention is to provide a photosensitive resin composition that can be fully crosslinked and cured at low temperature and has excellent chemical resistance, developability, and pattern resolution, and a photosensitive resin composition prepared therefrom. Black matrix. The solution to the problem

In order to achieve the above object, the present invention provides a photosensitive resin composition comprising (A) a copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant; and (E) Multifunctional thiol compound.

In order to achieve another objective, the present invention provides a black matrix made of a photosensitive resin composition. Advantages of the present invention

The colored photosensitive resin composition of the present invention contains a multifunctional thiol compound and/or a compound containing a double bond and a hydroxyl group, whereby it can sufficiently form a cured film even at low temperatures. In addition, the photosensitive resin composition of the present invention has a fast developing speed, excellent resolution and chemical resistance.

Best mode for carrying out the present invention The present invention is not limited to those described below. On the contrary, as long as the gist of the present invention is not changed, it can be modified into various forms.

Throughout this specification, unless expressly stated otherwise, when a part is referred to as "comprising" one element, it should be understood that other elements may be included instead of excluding other elements. In addition, unless expressly stated otherwise, all numbers and expressions related to the amounts of components, reaction conditions, etc. used herein should be understood as modified by the term "about".

The present invention provides a photosensitive resin composition comprising (A) a copolymer; (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a coloring agent; and (E) a multifunctional thiol compound .

The composition may optionally further comprise (F) a compound containing two or more double bonds and two or more hydroxyl groups, (G) a photobase generator, (H) an epoxy compound, (I) Adhesion promoter, (J) surfactant and/or (K) solvent.

As used herein, the term "(meth)acryl" refers to "acryl" and/or "methacryl", and the term "(meth)acrylate" refers to "acrylate" And/or "methacrylate".

Measure the weight average molecular weight (g/mol or Da) of each component as described below by gel permeation chromatography (GPC, eluent: tetrahydrofuran) (refer to polystyrene standards). (A) Copolymer

The copolymer (A) may contain at least one selected from the group consisting of: (a1) a structural unit derived from an unsaturated monomer containing an acid group; (a2) a structural unit derived from an alicyclic epoxy group Structural units of unsaturated monomers; (a3) Structural units derived from unsaturated monomers containing acyclic epoxy groups; and (a4) Different from (a1) to (a3) derived from unsaturated monomers Structural units.

In particular, the copolymer (A) may include two or more, three or more, or four or more selected from the group consisting of structural units (a1) to (a4).

More specifically, the copolymer (A) may include a structural unit (a4) and may further include (a1), (a2), and/or (a3). (a1) Structural units derived from unsaturated monomers containing acid groups

The copolymer (A) may contain (a1) a structural unit derived from an unsaturated monomer containing an acid group.

The structural unit (a1) in the present invention may be derived from an unsaturated monomer containing an acid group.

The unsaturated monomer containing an acid group may be an ethylenically unsaturated compound containing an acid group, particularly a succinate-based acrylate compound.

單-2-甲基丙烯醯氧基乙基琥珀酸酯

4-(2-(丙烯醯氧基)乙氧基)-4-側氧基丁酸

4-(3-(甲基丙烯醯氧基)丙氧基)-4-側氧基丁酸

4-((5-(甲基丙烯醯氧基)戊基)氧基)-4-側氧基丁酸

Examples of the succinate-based acrylate compound include at least one selected from the group consisting of: mono-2-propenoxyethyl succinate, mono-2-methacryloxyethyl succinic acid Ester, 4-(2-(acryloyloxy)ethoxy)-4-oxobutanoic acid, 4-(3-(methacryloyloxy)propoxy)-4-oxobutanoic acid Acid, and 4-((5-(methacryloxy)pentyl)oxy)-4-oxobutyric acid. [Table 1] Mono-2-propenyloxyethyl succinate

Mono-2-methacryloxyethyl succinate

4-(2-(propenyloxy)ethoxy)-4-oxobutyric acid

4-(3-(methacryloxy)propoxy)-4-oxobutanoic acid

4-((5-(Methacryloxy)pentyl)oxy)-4-oxobutyric acid

The amount of the structural unit (a1) may be 5 mol% to 50 mol%, 5 mol% to 40 mol%, 5 mol% to 50 mol%, based on the total number of mol% of the structural units constituting the copolymer (A) 30 mol%, 5 mol% to 20 mol%, or 5 mol% to 15 mol%. Within the above range, the solubility of the composition is improved so that the pattern does not come off during development, and excellent pattern flatness and resolution can be obtained. (a2) Structural units derived from unsaturated monomers containing alicyclic epoxy groups

The copolymer (A) may contain (a2) a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group.

The structural unit (a2) in the present invention may be derived from an unsaturated monomer containing an alicyclic epoxy group.

The unsaturated monomer (a2) containing an alicyclic epoxy group can be 2,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate, or 3,4-cyclic Oxycyclohexyl methacrylate.

The amount of the structural unit (a2) may be 5 mol% to 50 mol%, 5 mol% to 40 mol%, 5 mol% to 50 mol% based on the total number of mol% of the structural units constituting the copolymer (A) 30 mol%, 5 mol% to 20 mol%, 10 mol% to 50 mol%, 10 mol% to 40 mol%, 10 mol% to 30 mol%, 10 mol% to 20 mol%, or 10 mol% to 15 mol%. Within the above range, the storage stability of the composition is maintained, and the film retention rate is enhanced. (a3) Structural units derived from unsaturated monomers containing acyclic epoxy groups

The copolymer (A) may contain (a3) a structural unit derived from an unsaturated monomer containing an acyclic epoxy group.

The structural unit (a3) in the present invention may be derived from an unsaturated monomer containing an acyclic epoxy group.

The unsaturated monomer containing an acyclic epoxy group may be glycidyl acrylate, glycidyl methacrylate, or 4-hydroxybutyl acrylate glycidyl ether.

The amount of the structural unit (a3) may be 5 mol% to 50 mol%, 5 mol% to 40 mol%, 5 mol% to 50 mol%, based on the total number of mol% of the structural units constituting the copolymer (A) 30 mol%, 5 mol% to 20 mol%, or 5 mol% to 15 mol%. Within the above range, the storage stability of the composition is maintained, and the film retention rate is enhanced.

If the copolymer (A) contains both structural units (a2) and (a3), the total amount of the structural units (a2) and (a3) may be 5 moles based on the total number of moles of the structural units of the copolymer (A). Ear% to 60 mol%, 10 mol% to 60 mol%, 10 mol% to 50 mol%, or 10 mol% to 45 mol%. In addition, the molar ratio of the structural units (a2) and (a3) may be 50 to 99: 50 to 1, 50 to 90: 50 to 10, 50 to 85: 50 to 15, 50 to 80: 50 to 20, or 50 to 75: 50 to 25. Within the above range, it is possible to achieve excellent stability, heat resistance, and chemical resistance over time at room temperature, and enhanced pattern formation. And (a4) structural units derived from unsaturated monomers that are different from (a1) to (a3)

The copolymer (A) may contain (a4) structural units derived from unsaturated monomers other than (a1) to (a3). In this case, the structural unit (a4) may be derived from one or more, two or more, or three or more unsaturated monomers.

The copolymer (A) in the present invention may further include (a4) structural units different from (a1) to (a3). The structural unit (a4) may be derived from an ethylenically unsaturated compound other than the structural unit described above.

In particular, the structural unit (a4) may be derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof. Examples of them include: unsaturated monocarboxylic acids, such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and their anhydrides, such as maleic acid, maleic anhydride, and fumaric acid , Itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; and trivalent or higher unsaturated polycarboxylic acids and their anhydrides.

In addition, it may be at least one selected from the group consisting of: ethylenically unsaturated compounds having an aromatic ring, such as phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxy Ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (Meth) acrylate, tribromophenyl (meth)acrylate, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, three Ethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, methoxy styrene , Ethoxystyrene, propoxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene, vinyl toluene, divinylbenzene, vinylphenol, o-vinylbenzylmethyl Base ether, m-vinyl benzyl methyl ether, and p-vinyl benzyl methyl ether; unsaturated carboxylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) ) Butyl acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) Ethylhexyl acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethacrylate, ethyl α-hydroxymethacrylate, α-hydroxypropyl methacrylate, α-hydroxyl Butyl methacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytri Ethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, tetrafluoropropyl (meth)acrylate, (methyl) ) 1,1,1,3,3,3-hexafluoroisopropyl acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, Dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; N-vinyl tertiary amines containing N-vinyl groups, such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinyl 𠰌line; unsaturated ethers, such as vinyl methyl ether and vinyl Diethyl ether; and unsaturated amides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide and N-Cyclohexylmaleimide.

The amount of the structural unit (a4) may be 50 mol% to 99 mol%, 50 mol% to 90 mol%, 55 mol% to 85% based on the total number of mol of the structural units of the copolymer (A) Mol%, or 60 mol% to 80 mol%. Within the above range, the reactivity of the copolymer (A) can be controlled and its solubility can be increased, so as to significantly enhance the coatability of the photosensitive resin composition.

The copolymer (A) used in the present invention may have a weight average molecular weight of 10,000 Da or more, or less than 10,000 Da. In this case, the copolymer (A) having a weight average molecular weight of less than 10,000 Da cannot be used alone. It must be used in combination with a copolymer having 10,000 Da or more. In particular, the copolymer (A) used in the present invention may have a weight average molecular weight of 10,000 Da or more, 15,000 Da or more, 10,000 to 50,000 Da, 12,000 to 45,000 Da, or 15,000 to 40,000 Da. In addition, the copolymer (A) used in the present invention may have a weight average molecular weight of 5,000 Da to less than 10,000 Da, 5,000 to 9,000 Da, 5,000 to 8,000 Da, or 5,000 to 7,000 Da. If it has a weight average molecular weight within the above range, the adhesion to the substrate is excellent, the physical and chemical properties are favorable, and the viscosity is appropriate.

The copolymer (A) used in the present invention may include at least one selected from the group consisting of structural units (a1) to (a4) as described above. For example, the copolymer (A) may include a combination of structural units (a1) to (a4), a combination of (a2) to (a4), a combination of (a2) and (a3), a combination of (a2) and (a4) , And the combination of (a3) and (a4).

The copolymer (A) used in the present invention can be synthesized by copolymerization known in the art. The range of the amount of the copolymer (A) may be 10 to 50% by weight, 10 to 40% by weight, 10 to 35% by weight, 15 to 40% by weight based on the total weight of the photosensitive resin composition (excluding the remainder of the solvent). %, 15 to 35% by weight, or 20 to 35% by weight. Within the above range, the pattern profile after development may be advantageous, and properties such as film retention rate and chemical resistance may be enhanced. (B) Photopolymerizable compound

The photopolymerizable compound (or monomer) used in the present invention is a compound that is polymerizable under the action of a photopolymerization initiator. It may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated group. From the viewpoint of chemical resistance, it may preferably be a polyfunctional compound having at least two functional groups.

The polymerizable compound may be at least one selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin Tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tri(meth)acrylate and monoester of succinic acid , Neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, dine pentaerythritol penta (meth) acrylate Monoester and succinic acid, caprolactone-modified dineopentaerythritol hexa(meth)acrylate, neopentaerythritol triacrylate-hexamethylene diisocyanate (neopentylerythritol three The reaction product of acrylate and hexamethylene diisocyanate), trineopentaerythritol hepta(meth)acrylate, trineopentaerythritol octa(meth)acrylate, bisphenol A epoxy acrylate , And ethylene glycol monomethyl ether acrylate, but it is not limited to this.

Examples of commercially available photopolymerizable compounds may include monofunctional (meth)acrylates such as Aronix M-101, M-111, and M-114 manufactured by Toagosei Co., Ltd. , KAYARAD TC-110S and TC-120S manufactured by Nippon Kayaku Co., Ltd., and V manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd. -158 and V-2311; bifunctional (meth)acrylates, such as Aronix M-210, M-240 and M-6200 manufactured by Toagosei Co., Ltd., and KAYARAD HDDA, HX manufactured by Nippon Kayaku Co., Ltd. -220 and R-604, and V-260, V-312 and V-335 HP manufactured by Disproportionate Chemical Industry Co., Ltd. in Osaka; and trifunctional and higher-functional (meth)acrylates such as Aronix M- 309, M-400, M-403, M-405, M-450, M-7100, M-8030, M-8060, and TO-1382 manufactured by Toagosei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. KAYARAD TMPTA, DPHA, DPHA-40H, DPCA-20, DPCA-30, DPCA-60 and DPCA-120, as well as V-295, V-300, V-360, V- GPT, V-3PA and V-400.

The photopolymerizable compound may be used alone or in a combination of two or more thereof. 10 to 100 parts by weight, 10 to 90 parts by weight, 10 to 80 parts by weight, 20 to 90 parts by weight, 20 to 80 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) can be used. Parts by weight, 25 to 80 parts by weight, or 25 to 60 parts by weight of the photopolymerizable compound. Within the above range, pattern development is advantageous, and excellent chemical resistance and elastic recovery can be achieved. (C) Photopolymerization initiator

The photopolymerization initiator used in the present invention may be any known photopolymerization initiator.

The photopolymerization initiator may be selected from the group consisting of: acetophenone-based compounds, non-imidazole-based compounds, tris-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds Compounds, polynuclear quinone-based compounds, thioketone-based compounds, diazonium-based compounds, imine sulfonate-based compounds, oxime-based compounds, carbazole-based compounds, and boric acid-based compounds , Ketone-based compounds, and their mixtures. In particular, the photopolymerization initiator may be at least one selected from the group consisting of an oxime-based compound, a tris-based compound, or a ketone-based compound. More specifically, the photopolymerization initiator may be a combination of an oxime-based compound and a tris-based compound, or a combination of an oxime-based compound, a tris-based compound, and a ketone-based compound.

Specific examples of the photopolymerization initiator include 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethyl Valeronitrile), benzyl peroxide, laurel peroxide, tertiary butyl peroxypivalate, 1,1-bis(tertiary butylperoxy)cyclohexane, p-dimethylamine Acetophenone, 2-benzyl-2-(dimethylamino)-1-[4-(4-𠰌olinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl- 1-Phenyl-propan-1-one, benzyl dimethyl ketal, benzophenone, benzoin propyl ether, diethyl thioketone, 2,4-bis(trichloromethyl) )-6-p-methoxyphenyl-s-tris, 2-trichloromethyl-5-styryl-1,3,4-diazole, 9-phenylacridine, 3-methyl 5-amino-((s-tris-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl Polymer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2- Dione-2-(ortho-benzyl oxime), o-benzyl-4'-(phenylmercapto)benzyl-hexyl ketoxime, 2,4,6-trimethylphenylcarbonyl- Diphenylphosphino oxide, hexafluorophosphoric acid-trialkylphenyl sulfonate, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, (E)-2-(4- Styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris, 2-dimethylamino-2-(4-methylbenzyl)-1-( 4-𠰌lin-4-ylphenyl)-butan-1-one, and mixtures thereof, but it is not limited thereto.

For reference, examples of commercially available oxime-based photopolymerization initiators include SPI-03 (Sanyo, Korea), OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), N -1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 (ADEKA). In addition, examples of commercially available tris-based photopolymerization initiators include tris-Y (Tronly) and tris-Y (medical synthesis).

The amount of 10 to 30 parts by weight, 10 to 25 parts by weight, 10 to 20 parts by weight, or 10 to 18 parts by weight based on 100 parts by weight of the copolymer (A) (based on the solid content) can be used. Photopolymerization initiator.

In particular, 1 to 20 parts by weight, 1 to 18 parts by weight, 5 to 20 parts by weight, 5 to 18 parts by weight, based on 100 parts by weight (based on the solid content) of the copolymer (A) can be used. An oxime-based photopolymerization initiator in an amount of 8 to 20 parts by weight or 8 to 18 parts by weight. Can be used 1 to 10 parts by weight, 1 to 9 parts by weight, 1 to 8 parts by weight, 2 to 10 parts by weight, 2 to 8 parts by weight, or 3 to 6 parts by weight based on three 𠯤 Photopolymerization initiator. The ketone-based light can be used in an amount of 1 to 10 parts by weight, 1 to 9 parts by weight, 1 to 8 parts by weight, 2 to 10 parts by weight, 2 to 8 parts by weight, or 2 to 6 parts by weight. Polymerization initiator.

If the oxime-based photopolymerization initiator is used in an amount within the above range, the development and coating characteristics can be enhanced while having high sensitivity. In addition, if the tri-based photopolymerization initiator is used in an amount within the above range, a coating film having excellent chemical resistance and taper angle together with high sensitivity after pattern formation can be obtained. (D) Coloring agent

The colored photosensitive resin composition of the present invention contains a coloring agent that imparts light-shielding properties to it. The coloring agent used in the present invention may be a mixture of two or more inorganic or organic coloring agents. It preferably has high color yield and high heat resistance.

Colorants include black colorants and colorants (d3) other than black colorants.

The black colorant may be a black inorganic colorant (d2), a black organic colorant (d1), or a combination thereof. In particular, the black colorant may include a black inorganic colorant and may be used in an amount of 0.01 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

Any black inorganic colorant, any black organic colorant, and any coloring agent other than black pigments known in the art can be used. For example, any compound classified as a pigment in the Color Index (published by the Society of Dyers and Colourists) and any dye known in the art can be used.

Specific examples of the black inorganic colorant may include carbon black, titanium black, metal oxides such as Cu-Fe-Mn-based oxides and synthetic iron black, and the like. From the viewpoint of pattern characteristics and chemical resistance, it is preferable to use carbon black among them.

Specific examples of the black organic colorant may include nigrosine, internal amides black, perylene black, and the like. From the viewpoints of optical density, dielectric properties, etc., among them, internal amide black (for example, black 582 from BASF) is preferable.

Specific examples of coloring agents other than black colorants may include CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148 , 150, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9 , 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 13, 14, 19, 23, 25, 27, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 etc.), 16, 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; and CI Pigment Brown 28. In particular, the coloring agent other than the black coloring agent may be a blue coloring agent, a purple coloring agent, or a combination thereof. For the purpose of preventing light leakage and light blurring and from the viewpoint of dispersibility and chemical resistance of the colored dispersion composition, preferred among them is CI Pigment Blue 15: 6 and 60, or CI Pigment Violet twenty three.

The amount of the colorant may be 5 to 70% by weight or 8 to 60% by weight based on the total weight of the solid content of the colored photosensitive resin composition (ie, the weight excluding the solvent). In particular, the colorant may include 0.01 to 50% by weight of the black colorant and 0.01 to 20% by weight of the black colorant based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the weight of the solvent). Outside the coloring agent. More specifically, the colorant includes a black inorganic colorant or a black organic colorant and may include 0 to 15% by weight of the black inorganic colorant based on the total weight of the solid content of the colored photosensitive resin composition (ie, the weight excluding the solvent). Colorant, 0 to 40% by weight of black organic colorant, and 0.01 to 20% by weight of coloring agent other than black colorant. Preferably, it may include 0 to 8.2% by weight of black inorganic colorant and 0 to 45% by weight of black organic Coloring agent and 0.01 to 15% by weight of coloring agent other than black coloring agent. If the amount of the colorant is within the above range, the pattern profile after development may be advantageous, properties such as chemical resistance and elastic restoring force may be enhanced, and desired optical density and light transmittance may be achieved.

The display including the black matrix of the present invention must have a transmittance of 5% or less in the 700 nm wavelength band in order to prevent red or green light blur when the cured film is formed with a thickness of 3 μm. In addition, the transmittance in the range of 900 to 950 nm must be 10% or higher to facilitate recognition of the alignment code in the process of placing the mask for exposure.

At the same time, the coloring agent used in the present invention may be added to the colored photosensitive resin composition in the form of a mill base, a solvent, etc. mixed with the dispersion resin.

The dispersion resin is used to uniformly disperse the colorant (or pigment) in the solvent and may particularly be at least one selected from the group consisting of a dispersant and a dispersion binder.

Examples of the dispersant may include any known dispersants used for colorants. Specific examples of them include cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicone-based surfactants, fluorine-based surfactants, polyester-based surfactants Compounds, polycarboxylate-based compounds, unsaturated polyamide-based compounds, polycarboxylic acid-based compounds, polycarboxyalkyl salt compounds, polyacrylic acid compounds, polyethyleneimine-based compounds, polyurethane-based compounds , Polyamine ester, polycarboxylate represented by polyacrylate, unsaturated polyamide, polycarboxylic acid, amine salt of polycarboxylic acid, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polysilicon Oxanes, long-chain polyamino amide phosphates, polycarboxylates with substituted hydroxyl groups and their modified products, composed of polyesters with free carboxyl groups and poly(lower alkylene imines) or Amide formed by the reaction of salt, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin Or water-soluble polymer compounds, such as polyvinylpyrrolidone, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. Commercially available dispersants may include Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, and -2164 from BYK Co.. They can be used alone or in combination of two or more kinds thereof. The dispersant may have an amine group and/or an acid group as a pigment affinity group and may be an ammonium salt type as necessary.

The dispersant may be added to the colorant in advance by surface-treating the colorant with it or added together with the coloring agent when preparing the colored photosensitive resin composition.

The amine value of the dispersant may be 5 to 200 mg KOH/g, 10 to 200 mg KOH/g, or 50 to 150 mg KOH/g. If the amine value of the dispersant is within the above range, the dispersibility and storage stability of the colorant are excellent, and the surface roughness of the cured film prepared from the resin composition is improved.

The dispersant may be used in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total weight of the colored dispersion. If the amount of the dispersant is within the above range, the colorant is effectively dispersed to improve dispersion stability, and the optical, physical, and chemical properties are improved by maintaining an appropriate viscosity during its application. Therefore, it is desirable in terms of an excellent balance between dispersion stability and viscosity.

If the dispersion binder has an acid value, it may contain monomers having carboxyl groups and unsaturated bonds. Specific examples of monomers having carboxyl groups and unsaturated bonds include: monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and dicarboxylic acids Acid anhydrides; mono(meth)acrylates of polymers with carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylates, etc. Preferred are acrylic acid and methacrylic acid.

In addition, the dispersion binder may include a monomer having an unsaturated bond which is copolymerizable with a monomer having a carboxyl group and an unsaturated bond. Examples of monomers having copolymerizable unsaturated bonds may include, for example, aromatic vinyl compounds such as styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene , M-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-ethylene Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; alkyl (meth)acrylates, such as methyl (meth)acrylate, (methyl) Ethyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, And (meth) acrylate tertiary butyl ester; alicyclic (meth) acrylate, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (methyl) ) Acrylate, tricyclo[5.2.1.0 ^2,6 ] dec-8-yl (meth)acrylate, 2-dicyclopentyloxyethyl (meth)acrylate, and isobornyl (methyl) ) Acrylic esters; aryl (meth)acrylates, such as phenyl (meth)acrylate and benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (methyl) Acrylate and 2-hydroxypropyl (meth)acrylate; N-substituted maleimide compounds, such as N-cyclohexylmaleimide, N-benzylmaleimide, N-benzene Maleimines, N-o-hydroxyphenylmaleimines, N-m-hydroxyphenylmaleimines, N-p-hydroxyphenylmaleimines, N-o- Methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide Imines, N-m-methoxyphenylmaleimines, and N-p-methoxyphenylmaleimines; unsaturated amide compounds, such as (meth)acrylamide and N , N-Dimethyl(meth)acrylamide; and unsaturated oxetane compounds, such as 3-(methacryloxymethyl)oxetane, 3-(methacrylamide Oxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl) Methyl)-2-phenyloxetane, 2-(methacryloxymethyl)oxetane, and 2-(methacryloxymethyl)-4-trifluoro Methyloxetane, which can be used alone or in combination of two or more.

The dispersion binder may include 30 mol% or less of the maleimide monomer based on the total mol number of the constituent units.

The dispersion binder may be used in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total weight of the colored dispersion. If a dispersion binder within the above range is used, the resin composition can maintain a suitable viscosity level and it is better in terms of dispersion stability and developability.

The amount of 100 to 300 parts by weight, 100 to 250 parts by weight, 100 to 200 parts by weight, or 100 to 180 parts by weight based on 100 parts by weight of the copolymer (A) (based on the solid content) can be used. Dispersion binder. (E) Multifunctional thiol compound

The colored photosensitive resin composition of the present invention may contain a multifunctional thiol compound to increase the crosslinking efficiency during curing. In particular, the multifunctional thiol compound has high reactivity by light and heat so that it enables the colored photosensitive resin composition to be crosslinked even at a low temperature of 100° C. or lower to form a cured film. More specifically, the functional group of the multifunctional thiol compound reacts to light and heat so that it allows crosslinking and curing by light and heat to appropriately proceed during the curing step. In addition, it removes unreacted functional groups.

The multifunctional thiol compound may be a compound having 2 or more, 3 or more, or 4 or more mercapto groups. In the case of a compound having one mercapto group, the reactivity of the polyfunctional thiol compound and the compound containing a double bond and a hydroxyl group decreases, making it possible to deteriorate durability and adhesion.

Examples of polyfunctional thiol compounds having two mercapto groups include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol , 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9- Nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, toluene-3,5-dithiol , 3,6-Dichloro-1,2-benzenedithiol, 1,5-naphthalene dithiol, 1,2-benzenedimethylthiol, 1,3-benzenedimethylthiol, 1,4- Benzene dimethyl mercaptan, 4,4-thiobisphenyl mercaptan, 2-di-n-butylamino-4,6-dimercapto-s-tris, trimethylolpropane tris(β-thio Propionate), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, and 1,5-dimercapto-3-sulfur Heteropentane.

Examples of multifunctional thiol compounds having three mercapto groups include thioglycerol, 1,3,5-tris-2,4,6-trimercaptotris, trimethylolpropane trithioglycolate , Trimethylolpropane trithiopropionate, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 2,4,6-tris(mercapto Methyl)methyl nitrite, tris(mercaptomethyl)isocyanurate, tris(3-mercaptopropyl)isocyanurate, 2,4,6-tris(mercaptomethyl)-1, 3-dithiolane, 1,3,5-tris-2,4,6-trimercaptotris, tris(3-mercaptopropionyloxy)ethyl isocyanurate, and trimethylol Propane tri-3-mercaptopropionate.

Examples of polyfunctional thiol compounds having four mercapto groups include neopentyl erythritol tetrathioglycolate, neopentyl erythritol tetrathiopropionate, 1,2,4,5-tetra(mercaptomethyl ) Benzene, tetramercaptobutane, neopentylerythritol tetra-3-mercaptopropionate, and dineopentaerythritol tetra-3-mercaptopropionate.

Preferably, the multifunctional thiol compound may be at least one selected from the group consisting of: tris(3-mercaptopropoxy)ethyl isocyanurate, trimethylolpropane tri-3- Mercaptopropionate, neopentylerythritol tetra-3-mercaptopropionate, and dineopentaerythritol tetra-3-mercaptopropionate.

10 to 50 parts by weight, 10 to 30 parts by weight, 10 to 25 parts by weight, 10 to 20 parts by weight, 15 to 25 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) can be used. Parts by weight or a multifunctional thiol compound in an amount of 15 to 20 parts by weight.

Within the above range, the pattern profile after development is favorable, and excellent chemical resistance and elastic recovery can be achieved. If it is less than the above range, post-baking does not fully proceed (that is, curing does not fully proceed). If it exceeds the above range, it is difficult to control the crosslinking efficiency because the reactivity by light and heat is too high, so that defects such as peeling or protrusions may occur on the pattern during development. Further, the flatness and resolution of the pattern may also be deteriorated. (F) Compounds containing two or more double bonds and two or more hydroxyl groups

The colored photosensitive resin composition of the present invention may further include a compound containing a double bond and a hydroxyl group to more easily form a pattern. In particular, the compound containing a double bond and a hydroxyl group may contain two or more double bonds and two or more hydroxyl groups.

The compound containing a double bond and a hydroxyl group may be at least one selected from the group consisting of: 1,3-diglyceryl alkyd diacrylate, glycerol 1,3-diglyceryl alkyd diacrylate, ((oxygen Bis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate, ((propane-2,2-diylbis(4, 1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate, and (Spiro[茀-9,9'-𠮿口星]-3', 6'-Diylbis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate.

In addition, it may further include a compound having a linear alkylene group and an alicyclic structure having two or more isocyanate groups with a molecule having one or more hydroxyl groups and three , A polyfunctional urethane acrylate compound obtained by the reaction of four or five acryloxy groups and/or methacryloxy groups.

As described above, the compound containing a double bond and a hydroxyl group achieves high resolution by appropriately controlling the reactivity of the polyfunctional thiol compound by heat and light during post-baking. In particular, the hydroxyl group of the compound containing a double bond and a hydroxyl group increases the development speed in the unexposed part, and the hydroxyl group participates in the crosslinking reaction with the thiol group of the multifunctional thiol compound in the exposed part , Thereby improving the degree of curing.

10 to 50 parts by weight, 10 to 45 parts by weight, 10 to 30 parts by weight, 15 to 40 parts by weight, or 15 to 30 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) can be used. A compound containing a double bond and a hydroxyl group in parts by weight.

Within the above range, the pattern profile after development is favorable, and excellent chemical resistance and elastic recovery can be achieved. If it is less than the above range, the solubility of the composition decreases. If it exceeds the above range, the solubility is too large, so that the rate of decrease in the thickness of the pattern increases during the development step and the pattern may be detached at a high resolution of 10 μm or less. (G) Photobase generator

The colored photosensitive resin composition of the present invention may contain a photobase generator to increase the crosslinking and curing efficiency in the composition.

In particular, the colored photosensitive resin composition of the present invention uses a photoradical polymerization initiator together with a photobase generator during curing, so that the photoradical polymerization reaction and the base generation reaction from the base generator proceed simultaneously, which improves the composition. The cross-linking efficiency in the material.

The photobase generator is not particularly limited, and may be, for example, a photobase compound that generates a base in response to a short wavelength or a long wavelength, or an ammonium salt having an anion and an ammonium ion having a pKa of 0 to 4.

The base generated from the photobase generator may be a secondary amine, a tertiary amine, etc., and the base may have a boiling point of 80°C or higher. In addition, the base may have a weight average molecular weight of 80 to 2,000 Da.

An amount of 1 to 10 parts by weight, 1 to 8 parts by weight, 1 to 5 parts by weight, or 1 to 3 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) can be used. Photo base generator. Within the above range, thermal curing and photocuring are performed well even at low temperatures, so that a cured film with good pattern development can be formed. (H) Epoxy compound

The colored photosensitive resin composition of the present invention may contain an epoxy compound to increase the internal density of the resin, thereby improving the chemical resistance of the cured film formed thereby.

The epoxy compound may be an unsaturated monomer containing at least one epoxy group, or a homo-oligomer or hetero-oligomer. Examples of unsaturated monomers containing at least one epoxy group may include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3 (meth)acrylate -Epoxycyclopentyl ester, 3,4-epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate , N-(4-(2,3-glycidoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-glycidoxy)-3 ,5-Dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methyl allyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether , P-vinyl benzyl glycidyl ether, or a mixture thereof. Specifically, glycidyl (meth)acrylate can be used.

Examples of commercially available homo-oligomers of unsaturated monomers containing at least one epoxy group may include GHP-03HP (glycidyl methacrylate homopolymer, Miwon Corporation).

The epoxy compound may further include the following structural unit.

Specific examples thereof may include any structural unit derived from: styrene; styrene with alkyl substituents, such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, two Ethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; styrene with halogen, such as fluorostyrene, chlorostyrene, Bromostyrene and iodostyrene; styrenes with alkoxy substituents, such as methoxystyrene, ethoxystyrene and propoxystyrene; p-hydroxy-α-methylstyrene, acetoxy Styrene; ethylenically unsaturated compounds with aromatic rings, such as divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p-vinylbenzyl methyl ether; no Saturated carboxylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate Ester, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, α-hydroxymethyl Methyl acrylate, α-hydroxy ethyl methacrylate, α-hydroxy propyl methacrylate, α-hydroxy butyl methacrylate, 2-methoxyethyl (meth)acrylate, (meth)acrylic acid 3 -Methoxybutyl ester, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethyl) Glycol) methyl ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth) Base) acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, (methyl) ) 1,1,1,3,3,3-hexafluoroisopropyl acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate , Isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate and dicyclopentyl (meth)acrylate Cyclopentenoxyethyl; tertiary amines with N-vinyl groups, such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinyl 𠰌line; unsaturated ethers, such as vinyl methyl ether And vinyl ether; unsaturated amides, such as N-phenylmaleimines, N-(4-chlorophenyl)maleimines, N-(4-hydroxyphenyl)maleimines Amine and N-cyclohexylmaleimide. The structural unit derived from the above-exemplified compound may be included in the epoxy compound alone or in a combination of two or more thereof.

The epoxy compound may have a weight average molecular weight of 100 to 30,000 Da. Specifically, the epoxy compound may have a weight average molecular weight of 100 to 10,000 Da. If the weight average molecular weight of the epoxy compound is 100 Da or more, the hardness of the cured film can be more excellent. If it is 30,000 Da or less, the thickness of the film becomes uniform with a smaller step difference, which is more suitable for planarization.

The amount of the epoxy compound may be 1 to 20 parts by weight, 1 to 10 parts by weight, 5 to 20 parts by weight, 5 to 15 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) Number or 5 to 10 parts by weight. Within the above range, the pattern profile after development can be advantageous, properties such as chemical resistance and elastic restoring force can be enhanced, and problems of separation or deterioration of the storage stability of the composition can be prevented during the development step. (I) Adhesion promoter

The colored photosensitive resin composition according to the present invention may further include an adhesion promoter to enhance adhesion to the substrate.

The adhesion promoter may have at least one reactive group selected from the group consisting of: carboxyl group, (meth)acrylic group, isocyanate group, amine group, mercapto group, vinyl group And epoxy groups.

The type of adhesion promoter is not particularly limited. It may be at least one selected from the group consisting of: trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane Silane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylamino Propyl trimethoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane Silane, and their mixtures.

Preferably, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-isocyanate propyltriethoxysilane, N-phenyl-3-amine Propyl propyl trimethoxy silane, or N-phenylamino propyl trimethoxy silane, which can enhance the film retention and adhesion to the substrate.

The amount of adhesion promoter may be 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight based on 100 parts by weight of the copolymer (A) (based on the solid content) Number, 1 to 5 parts by weight, or 1 to 3 parts by weight. Within the above range, the adhesion to the substrate can be further enhanced. (J) Surfactant

The colored photosensitive resin composition of the present invention may further contain a surfactant in order to enhance coatability and prevent the occurrence of defects.

Although the kind of surfactant is not particularly limited, for example, a fluorine-based surfactant or a silicone-based surfactant may be used.

Commercially available silicone-based surfactants can include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone, TSF-4440, TSF-4300, TSF-4445, TSF-4445 from GE Toshiba Silicone TSF-4446, TSF-4460 and TSF-4452, BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354 and BYK-399 etc. from BYK. They can be used alone or in combination of two or more kinds thereof.

Commercially available fluorine-based surfactants may include Megaface F-470, F-471, F-475, F-482, F-489, and F-563 from Dainippon Ink Chemical Industry Co., Ltd. (DIC) and from Chiba's F-563.

From the viewpoint of the coatability of the composition, preferred among these surfactants may be BYK-333 and BYK-307 from BYK and F-563 from Chiba.

The amount of the surfactant may be 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.1 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the copolymer (A) (based on the solid content) number. Within the above range, the colored photosensitive resin composition can be applied smoothly. (K) Solvent

The colored photosensitive resin composition of the present invention can preferably be prepared as a liquid composition (in which the above components are mixed with a solvent). Any solvent known in the art (compatible with but not reactive with the components in the colored photosensitive resin composition) can be used to prepare the colored photosensitive resin composition.

Examples of the solvent may include glycol ethers, such as ethylene glycol monoethyl ether; glycol alkyl ether acetates, such as ethyl cellosolve acetate; esters, such as ethyl 2-hydroxypropionate; Alcohols, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and alkoxyalkyl acetates, such as 3-methoxy acetate Butyl butyl ester. The solvent can be used alone or in combination of two or more.

From the viewpoint of coatability and stability of the finally obtained colored photosensitive resin composition, the amount of the solvent is not particularly limited, but it may be 50 to 50 based on the total weight of the finally prepared colored photosensitive resin composition. 90% by weight or 70 to 85% by weight. If the amount of the solvent is within the above range, the resin composition is smoothly coated, and the delay margin that may occur during operation is small.

In addition, the colored photosensitive resin composition of the present invention may contain other additives, such as antioxidants and stabilizers, as long as it does not adversely affect the physical properties of the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention containing the above-described components can be prepared by a common method, for example, by the following method.

First, the colorant is mixed with a dispersion resin, a dispersant, and a solvent in advance and dispersed therein using a bead mill until the average particle diameter of the colorant reaches a desired value, thereby preparing a colored dispersion. In this case, the surfactant and/or copolymer may be partially or completely blended. Added to the dispersion liquid are the remaining copolymers and surfactants, photopolymerizable compounds, photopolymerization initiators, polyfunctional thiol compounds, and compounds containing double bonds and hydroxyl groups. If necessary, additives such as epoxy compounds or another solvent are further blended to a certain concentration, and then they are sufficiently stirred to obtain the desired colored photosensitive resin composition.

The invention also provides a light-shielding black matrix prepared from the colored photosensitive resin composition.

The black matrix can be prepared by a coating forming step, an exposure step, a development step, and a heating step.

In the coating forming step, the colored photosensitive resin composition according to the present invention is applied to a desired thickness (for example, 1 To 25 µm) is coated on the pretreated substrate, which is then pre-baked at a temperature of 70 to 100°C for 1 to 10 minutes to form a coated film by removing the solvent therefrom.

In order to form a pattern on the coated film, a mask having a predetermined shape is placed thereon, and then the mask is irradiated with 200 to 500 nm activating rays. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used. If desired, X-rays, electron rays, etc. can also be used. The exposure dose may vary according to the types and composition ratios of the components of the composition and the thickness of the dried coating. If a high-pressure mercury lamp is used, it can be 500 mJ/cm ² or lower (at a wavelength of 365 nm).

After the exposure step, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc. is used as a developer to dissolve and remove unnecessary parts, whereby only the exposed part remains to form a pattern. The image pattern obtained by the development is cooled to room temperature and post-baked in a hot air circulating drying oven at a temperature of 50 to 100°C, 50 to 90°C or 60 to 90°C for 10 to 60 minutes, So as to get the final pattern.

Because the light-shielding black matrix prepared in this way has excellent characteristics, it can be advantageously used in electronic devices of liquid crystal displays and quantum dot displays. Therefore, the present invention provides an electronic device including a light-shielding black matrix.

In addition to having the black matrix of the present invention, liquid crystal displays and quantum dot displays may include other components known to those skilled in the art. In other words, liquid crystal displays and quantum dot displays to which the black matrix of the present invention can be applied can fall within the scope of the present invention. Implementation of the present invention

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

In the following preparation examples, the weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) with reference to polystyrene standards. Preparation of the copolymer (A-1) is: EXAMPLES Example 1 Preparation of

In a nitrogen atmosphere, a 250 ml round bottom flask (equipped with a reflux condenser and stirrer) was charged with a monomer mixture dissolved in 107.98 g of propylene glycol monomethyl ether acetate (PGMEA) together with a radical polymerization initiator. 2.34 g (3.0 mol%) of V-65, the monomer mixture contains 10.68 g (32 mol%) of styrene, 8.01 g (25 mol%) of methyl methacrylate, 10.43 g (15 mol%) Ear%) 2-propenyloxyethyl succinate, 11.32 g (18 mol%) 2,4-epoxycyclohexyl methyl methacrylate and 4.56 g (10 mol%) formaldehyde Glycidyl acrylate. Thereafter, polymerization was carried out at 65°C and continued for 18 hours to obtain a copolymer (A-1) having a solid content of 31.32% by weight. The copolymer thus prepared has an acid value of 19.93 mg KOH/g, a polydispersity (Mw/Mn) of 4.38, and a weight average molecular weight (Mw) of 35,000 Da. Preparation of Copolymer (A-2): The preparation of Example 2

A 500 ml round bottom flask (equipped with reflux condenser and stirrer) was charged with 100 g of the monomer mixture together with 300 g of propylene glycol methyl ether acetate (PGMEA) as a solvent and 3 g as a radical polymerization initiator. 2,2'-Azobis(2,4-dimethylvaleronitrile), the monomer mixture contains 43 mol% styrene, 27.5 mol% methyl methacrylate, 20.5 mol% formaldehyde Acrylic acid and 9 mole% glycidyl methacrylate. Then, the mixture was heated to 70° C. and stirred for 5 hours to obtain a copolymer (A-2) having a solid content of 29.8% by weight. The copolymer thus prepared had an acid value of 28 mg KOH/g and a weight average molecular weight (Mw) of 6,500 Da. Preparation of Copolymer (A-3): The preparation of Example 3

A 500 ml round bottom flask (equipped with a reflux condenser and stirrer) was charged with 100 g of the monomer mixture together with 300 g of propylene glycol methyl ether acetate (PGMEA) as a solvent and 2 g as a radical polymerization initiator. 2,2'-Azobis(2,4-dimethylvaleronitrile), the monomer mixture contains 51mol% N-phenylmaleimide, 4mol% styrene, 10mol% Ear% 4-hydroxybutyl acrylate glycidyl ether and 35 mol% methacrylic acid. Then, the mixture was heated to 70°C and stirred for 5 hours to obtain a copolymer (A-3) having a solid content of 31.3% by weight. The copolymer thus prepared had an acid value of 31.7 mg KOH/g and a weight average molecular weight (Mw) of 20,545 Da. Examples and comparative examples: Preparation of photosensitive resin composition

The components used in the following examples and comparative examples are as follows. [Table 2] Component Solid content (wt%) manufacturer Copolymer (A) Preparation example 1 31.32 - Preparation example 2 29.8 - Preparation example 3 31.3 - Photopolymerizable compound (B) Dineopentaerythritol hexaacrylate (DPHA) 100 Nippon Kayaku Co., Ltd. Photopolymerization initiator (C) C-1 Oxime-based photopolymerization initiator 100 Sanyang Company C-2 (E)-2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris (tris-Y) 100 Pharmaceutical Synthesis Colorant (D) D-1 Organic carbon (organic black colorant) + dispersant + binder BK-7544 20.1 Tokuishi Co., Ltd. D-2 Carbon black + dispersant + binder BK-7539 21.3 Tokuishi Co., Ltd. D-3 Pigment Blue (15: 6) + Dispersant + Binder Blue B2 16.97 IRIDOS Multifunctional thiol compound (E) Neopentylerythritol tetrakis (3-mercaptopropionate) (PETMP) 100 Aldrich Compounds containing double bonds and OH groups (F) F-1 1,3-Diglycerol alkyd diacrylate 100 Aldrich F-2 LTM II 100 BASF Corporation Photo base generator (G) 9-anthrylmethyl N,N-ethyl carbamate 100 Contolux Co., Ltd. Epoxy compound (H) Glycidyl methacrylate homopolymer (GHP-03) 100 Miwon Corporation Adhesion promoter (I) N-phenyl-3-aminopropyl trimethoxysilane 100 JNC Surfactant (J) F-563 100 Chiba Solvent (K) Propylene glycol monomethyl ether acetate (PGMEA) - Chemtronix Example 1

100 parts by weight of the copolymer (A-1) of Preparation Example 1, 32.143 parts by weight of dineopentaerythritol hexaacrylate as the photopolymerizable compound (B), and 10.944 parts by weight of oxime-based light Polymerization initiator (C-1), 3.648 parts by weight of three-based photopolymerization initiator (C-2), 112.359 parts by weight of coloring agent (D-1), 16.051 parts by weight of coloring agent (D -2), 32.103 parts by weight of coloring agent (D-3), 19.644 parts by weight of multifunctional thiol compound (E), 26.785 parts by weight containing two or more double bonds and two or more Compound with multiple hydroxyl groups (F-1), 1.824 parts by weight of photobase generator (G), 7.296 parts by weight of epoxy compound (H) GHP-03, 1.459 parts by weight of adhesion promoter ( I) and 0.547 parts by weight of F-563 as the surfactant (J) are uniformly mixed. Here, the corresponding contents are based on those excluding the solid content of the solvent. The mixture was dissolved in PGMEA so that the solid content of the mixture was 19% by weight. The resultant was mixed for 2 hours to prepare a liquid-phase photosensitive resin composition. Examples 2 to 4 and Comparative Examples 1 to 10

The photosensitive resin compositions were each prepared in the same manner as in Example 1, except that the types and/or contents of the corresponding components were changed as shown in Tables 3 and 4 below. [table 3] Copolymer (A) Photopolymerizable compound (B) Photopolymerization initiator (C) Colorant (D) A-1 A-2 A-3 C-1 C-2 D-1 D-2 D-3 Example 1 100 - - 32.143 10.944 3.648 112.359 16.051 32.103 Example 2 64.286 35.714 - 32.143 10.515 3.505 107.949 15.421 30.843 Example 3 - - 100 32.143 10.944 3.648 112.36 16.051 32.103 Example 4 100 - - 32.143 10.944 3.648 112.359 16.051 32.103 Comparative example 1 - - 100 - 10.515 3.505 107.949 15.421 30.843 Comparative example 2 100 - - - 10.515 3.505 107.949 15.421 30.843 Comparative example 3 - - 100 78.572 10.515 3.505 107.949 15.421 30.843 Comparative example 4 - 100 - 78.572 10.514 3.505 107.949 15.421 30.843 Comparative example 5 100 - - 58.929 10.515 3.505 107.949 15.421 30.843 Comparative example 6 100 - - 39.285 10.515 3.505 107.949 15.421 30.843 Comparative example 7 100 - - - 10.515 3.505 107.949 15.421 30.843 Comparative example 8 100 - - 67.857 6.809 - 104.862 14.98 29.961 Comparative example 9 100 - - 39.286 6.809 - 104.862 14.98 29.961 Comparative example 10 100 - - 78.571 6.809 - 104.862 14.98 29.961 [Table 4] Multifunctional thiol compound (E) Compounds containing double bonds and OH groups (F) Photo base generator (G) Epoxy compound (H) Adhesion promoter (I) Surfactant (J) F-1 F-2 Example 1 19.644 26.785 - 1.824 7.296 1.459 0.547 Example 2 19.644 26.785 26.786 1.752 - 1.402 0.526 Example 3 19.644 26.785 - 1.824 7.296 1.459 0.547 Example 4 19.644 26.785 - 1.824 7.296 1.459 0.547 Comparative example 1 - 78.572 - 1.752 - 1.402 0.526 Comparative example 2 - 78.572 - 1.752 - 1.402 0.526 Comparative example 3 - - - 1.752 - 1.402 0.526 Comparative example 4 - - - 1.752 - 1.402 0.526 Comparative example 5 19.644 - - 1.752 - 1.402 0.526 Comparative example 6 39.286 - - 1.752 - 1.402 0.526 Comparative example 7 78.571 - - 1.752 - 1.402 0.526 Comparative example 8 10.714 - - 3.405 - 1.362 0.511 Comparative example 9 - 39.286 - 3.405 - 1.362 0.511 Comparative example 10 - - - 3.405 - 1.362 0.511 Preparation of cured film

The photosensitive resin compositions obtained in Examples and Comparative Examples were each coated on a glass substrate using a spin coater, and prebaked at 85°C for 150 seconds to form a coated film with a thickness of 1.6 µm. A mask prepared in order to form a line pattern having a size of 5 μm by 100% exposure was placed on the coated film at a distance of 50 μm from the substrate, and then subjected to exposure. After that, use an aligner (model name: MA6) to ^{irradiate the coated film with light at an exposure dose of 50 mJ/cm 2} (based on a wavelength of 365 nm) for a certain period of time. The aligner emits wavelengths from 200 nm to 450 nm light. Thereafter, it was developed with an aqueous potassium hydroxide solution diluted to a concentration of 0.04% by weight at 24°C until the unexposed part was completely washed out. The pattern thus formed was post-baked in an oven at 85°C for 60 minutes to obtain a cured film. Evaluation example 1 : Evaluation of development time and detachability

Prepare a cured film having a total thickness of 1.5 (± 0.1) µm after post-baking according to the method for preparing a cured film as described above. In this case, in the process of preparing the cured film, the time for the unexposed part to be completely washed out with a 0.04% by weight potassium hydroxide aqueous solution (until the O-ring part is completely visible behind the substrate at the stage of the developing device) is measured As the development time. In addition, the degree of detachment during development was evaluated visually. The results are shown in Table 5 below.

Development time/Releasability

◎: 16 seconds to 75 seconds / no defect after visual inspection

○: more than 75 seconds to 150 seconds / the unexposed part breaks off into fine grains

×: Less than 16 seconds or more than 150 seconds/Unexposed part breaks off into irregular blocks Evaluation Example 2 : Evaluation of pattern flatness and adhesion

The thickness and critical dimension of a cured film with a thickness of 1.5 (± 0.1) µm prepared by the same method as in Evaluation Example 1 were measured using SNU equipment. In addition, an optical microscope was used to visually check the flatness of the line pattern formed on the cured film and whether there was any loss of the pattern. The results are shown in Table 5 below and in Figures 1 and 2.

◎: Form parallel patterns without defects such as protrusions (good straightness)

○: Defects such as protrusions on the pattern

×: Many defects such as protrusions on the pattern Evaluation Example 3 : Evaluation of chemical resistance

A cured film having a thickness of 1.5 (±0.1) µm prepared by the same method as in Evaluation Example 1 was cut into a size of 2 cm × 1 cm to prepare samples. Load 10 ml of PGMEA into a chemical-resistant container, close the lid, and perform a water bath at 85°C. The sample was then submerged and soaked for 10 minutes. The sample was taken out after 10 minutes, cooled to room temperature, and washed with running water. Use SNU equipment to measure the thickness of the sample before and after immersion in the solvent. The results are shown in Table 5 below.

◎: 10% or less thickness change

○: Thickness change greater than 10% to 20%

×: Thickness change greater than 20% [Table 5] Developability Break away Flatness Adhesion Chemical resistance Example 1 ○ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ○ ○ ◎ ◎ Example 4 ○ ◎ ◎ ◎ ◎ Comparative example 1 ◎ X X X ◎ Comparative example 2 Undeveloped - - - ◎ Comparative example 3 ◎ ◎ ◎ ◎ X Comparative example 4 ◎ ◎ ◎ X X Comparative example 5 ○ ◎ X X ○ Comparative example 6 ○ X X X ◎ Comparative example 7 Undeveloped - - - ◎ Comparative example 8 X X ◎ ◎ X Comparative example 9 Part of the film detached during the development step. Comparative example 10 Part of the film detached during the development step.

As can be seen from the results in Table 5 and Figures 1 and 2, the cured films formed from the photosensitive resin compositions of Examples 1 to 4 all have a fast development time and show good flatness and adhesion during development. There are no defects such as pattern detachment or protrusion. Furthermore, they are excellent in chemical resistance. The cured films prepared in Comparative Examples 1 to 10 were not developed or developed for too long, the patterns were detached or lost, and defects such as protrusions were observed on some of the formed patterns. Further, they are inferior to the examples in terms of chemical resistance.

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[Figure 1] A photograph of the surface of a cured film prepared from the composition of the example taken with an optical microscope.

[Figure 2] A photograph of the surface of a cured film prepared from the composition of the comparative example taken with an optical microscope.

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Claims (15)

A photosensitive resin composition comprising: (A) Copolymer; (B) Photopolymerizable compound; (C) Photopolymerization initiator; (D) Colorants; and (E) Multifunctional thiol compound. The photosensitive resin composition according to claim 1, which further comprises (F) a compound containing two or more double bonds and two or more hydroxyl groups. The photosensitive resin composition according to claim 1, wherein the multifunctional thiol compound (E) is at least one selected from the group consisting of: tris-(3-mercaptopropoxy)ethyl isocyanurate Acid esters, trimethylolpropane tri-3-mercaptopropionate, neopentylerythritol tetra-3-mercaptopropionate and dineopentylerythritol tetra-3-mercaptopropionate. The photosensitive resin composition according to claim 1, which contains the multifunctional thiol compound (E) in an amount of 10 to 50 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content . The photosensitive resin composition according to claim 2, wherein the compound (F) containing two or more double bonds and two or more hydroxyl groups is at least one selected from the group consisting of: 1,3-Diglyceryl alkyd diacrylate, glycerol 1,3-diglyceryl alkyd diacrylate, ((oxybis(4,1-phenylene))bis(oxy))bis(2- Hydroxypropane-3,1-diyl) diacrylate, ((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3, 1-diyl) diacrylate and (spiro[茀-9,9'-𠮿口星]-3',6'-diylbis(oxy))bis(2-hydroxypropane-3,1-di Base) diacrylate. The photosensitive resin composition according to claim 1, which contains the compound (F) in an amount of 10 to 50 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content. The photosensitive resin composition according to claim 1, wherein the copolymer (A) comprises at least one selected from the group consisting of: (a1) a structural unit derived from an unsaturated monomer containing an acid group; a2) a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group; (a3) a structural unit derived from an unsaturated monomer containing an acyclic epoxy group; and (a4) different from (a1 ) To (a3) structural units derived from unsaturated monomers. The photosensitive resin composition according to claim 7, wherein the unsaturated mono-system containing an acid group is based on a succinate-based acrylate compound. The photosensitive resin composition according to claim 8, wherein the succinate-based acrylate compound is at least one selected from the group consisting of: mono-2-propenoxyethyl succinate, mono- 2-methacryloxyethyl succinate, 4-(2-(acryloxy)ethoxy)-4-oxobutanoic acid, 4-(3-(methacryloxy) ) Propoxy)-4-oxobutanoic acid, and 4-((5-(methacryloxy)pentyl)oxy)-4-oxobutanoic acid. The photosensitive resin composition according to claim 7, wherein the range of the total content of the structural unit (a2) and the structural unit (a3) is 10 based on the total molar number of the structural unit of the copolymer (A) Mole% to 50 Mole%. The photosensitive resin composition according to claim 7, wherein the molar ratio of the structural unit (a2) and the structural unit (a3) is 50 to 99: 50 to 1. The photosensitive resin composition according to claim 1, wherein the colorant (D) includes a black colorant, and the black colorant is a black inorganic colorant (d2), a black organic colorant (d1), or a combination thereof . The photosensitive resin composition according to claim 12, wherein the colorant (D) includes a colorant (d3) other than the black colorant, and the colorant (d3) other than the black colorant is blue Colorants, purple colorants, or combinations thereof. The photosensitive resin composition according to claim 1, which further contains a photobase generator (G). A black matrix made of the photosensitive resin composition as described in claim 1.

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