KR20210082067A - Colored photosensitive resin composition and black matrix prepared therefrom - Google Patents

Abstract

A colored photosensitive resin composition of the present invention can fully form a cured film even at a low temperature by introducing a polyfunctional thiol compound and a compound having a double bond and a hydroxyl group. In addition, the colored photosensitive resin composition of the present invention has a fast developing speed and excellent resolution and chemical resistance.

Description

Colored photosensitive resin composition and black matrix prepared therefrom {COLORED PHOTOSENSITIVE RESIN COMPOSITION AND BLACK MATRIX PREPARED THEREFROM}

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

A colored photosensitive resin composition is widely used in LCD, OLED, and quantum dot (QD)-based display devices.

The LCD is composed of upper and lower substrates and liquid crystal between both substrates, and a touch screen panel (TSP) may be connected to the upper substrate as necessary. In general, the TSP is manufactured after the assembly process of bonding the color filter and the thin film transistor (TFT). Accordingly, the cured film should be cured at a low temperature in order to minimize the effect on the color filter that has already been manufactured. However, there is a problem that a cured film is not formed because the composition is not sufficiently crosslinked during low temperature curing, or the strength is not sufficient, so a composition capable of low temperature curing is required. In addition, since the OLED and quantum dot (QD)-based display devices are manufactured at a low temperature, a composition suitable for low-temperature curing is required.

On the other hand, a technique for producing a cured film by curing a composition containing an acrylate-based resin as a binder at a low temperature is known in the field (Korean Patent Application Laid-Open No. 2010-0029479), but it was not sufficient to satisfy chemical resistance.

In a general low-temperature curing type coloring composition, an excessive amount of a thermosetting agent such as an epoxy compound is used to increase the degree of curing at a low temperature, or an additive is used to lower the reaction energy. However, these materials have a problem in storage stability, causing problems such as peeling, pattern tearing, and lack of resolution during the cured film manufacturing process.

Korean Patent Publication No. 2010-0029479

Accordingly, an object of the present invention is to provide a colored photosensitive resin composition capable of sufficiently crosslinking and curing even at a low temperature, and excellent in chemical resistance, chemical resistance, developability and resolution of a pattern, and a black matrix prepared therefrom.

In order to achieve the above object, the present invention is (A) a copolymer; (B) a photopolymerizable compound; (C) a photoinitiator; (D) colorants; And (E) a polyfunctional thiol compound; it provides a photosensitive resin composition comprising.

In order to achieve the above other object, the present invention provides a black matrix formed using the photosensitive resin composition.

The coloring photosensitive resin composition of this invention can fully form a cured film also at low temperature by introduce|transducing the compound containing a polyfunctional thiol compound and/or a double bond and a hydroxyl group. In addition, the colored photosensitive resin composition of the present invention has a high development speed and excellent resolution and chemical resistance.

1 is a photograph taken with an optical microscope of the surface of a cured film prepared from the composition of Example.
2 is a photograph taken with an optical microscope of the surface of a cured film prepared from the composition of Comparative Example.

The present invention is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the present invention is not changed.

In the present specification, "comprising" means that other components may be further included unless otherwise specified. In addition, it should be understood that all numbers and expressions indicating amounts of components, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.

The present invention relates to (A) a copolymer; (B) a photopolymerizable compound; (C) a photoinitiator; (D) colorants; And (E) a polyfunctional thiol compound; provides a photosensitive resin composition comprising.

The composition optionally comprises (F) a compound comprising at least two each of a double bond and a hydroxyl group, (G) a photobase generator, (H) an epoxy compound, (I) an adhesion aid, (J) a surfactant and/or (K) may further include a solvent.

As used herein, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate".

The weight average molecular weight for each of the following components refers to the weight average molecular weight (g/mol or Da) in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as the elution solvent).

(A) copolymer

The copolymer (A) may include (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 a non-alicyclic epoxy group; and (a4) a structural unit derived from an unsaturated monomer different from the above (a1) to (a3); may include at least one selected from the group consisting of.

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

More specifically, the copolymer (A) may include the structural unit (a4), and may further include (a1), (a2) and/or (a3).

(a1) a structural unit derived from an unsaturated monomer containing an acid group

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

In the present invention, the structural unit (a1) 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, and specifically, a succinate-based acrylate compound.

For example, the succinate-based acrylate compound, mono-2-acryloyloxyethyl succinate (mono-2-acryloylethyl succinate), mono-2-methacryloyloxyethyl succinate (mono-2-methacryloylethyl) succinate), 4-(2-(acryloyloxy)ethoxy)-4-oxobutanoic acid (4-(2-(acryloyloxy)ethoxy)-4-oxobutanoic acid), 4-(3-(methacryl) Royloxy)propoxy)-4-oxobutanoic acid (4-(3-(methacryloyloxy)propoxy)-4-oxobutanoic acid) and 4-((5-(methacryloyloxy)pentyl)oxy)- It may be at least one selected from the group consisting of 4-oxobutanoic acid (4-((5-(methacryloyloxy)pentyl)oxy)-4-oxobutanoic acid).

The content of the structural unit (a1) is 5 to 50 mol%, 5 to 40 mol%, 5 to 30 mol%, 5 to 20 mol%, based on the total number of moles of the structural units constituting the copolymer (A). or 5 to 15 mol%. When within the above range, the solubility of the composition is improved, the pattern is not peeled off during development, and excellent pattern straightness and resolution can be obtained.

(a2) a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group

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

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

The unsaturated monomer containing the alicyclic epoxy group may be 2,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate.

The content of the structural unit (a2) is 5 to 50 mol%, 5 to 40 mol%, 5 to 30 mol%, 5 to 20 mol%, based on the total number of moles of the structural units constituting the copolymer (A). , 10 mol% to 50 mol%, 10 to 40 mol%, 10 to 30 mol%, 10 to 20 mol%, or 10 to 15 mol%. When within the above range, the storage stability of the composition is maintained and the film remaining rate is improved.

(a3) a structural unit derived from an unsaturated monomer containing a non-alicyclic epoxy group

The copolymer (A) may include (a3) a structural unit derived from an unsaturated monomer containing a non-alicyclic epoxy group.

In the present invention, the structural unit (a3) may be derived from an unsaturated monomer containing a non-alicyclic epoxy group.

The unsaturated monomer containing the non-alicyclic epoxy group may be glycidyl acrylate, glycidyl methacrylate or 4-hydroxybutyl acrylate glycidyl ether.

The content of the structural unit (a3) is 5 to 50 mol%, 5 to 40 mol%, 5 to 30 mol%, 5 to 20 mol%, based on the total number of moles of the structural units constituting the copolymer (A). , or 5 to 15 mol%. When within the above range, the storage stability of the composition is maintained and the film remaining rate is improved.

When the copolymer (A) contains the constituent units (a2) and (a3) at the same time, the total content of the constituent units (a2) and (a3) is based on the total number of moles of the constituent units of the copolymer (A) 5 to 60 mol%, 10 to 60 mol%, 10 to 50 mol%, or 10 to 45 mol%. In addition, the structural units (a2) and (a3) are 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 molar ratios. In the above range, excellent stability over room temperature, heat resistance and chemical resistance can be obtained, and pattern implementation is improved.

(a4) a structural unit derived from an unsaturated monomer different from the above (a1) to (a3)

The copolymer (A) may include (a4) a constituent unit derived from an unsaturated monomer different from those of (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) of the present invention may further include a structural unit (a4) different from the structural units (a1) to (a3). The structural unit (a4) may be derived from an ethylenically unsaturated compound different from the previously presented compound.

Specifically, the structural unit (a4) may be derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof. unsaturated monocarboxylic acids such as, for example, (meth)acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; and trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof.

In addition, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (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, triethyl styrene, propyl styrene, Butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodine styrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene , vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether, and aromatic ring-containing ethylenically unsaturated compounds including p-vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl ( Meth) acrylate, ethylhexyl (meth) acrylate, tetrahydropuffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- Chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethyl Acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol ( Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3 -hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, unsaturated carboxylic acid esters including dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate; N-vinyl tertiary amines including N-vinyl such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers including vinyl methyl ether and vinyl ethyl ether; and at least one selected from the group consisting of unsaturated imides including N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. may be more than one species.

The content of the structural unit (a4) may be 50 to 99 mol%, 50 to 90 mol%, 55 to 85 mol%, or 60 to 80 mol% based on the total number of moles of the structural units of the copolymer (A). . In the above range, it is possible to increase the reactivity control and solubility of the copolymer (A), thereby significantly improving the applicability 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 and/or less than 10,000 Da. At this time, the copolymer (A) having a weight average molecular weight of less than 10,000 Da cannot be used alone, and is used in combination with a copolymer of 10,000 Da or more. Specifically, 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 an average molecular weight of 5,000 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. In the case of having a weight average molecular weight within the above range, adhesion to the substrate is excellent, physical and chemical properties are good, and the viscosity is appropriate.

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

The copolymer (A) used in the present invention may be synthesized by copolymerization by a known method. The content of the copolymer (A) is 10 to 50% by weight, 10 to 40% by weight, 10 to 35% by weight, 15 to 40% by weight, 15 to 35% by weight based on the total weight of the photosensitive resin composition excluding the remainder of the solvent. % or 20 to 35% by weight. When it is in the said range, the pattern development after development is favorable, and characteristics, such as a residual film rate and chemical resistance, improve.

(B) photopolymerizable compound

The photopolymerizable compound (monomer) used in the present invention is a compound that can be polymerized by the action of a photopolymerization initiator, and may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated group. , In terms of chemical resistance, it may be preferably a bifunctional or more polyfunctional compound.

The photopolymerizable compound is 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, pentaerythritol tri(meth) Acrylate, monoester product of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , monoester of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (with pentaerythritol triacrylate and 1 selected from the group consisting of hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol A epoxy acrylate and ethylene glycol monomethyl ether acrylate More than one species may be used, but is not limited thereto.

Commercially available photopolymerizable monomers include monofunctional (meth)acrylates, Aronix M-101, Copper M-111, Copper M-114 (manufactured by Toagosei Co., Ltd.), AKAYARAD TC-110S , copper TC-120S (manufactured by Nippon Chemical Co., Ltd.), V-158, V-2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), etc., as a commercial product of bifunctional (meth)acrylate, Aronix M-210, Dong M-240, Dong M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, Dong HX-220, Dong R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335 HP (Osaka Yuki Chemical Co., Ltd. product), etc., and commercially available products of trifunctional or higher (meth)acrylates include Aronix M-309, Copper M-400, Copper M-403, Copper M-405, Copper M- 450, Dong M-7100, Dong M-8030, Dong M-8060, TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, Dong DPHA, Dong DPHA-40H, Dong DPCA-20, Dong-30, Bronze -60, Dong-120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, Dong-300, Dong-360, Dong-GPT, Dong-3PA, Dong-400 (manufactured by Osaka Yuki Chemical High School) and the like.

The said photopolymerizable compound can be used individually or in combination of 2 or more types. The photopolymerizable compound is 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). , 25 to 80 parts by weight or 25 to 60 parts by weight. In the above range, while the pattern development is good, excellent chemical resistance and elastic restoring force can be obtained.

(C) photoinitiator

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

The photopolymerization initiator is an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, a polynuclear quinone-based compound, a thioxanthone-based compound, a diazo-based compound, an imide sulfo It may be selected from the group consisting of a nate-based compound, an oxime-based compound, a carbazole-based compound, a sulfonium borate-based compound, a ketone-based compound, and mixtures thereof. Specifically, the photopolymerization initiator may be at least one selected from the group consisting of an oxime-based compound, a triazine-based compound, and a ketone-based compound. More specifically, the photopolymerization initiator may use a combination of an oxime-based compound and a triazine-based compound or a combination of an oxime-based compound, a triazine-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-dimethylvaleronitrile), benzoyl Peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethylketal, benzophenone, benzoinpropyl ether, di Ethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenyl Midazolyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2- (o-benzoyloxime), o-benzoyl-4'-(benzmercapto)benzoylhexylketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphoro-trialkylphenyl Sulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyldisulfide, (E)-2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and mixtures thereof; it's not going to be

For reference, examples of commercially available oxime-based photopolymerization initiators include SPI-03 (Samyang Corporation), OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA), NCI-831 (ADEKA), etc. are mentioned. In addition, examples of commercially available triazine-based photopolymerization initiators include Triazine-Y (Tronly), Triazine-Y (Pharmasynthese), and the like.

The photopolymerization initiator may be used in an 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 (based on the solid content) of the copolymer (A).

Specifically, the oxime-based photopolymerization initiator is 1 to 20 parts by weight, 1 to 18 parts by weight, 5 to 20 parts by weight, 5 to 18 parts by weight, 8 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A) to 20 parts by weight or 8 to 18 parts by weight. The triazine-based photopolymerization initiator may be 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. The ketone-based photopolymerization initiator may be 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.

When an oxime-based photopolymerization initiator within the above range is used, the development and coating film characteristics may be improved while being highly sensitive. In addition, when a triazine-based photopolymerization initiator within the above range is used, a coating film having high sensitivity and excellent chemical resistance and taper angle during pattern formation can be manufactured.

(D) colorant

The coloring photosensitive resin composition of this invention contains a coloring agent in order to provide light-shielding property. The colorant used in the present invention may be a mixed colorant of two or more types of inorganic or organic colorants, and is preferably a colorant having high color development and high heat resistance.

The colorant includes a black colorant and a colorant other than black (d3).

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

As the black inorganic colorant, black organic colorant, and colorant other than black, any known colorant can be used, for example, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colorists) may include, and may include a known dye.

Specific examples of the black inorganic colorant include carbon black, titanium black, Cu-Fe-Mn-based oxides, and metal oxides such as synthetic iron black. It is preferable in terms of chemical properties.

Specific examples of the black organic colorant include aniline black, lactam black, and perylene black. Among them, lactam black (eg, Black 582 manufactured by BASF) is preferably used in terms of optical density, permittivity, etc. .

Specific examples of the colorant other than the black include C.I. 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; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 215, 216, 224, 242, 254, 255 and 264; C.I. Pigment Violet 13, 14, 19, 23, 25, 27, 29, 32, 33, 36, 37 and 38; C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64 and 76; C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; and C.I Pigment Brown 28. Specifically, the colorant other than the black may be a blue colorant, a purple colorant, or a mixture thereof. Among them C.I Pigment Blue 15:6 and 60, or C.I. The use of Pigment Violet 23 is preferable in terms of preventing light leakage and light scattering, and dispersibility and chemical resistance of the colored dispersion composition.

The content 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). Specifically, the colorant may include 0.01 to 50% by weight of a black colorant and 0.01 to 20% by weight of a colorant other than black based on the total weight of the solid content of the colored photosensitive resin composition (ie, weight excluding the solvent). More specifically, the colorant includes a black inorganic colorant or a black organic colorant, and 0 to 15% by weight of the black inorganic colorant, 0 to 40% by weight based on the total solids weight of the colored photosensitive resin composition (that is, the weight excluding the solvent) of a black organic colorant and 0.01 to 20% by weight of a colorant other than black. Preferably, 0 to 8.2% by weight of a black inorganic colorant, 0 to 45% of a black organic colorant, and 0.01 to 15% by weight of a colorant other than black based on the total solids weight of the colored photosensitive resin composition (that is, the weight excluding the solvent) may include. When the content of the colorant is within the above range, pattern development after development is good, properties such as chemical resistance and elastic restoring force may be improved, and desired optical density and light transmittance may be obtained.

In the case of the display including the black matrix of the present invention, the transmittance in the wavelength band of 700 nm should be at least 5% when the cured film is formed to a thickness of 3 μm in order to prevent light bleeding such as red or green. In addition, in order to facilitate the recognition of the alignment key in the process of arranging the mask during exposure, the transmittance at 900 to 950 nm must satisfy at least 10% or more.

Meanwhile, the colorant used in the present invention may be added to the colored photosensitive resin composition in the form of a colored dispersion (mill base) mixed with a dispersion resin, a solvent, and the like.

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

Examples of the dispersant include any known dispersant for colorants, and specific examples include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, and fluorine surfactants. , polyester compound, polycarboxylic acid ester compound, unsaturated polyamide compound, polycarboxylic acid compound, polycarboxylic acid alkyl salt compound, polyacrylic compound, polyethyleneimine compound, polyurethane compound, polyurethane, polyacrylic Polycarboxylic acid ester, unsaturated polyamide, polycarboxylic acid, amine salt of polycarboxylic acid, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate Salts, esters of polycarboxylic acids substituted with hydroxyl groups and modified products thereof, amides or salts thereof formed by the reaction of polyesters having free carboxyl groups with poly (lower alkyleneimines), (meth)acrylic acid -Styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin or water-soluble polymer compound such as polyvinyl pyrrolidone, modified polyacrylate, adducts of ethylene oxide/propylene oxide, phosphate esters, and the like. Commercially available dispersants include BYK's Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, and -2164. These can be used individually or in combination of 2 or more types. The dispersant may have an amine group and/or an acid group as a pigment affinity group, and may be an ammonium salt type in some cases.

The dispersing agent may be used by being internally added to the colorant in a manner of surface-treating the colorant in advance, or may be added and used together with the colorant when preparing the colored photosensitive resin composition.

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

The dispersant may be included in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total amount of the colored dispersion. When the content of the dispersant is within the above range, effective dispersion of the colorant is achieved to improve dispersion stability, and as the optical, physical and chemical quality is improved when the product is applied by maintaining an appropriate viscosity, it is preferable in terms of dispersion stability and excellent balance of viscosity Do.

When the dispersion binder has an acid value, it may include a monomer having a carboxyl group and an unsaturated bond. Specific examples of the monomer having the carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.

In addition, the dispersion binder may include a monomer having the carboxyl group and an unsaturated bond and a monomer having an unsaturated bond copolymerizable therewith. The monomer having a copolymerizable unsaturated bond is, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl aromatic vinyl compounds such as benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, or p-vinyl benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate or t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds, such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane or 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds, and these may be used alone or in combination of two or more.

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

The dispersion binder may be included in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total amount of the colored dispersion. When within the above range, the resin composition can maintain an appropriate viscosity, and is preferable in terms of dispersion stability and developability.

The colored dispersion may be included in an 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 (based on the solid content) of the copolymer (A).

(E) polyfunctional thiol compound

The colored photosensitive resin composition of the present invention may include a polyfunctional thiol compound to increase crosslinking efficiency during curing. Specifically, the polyfunctional thiol compound has a high reactivity with light and heat, so that the colored photosensitive resin composition is crosslinked even at a low temperature of 100° C. or less to form a cured film. More specifically, the functional group of the polyfunctional thiol compound reacts to light and heat so that crosslinking and curing by light and heat can be properly performed during the curing process. In addition, it removes unreacted functional groups.

The polyfunctional thiol compound may be a compound having two or more, three or more, or four or more mercapto groups. In the case of including one mercapto group, the reactivity of the polyfunctional thiol compound and the compound including a double bond and a hydroxy group may decrease, so that adhesiveness and durability may be reduced.

Examples of the polyfunctional thiol compound 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 Ol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, toluene-3,5-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1 ,5-naphthalenedithiol, 1,2-benzene dimanethiol, 1,3-benzene dimanethiol, 1,4-benzene dimanethiol, 4,4-thiobisbenzenethiol, 2-din-butylamino -4,6-dimercapto-s-triazine, trimethylol propane tris (β-thiopropion ester), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto- 3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, etc. are mentioned.

Examples of the polyfunctional thiol compound having three mercapto groups include thioglycerin, 1,3,5-triazine-2,4,6-trimercaptotriazine, trimethylolpropane tris thioglycolate, trimethylolpropane tris Thiopropion ester, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 2,4,6-tris(mercaptomethyl)methyl nitrite, tris(mer Captomethyl) isocyanurate, tris (3-mercaptopropyl) isocyanurate, 2,4,6-tris (mercaptomethyl) -1,3-dithiolane, 1,3,5-triazine- 2,4,6-trimercaptotriazine, tris(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropane tris-3-mercaptopropionate, etc. are mentioned.

Examples of the polyfunctional thiol compound having four mercapto groups include pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thiopropion ester, 1,2,4,5-tetrakis (mercaptomethyl) benzene, tetra Mercaptobutane, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc. are mentioned.

Preferably, the polyfunctional thiol compound is tris(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritoltetrakis-3-mercaptopropio It may be at least one selected from the group consisting of nitrate and dipentaerythritol tetrakis-3-mercaptopropionate.

The polyfunctional thiol compound is 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). It may be used in an amount of 15 to 20 parts by weight or 15 to 20 parts by weight.

When it is within the above range, the pattern shape after development is good, and excellent chemical resistance and elastic restoring force can be obtained. If it is less than the above range, the post-curing process progress is insufficient (curing is not complete), and if it is excessive than the above range, the reactivity by light and heat is excessively high, so it is difficult to control the crosslinking efficiency, so that peeling or peeling during development Defects such as protrusions may occur in the pattern. Furthermore, the straightness and resolution of the pattern may be deteriorated.

(F) a compound containing at least two double bonds and two or more hydroxyl groups, respectively

The colored photosensitive resin composition of the present invention may further include a compound including a double bond and a hydroxyl group in order to facilitate pattern formation. Specifically, the compound including a double bond and a hydroxyl group may include two or more double bonds and a hydroxyl group, respectively.

The compound containing the double bond and the hydroxyl group is 1,3-diglycerolate diacrylate, glycerol 1,3-diglycerolate 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, (spiro[fluorene-9,9'-xanthene]-3',6'-diylbis(oxy))bis(2-hydroxypropane-3,1-diyl ) may be at least one selected from the group consisting of diacrylates.

In addition, a compound having a straight-chain alkylene group and an alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxyl groups in the molecule and three, four or five acryloyloxy groups and/or methacryloyloxy groups It may further include a polyfunctional urethane acrylate compound obtained by reacting.

As described above, the compound including the double bond and the hydroxyl group enables high resolution by appropriately controlling the reactivity of the polyfunctional thiol compound by heat and light during post-curing. Specifically, in the non-exposed portion, the hydroxyl group of the compound including the double bond and the hydroxyl group improves the development speed, and in the exposed portion, the hydroxyl group participates in a crosslinking reaction with the thiol group of the polyfunctional thiol compound to improve the degree of curing.

The compound containing the double bond and the hydroxyl group is 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 40 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A). It may be used in an amount of 15 to 30 parts by weight.

When it is within the above range, the pattern shape after development is good, and excellent chemical resistance and elastic restoring force can be obtained. If it is less than the above range, the solubility of the composition is lowered, and when it is in excess of the above range, the solubility is excessive, so that the pattern thickness reduction rate during the development process increases, and at a high resolution of 10 μm or less, problems such as pattern dropout may occur. can

(G) photobase generator

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

Specifically, the colored photosensitive resin composition of the present invention uses a photo-radical polymerization initiator together with a photobase generator during curing, so that the photo-radical polymerization reaction and the base-generating reaction from the base generator proceed simultaneously, thereby improving the crosslinking efficiency in the composition can do it

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

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

The photobase generator may be used in 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). . When within the above range, thermal curing and photocuring may be smoothly performed even at a low temperature to form a cured film having good pattern development.

(H) Epoxy compound

The colored photosensitive resin composition of the present invention may further include an epoxy compound to increase the internal density of the resin to improve the chemical resistance of a cured film formed therefrom.

The epoxy compound may be an unsaturated monomer containing at least one epoxy group, or a homo-oligomer or hetero-oligomer thereof. Examples of the unsaturated monomer containing at least one epoxy group 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-epoxycyclopentyl (meth)acrylate, 3,4- Epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N-(4-(2,3- Epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allylglycidyl ether, 2-methyl allyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, or mixtures thereof, and specifically, glycidyl (meth) acryl It can be rate.

As a commercial item of the homo-oligomer of the unsaturated monomer containing at least one epoxy group, GHP-03HP (glycidyl methacrylate homopolymer, Miwon yarn) is mentioned.

The epoxy compound may further include the following structural units.

Specific examples include styrene; styrene having an alkyl substituent such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, and propoxystyrene; p-hydroxy-α-methylstyrene, acetylstyrene; aromatic ring-containing ethylenically unsaturated compounds such as divinylbenzene, vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether, and p-vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl ( Meth) acrylate, ethylhexyl (meth) acrylate, tetrahydropuffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- Chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethyl Acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol ( Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) ) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate , 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl ( Meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl ( unsaturated carboxylic acid esters such as meth)acrylate; tertiary amines having N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine; unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; and structural units derived from unsaturated imides such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. . The constituent units derived from the compounds exemplified above may be included in the epoxy compound alone or in combination of two or more.

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. When the weight average molecular weight of the epoxy compound is 100 Da or more, the hardness of the thin film may be more excellent, and when it is 30,000 Da or less, the thickness of the thin film becomes uniform and the step difference decreases, which is more suitable for planarization.

The content of the epoxy compound is 1 to 20 parts by weight, 1 to 10 parts by weight, 5 to 20 parts by weight, 5 to 15 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the copolymer (A) (based on the solid content) can be negative When within the above range, the pattern development after development is good, properties such as chemical resistance and elastic restoring force are improved, and it is possible to prevent problems such as peeling or deterioration of storage stability of the composition in the development process.

(I) Adhesive Aids

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

The adhesion aid may have at least one reactive group selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, and an epoxy group.

The type of the adhesive aid is not particularly limited, but for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanato Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, or mixtures thereof.

Preferably γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-phenyl The use of aminopropyltrimethoxysilane can further improve the remaining film ratio and adhesion to the substrate.

The content of the adhesive aid is 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, 1 to 5 parts by weight based on 100 parts by weight (based on the solid content) of the copolymer (A). parts or 1 to 3 parts by weight. When it is in the said range, adhesiveness with a board|substrate can be improved more.

(J) Surfactant

The colored photosensitive resin composition of the present invention may further include a surfactant to improve coating properties and prevent defect formation.

The type of the surfactant is not particularly limited, but may be, for example, a fluorine-based surfactant or a silicone-based surfactant.

Commercial products of the silicone-based surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 of Dow Corning Toray Silicone Co., Ltd. , BYK's BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, BYK-399, and the like. These can be used individually or in combination of 2 or more types.

Commercial products of the fluorine-based surfactant include Megaface F-470, F-471, F-475, F-482, F-489, F-563, Chiba's F of Dainippon Ink Chemical Co. (DIC). -563 and the like.

Among the surfactants, BYK-333, BYK-307 by BYK and F-563 by Chiba are preferable in terms of coating properties of the resin composition.

The content 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 (based on the solid content) of the copolymer (A). Within the above range In this case, the coating of the colored photosensitive resin composition may be smooth.

(K) solvent

The colored photosensitive resin composition of the present invention may be preferably prepared as a liquid composition in which the above-mentioned components are mixed with a solvent. As the solvent, any known solvent used for the colored photosensitive resin composition may be used as long as it has compatibility with the above-described colored photosensitive resin composition components but does not react with them.

Examples of such a solvent include glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Alkoxyalkyl acetates, such as 3-methoxybutyl acetate, are mentioned. The solvent may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but may be 50 to 90 wt%, or 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition from the viewpoint of applicability and stability of the final colored photosensitive resin composition. When the solvent content is within the above range, it is possible to obtain the effect that the coating of the resin composition is smooth and the delay margin that may occur in the working process is small.

In addition to this, the colored photosensitive resin composition of the present invention may include other additives such as antioxidants and stabilizers within a range that does not reduce physical properties.

The colored photosensitive resin composition of the present invention comprising the above components may be prepared by a conventional method, for example, may be prepared by the following method.

First, the colorant is mixed with a dispersing resin, a dispersing agent and a solvent in advance and dispersed using a bead mill or the like until the average particle size of the colorant is a desired level to prepare a colored dispersion. In this case, some or all of the surfactant and/or the copolymer may be blended. To this colored dispersion, the remainder of the copolymer and surfactant, a photopolymerizable compound, a photopolymerization initiator, a polyfunctional thiol compound, and a compound containing a double bond and a hydroxyl group are added, and, if necessary, an additive such as an epoxy compound or an additional solvent is added as required. After further mix|blending so that it may become a density|concentration of , it can fully stir and obtain the target coloring photosensitive resin composition.

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

The black matrix may be manufactured through a coating film forming step, an exposure step, a developing step, and a heat treatment step.

In the coating film forming step, a desired thickness, e.g., by using a method such as spin or slit coating method, roll coating method, screen printing method, applicator method, etc., on a substrate that has been pre-treated with the colored photosensitive resin composition according to the present invention For example, after coating to a thickness of 1 to 25 μm, a coating film can be formed by pre-curing at a temperature of 70 to 100° C. for 1 to 10 minutes to remove the solvent.

In order to form a pattern on the obtained coating film, a mask having a predetermined shape is interposed and then irradiated with actinic rays of 200 to 500 nm. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used. The exposure amount varies depending on the type, blending amount, and dry film thickness of each component of the composition, but may be 500 mJ/cm 2 (at a wavelength of 365 nm) or less when a high-pressure mercury lamp is used.

Following the exposure step, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, or tetramethylammonium hydroxide is used as a developer to dissolve and remove unnecessary portions, thereby leaving only the exposed portion to form a pattern. After cooling the image pattern obtained by development to room temperature, post-bake at 50 to 100°C, 50 to 90°C, or 60 to 90°C for 10 to 60 minutes in a hot air circulation drying furnace to obtain the desired final pattern. can

The light-shielding black matrix prepared as described above can be usefully used in electronic components such as liquid crystal displays and quantum dot displays due to excellent physical properties. Accordingly, the present invention provides an electronic component including the light-shielding black matrix.

The liquid crystal display device, quantum dot display, etc. may include configurations known to those skilled in the art, except for having the black matrix of the present invention. That is, liquid crystal displays and quantum dot displays to which the black matrix of the present invention can be applied may all be included in the present invention.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

The weight average molecular weight described in Preparation Examples below is a polystyrene conversion value measured by gel permeation chromatography (GPC).

[Example]

Preparation Example 1: Preparation of copolymer (A-1)

In a 250 ml round bottom flask equipped with a reflux condenser and stirrer under a nitrogen atmosphere, 10.68 g (32 mol%) of styrene, 8.01 g (25 mol%) of methyl methacrylate, 10.43 g of 2-acryloyloxyethyl succinate ( 15 mol%), a monomer mixture consisting of 11.32 g (18 mol%) of 2,4-epoxycyclohexylmethyl methacrylate and 4.56 g (10 mol%) of glycidyl methacrylate and V-65 2.34 as a radical polymerization initiator g (3.0 mol%) was dissolved in 107.98 g of propylene glycol methyl ether acetate (PGMEA). Then, polymerization was performed at 65° C. for 18 hours to obtain a copolymer (A-1) having a solid content of 31.32 wt%. The resulting copolymer had an acid value of 19.93 mgKOH/g, a polydispersity (Mw/Mn) of 4.38, and a weight average molecular weight (Mw) of 35,000 Da.

Preparation Example 2: Preparation of copolymer (A-2)

In a 500 ml round bottom flask equipped with a reflux condenser and stirrer, a monomer mixture 100 having a molar ratio of 43 mol% styrene, 27.5 mol% methyl methacrylate, 20.5 mol% methacrylic acid and 9 mol% glycidyl methacrylate g, 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator were added, and then raised to 70°C to 5 The copolymer (A-2) having a solid content of 29.8% was polymerized by stirring for a period of time. The resulting copolymer had an acid value of 28 mgKOH/g and a weight average molecular weight (Mw) of 6,500 Da.

Preparation Example 3: Preparation of copolymer (A-3)

In a 500 ml round-bottom flask equipped with a reflux condenser and stirrer, 51 mol% of N-phenylmaleimide, 4 mol% of styrene, 10 mol% of 4-hydroxybutyl acrylate glycidyl ether and 35 mol% of methacrylic acid 100 g of a monomer mixture having a molar ratio, 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator were added, The copolymer (A-3) having a solid content of 31.3% was polymerized by raising the temperature to 70°C and stirring for 5 hours. The resulting copolymer had an acid value of 31.7 mgKOH/g and a weight average molecular weight (Mw) of 20,545 Da.

Examples and Comparative Examples: Preparation of photosensitive resin composition

Information on the components used in the following Examples and Comparative Examples is as follows.

Example 1.

100 parts by weight of copolymer A-1 of Preparation Example 1, 32.143 parts by weight of dipentaerythritol hexaacrylate as the photopolymerizable compound (B), 10.944 parts by weight of the oxime-based photopolymerization initiator (C-1) as a photopolymerization initiator, triazine-based photopolymerization 3.648 parts by weight of initiator (C-2), 112.359 parts by weight of colorant (D-1), 16.051 parts by weight of colorant (D-2), 32.103 parts by weight of colorant (D-3), 19.644 parts by weight of polyfunctional thiol compound (E) 26.785 parts by weight of a compound (F-1) containing at least two parts, a double bond and two or more hydroxyl groups, 1.824 parts by weight of a photobase generator (G), 7.296 parts by weight of an epoxy compound (H) GHP-03, an adhesion aid ( I) 1.459 parts by weight and 0.547 parts by weight of F-563 as surfactant (J) were uniformly mixed. In this case, each of the above contents is the contents of the solid content except for the solvent. The mixture was dissolved in PGMEA so that the solids content was 19%. This was stirred for 2 hours to obtain a liquid photosensitive resin composition.

Examples 2 to 4 and Comparative Examples 1 to 10.

A photosensitive resin composition was obtained in the same manner as in Example 1, except that the type and/or content of each component was changed as described in Tables 3 and 4 below.

Preparation of cured film

The photosensitive resin compositions prepared in Examples and Comparative Examples were respectively coated on a glass substrate using a spin coater, and then pre-cured at 85° C. for 150 seconds to form a 1.6 μm thick coating film. A mask prepared to form a line pattern of 5 μm in size with 100% exposure to the coating film was applied to have a gap of 50 μm with the substrate, and then exposure was performed. Then, using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm, exposure was carried out for a predetermined time so as to be 50 mJ/cm 2 based on 365 nm. Thereafter, it was developed at 24° C. with an aqueous solution (potassium hydroxide aqueous solution) diluted to 0.04% by weight of potassium hydroxide until the unexposed part was completely washed out. The formed pattern was post-cured in an oven at 85° C. for 60 minutes to obtain a cured film.

Evaluation Example 1. Measurement of Development Time and Evaluation of Peelability

A cured film having a total thickness of 1.5 (±0.1) μm after post-curing was prepared according to the method for preparing the cured film. At this time, during the cured film manufacturing process, the time until the unexposed part is completely washed out (when the stage O-ring part of the developing equipment is completely visible from the back of the substrate) at 24°C with 0.04% by weight aqueous potassium hydroxide solution is measured as the developing time. recorded. In addition, the degree of peeling during development was visually evaluated. The results are shown in Table 5 below.

Development time/ Peelability

◎: 6 seconds or more to 75 seconds or less / No visual defects

○: More than 5 seconds to less than 150 seconds / Unexposed parts fall into fine particles and are recorded

×: less than 6 seconds and greater than 150 seconds/unexposed portions fall into irregular lumps

Evaluation Example 2. Evaluation of straightness and adhesion of the pattern

For the cured film having a thickness of 1.5 (±0.1) μm prepared in the same manner as in Evaluation Example 1, the thickness and the line width size (CD size) were measured using SNU equipment. In addition, the degree of straightness of the line pattern formed on the cured film and whether there was any loss in the pattern were visually confirmed using an optical microscope. The results are shown in Table 5 and FIGS. 1 and 2 below.

◎: side by side pattern formation without defects such as protrusions (good straightness)

○: Defects such as protrusions are seen in the pattern

×: Many defects such as projections are observed in the pattern

Evaluation Example 3. Chemical resistance evaluation

A specimen was prepared by cutting the cured film having a thickness of 1.5 (±0.1) μm prepared in the same manner as in Evaluation Example 1 to a size of 2 cm X 1 cm. After putting 10 ml of PGMEA in a chemical resistant container, the cap was closed and water bathed at 85° C., and then the specimen was immersed and bathed for 10 minutes. After 10 minutes, the specimen was taken out, cooled to room temperature, and washed with running water. The thickness of the specimen before and after solvent immersion was analyzed with SNU equipment. The results are shown in Table 5 below.

◎: thickness change of 10% or less

○: thickness change is more than 10% to 20% or less

×: thickness variation is more than 20%

Looking at the results in Table 5 and FIGS. 1 and 2, the cured films formed from the photosensitive resin compositions of Examples 1 to 4 all developed rapidly, and showed good straightness and adhesion without defects such as pattern peeling or protrusions during development. Furthermore, the chemical resistance evaluation result was also excellent. The cured films prepared in Comparative Examples 1 to 10 were not developed or the development time was too long, the patterns were peeled off or lost, and defects such as protrusions were observed in some of the formed patterns. Furthermore, the chemical resistance evaluation result was also poor compared to the Example.

Claims (15)

(A) copolymers;
(B) a photopolymerizable compound;
(C) a photoinitiator;
(D) colorants; and
(E) a polyfunctional thiol compound; containing, the photosensitive resin composition. According to claim 1,
The photosensitive resin composition further comprises a compound (F) each containing two or more double bonds and hydroxyl groups, the photosensitive resin composition. According to claim 1,
The polyfunctional thiol compound (E) is tris-(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritoltetrakis-3-mercaptopro At least one selected from the group consisting of cionate and dipentaerythritol tetrakis-3-mercaptopropionate, the photosensitive resin composition. According to claim 1,
The photosensitive resin composition comprising the polyfunctional 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. 3. The method of claim 2,
Compound (F) containing two or more of the double bond and the hydroxyl group, respectively, is 1,3-diglycerolate diacrylate, glycerol 1,3-diglycerolate diacrylate, ((oxybis(4,1-phenyl Ren))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, (spiro[fluorene-9,9'-xanthene]-3',6'-diylbis(oxy))bis(2-hydroxy At least one selected from the group consisting of propane-3,1-diyl) diacrylate, the photosensitive resin composition. According to claim 1,
The photosensitive resin composition comprises 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,
The copolymer (A) is (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 a non-alicyclic epoxy group; and (a4) a structural unit derived from an unsaturated monomer different from those of (a1) to (a3); comprising at least one selected from the group consisting of, the photosensitive resin composition. 8. The method of claim 7,
The unsaturated monomer containing the acid group is a succinate-based acrylate compound, the photosensitive resin composition. 9. The method of claim 8,
The succinate-based acrylate compound is mono-2-acryloyloxyethyl succinate, mono-2-methacryloyloxyethyl succinate, 4-(2-(acryloyloxy)ethoxy)-4- Oxobutanoic acid, 4-(3-(methacryloyloxy)propoxy)-4-oxobutanoic acid and 4-((5-(methacryloyloxy)pentyl)oxy)-4-oxobuta At least one selected from the group consisting of noic acid, the photosensitive resin composition. 8. The method of claim 7,
The total content of the constituent units (a2) and (a3) is 10 mol% to 50 mol% based on the total number of moles of the constituent units of the copolymer (A), the photosensitive resin composition. 8. The method of claim 7,
The molar ratio of the structural unit (a2): (a3) is 50 to 99: 50 to 1, the photosensitive resin composition. According to claim 1,
The colorant (D) includes a black colorant,
The photosensitive resin composition, wherein the black colorant is a black organic colorant (d1), a black inorganic colorant (d2), or a mixture thereof. 13. The method of claim 12,
The colorant (D) further comprises a colorant other than black (d3),
The photosensitive resin composition wherein the colorant other than black (d3) is a blue colorant, a purple colorant, or a mixture thereof. According to claim 1,
The photosensitive resin composition further comprises a photobase generator (G), the photosensitive resin composition. A black matrix formed using the photosensitive resin composition of claim 1 .

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