KR102437844B1 - Colored photosensitive resin composition and black column spacer prepared therefrom - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, comprising: a copolymer; an epoxy resin compound or a compound derived therefrom; photopolymerizable compounds; photoinitiator; And a colorant, wherein the photopolymerizable compound is the color photosensitive resin composition of the present invention comprising the compound of Formula 1 and the compound of Formula 3, the resolution of the black column spacer having a complex structure such as a two-ton structure and a colored photosensitive resin composition for a black column spacer having excellent surface properties.

Description

Colored photosensitive resin composition and black column spacer using the same

The present invention relates to a colored photosensitive resin composition suitable as a material for forming a spacer, a light-shielding portion, etc. used for a panel of a liquid crystal display (LCD) and an organic light emitting diode (OLED) display, etc., and a cured film formed from the composition, particularly a column spacer; It relates to a black column spacer (BCS) in which a black matrix is integrally formed.

Recently, in a liquid crystal cell of a liquid crystal display (LCD), a spacer formed using a photosensitive resin composition has been applied in order to maintain a constant distance between the upper and lower transparent substrates. Since the LCD is an electro-optical device driven by applying a voltage to the liquid crystal material injected at a constant gap between the transparent substrates, it is very important to keep the two substrates at a constant distance. If the distance between the transparent substrates is not constant, the voltage applied to the portion and the transmittance of the light passing through it are different, thereby causing a defect in which spatially non-uniform brightness is displayed. As LCDs gradually become larger, the importance of regular intervals between transparent substrates is increasing.

Such a spacer is manufactured by coating a photosensitive resin composition on a substrate, exposing it to ultraviolet light using a mask, and developing the spacer. As part of this effort, Korean Patent No. 1373984 discloses a photosensitive resin composition for a transparent column spacer in which a photopolymerizable compound having a caprolactone skeleton is introduced in a certain content range, and for the purpose of manufacturing a column spacer having a large amount of plastic deformation do it with

Meanwhile, in recent years, a process procedure has been simplified by developing a black column spacer in which the column spacer and the black matrix are integrated into one module. In addition, various attempts such as a black column spacer having a structure of two tones are in progress. However, even in a complex black column spacer that is not a simple structure, high resolution required for a transparent column spacer is required, and excellent surface properties are also required.

Korean Patent No. 1373984

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition for a black column spacer having excellent resolution and surface properties when manufacturing a black column spacer having a complex structure such as a two-ton structure.

In order to achieve the above object, the present invention

(a) copolymers;

(b) an epoxy resin compound or a compound derived therefrom;

(c) photopolymerizable compounds;

(d) a photopolymerization initiator; and

(e) a colorant;

The photopolymerizable compound provides a colored photosensitive resin composition comprising a first acrylic photopolymerizable unsaturated compound represented by the following Chemical Formula 1, and a second acrylic photopolymerizable unsaturated compound different from the first acrylic photopolymerizable unsaturated compound.

[Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, or a substituent represented by the following formula (2);

At least one of R ¹ to R ⁶ is a substituent represented by the following formula 2, wherein n is 1 or 2,

[Formula 2]

In Formula 2,

R ⁷ is an optionally substituted C _2-20 oxyalkylene group;

R ⁸ is H, or a methyl group;

n is an integer from 0 to 2.

The colored photosensitive resin composition of the present invention has excellent exposure margin and development margin, and satisfies the resolution and surface properties required for a black column spacer having a complex structure such as a two-ton structure. useful as a material.

1 schematically shows an example of a cross section of a black column spacer.
2 schematically shows a cured film composed of a 100% full-tone column spacer (CS) pattern and a 20% half-tone black matrix pattern.

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

Colored photosensitive resin composition

The colored photosensitive resin composition of this invention is (a) a copolymer; (b) an epoxy resin compound or a compound derived therefrom; (c) photopolymerizable compounds; (d) a photopolymerization initiator; and (e) a colorant, wherein the photopolymerizable compound includes a first acrylic photopolymerizable unsaturated compound of Formula 1 below, and a second acrylic photopolymerizable unsaturated compound different from the first acrylic photopolymerizable unsaturated compound.

[Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, or a substituent represented by the following formula (2);

At least one of R ¹ to R ⁶ is a substituent represented by the following formula 2, wherein n is 1 or 2,

[Formula 2]

In Formula 2,

R ⁷ is an optionally substituted C _2-20 oxyalkylene group;

R ⁸ is H, or a methyl group;

n is an integer from 0 to 2.

In addition, the colored photosensitive resin composition according to the present invention may further include (f) a solvent, (g) a surfactant, and/or (h) a silane coupling agent, if necessary.

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

Hereinafter, the coloring photosensitive resin composition is demonstrated concretely for each component.

(a) copolymer

The copolymer used in the present invention is (a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, and (a-2) derived from an aromatic ring-containing ethylenically unsaturated compound. It may include a structural unit, and additionally (a-3) a structural unit derived from an ethylenically unsaturated compound different from the above (a-1) and (a-2).

The copolymer is an alkali-soluble resin that implements developability in the developing step, and also serves as a base for forming a coating film after coating and a structure for implementing a final pattern.

(a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof

In the present invention, the structural unit (a-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof. The ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having one or more carboxyl groups in the molecule, and specific examples thereof include: (meth)acrylic acid, crotonic acid, alpha-chloroacrylic acid, unsaturated monocarboxylic acids such as 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; trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof; Mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids having divalence or higher, such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate and the like. The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more.

The content of the structural unit (a-1) may be 5 to 65 mol%, preferably 10 to 50 mol%, based on the total number of moles of the structural units constituting the copolymer. When it is within the above range, it may be easier to maintain developability.

(a-2) Structural unit derived from an aromatic ring-containing ethylenically unsaturated compound

The structural unit (a-2) is derived from an aromatic ring-containing ethylenically unsaturated compound, and specific examples of the aromatic ring-containing ethylenically unsaturated compound include 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) acrylates; 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; 4-hydroxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene; Vinyl toluene, divinyl benzene, vinyl phenol, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p -Vinyl benzyl glycidyl ether, etc. are mentioned.

The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more.

Among them, a styrenic compound is preferable from the viewpoint of polymerizability.

The content of the structural unit (a-2) may be 2 to 70 mol%, preferably 5 to 60 mol%, based on the total number of moles of the structural units constituting the copolymer. When it is within the above range, it may be more advantageous in terms of chemical resistance.

(a-3) a structural unit derived from an ethylenically unsaturated compound different from the above (a-1) and (a-2)

The copolymer used in the present invention may further include, in addition to (a-1) and (a-2), a structural unit derived from an ethylenically unsaturated compound different from (a-1) and (a-2). can

Specific examples of the ethylenically unsaturated compound different from the above (a-1) and (a-2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acryl Late, 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-hydroxymethylacrylate, butyl α-hydroxymethylacrylate, 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, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl ( unsaturated carboxylic acid esters such as meth)acrylate; tertiary amines containing N-vinyl such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; Glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy Heptyl (meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl Acrylate, α-n-butylglycidylacrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxy) Propoxy) -3,5-dimethylphenylpropyl) acrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether containing an epoxy group ethylenically unsaturated compounds; Unsaturated imides, such as N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide, etc. are mentioned.

The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more.

Preferably, among these, structural units derived from ethylenically unsaturated compounds and/or unsaturated imides containing an epoxy group, more preferably glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl A structural unit derived from cydyl ether and/or N-substituted maleimide may be more advantageous in terms of copolymerizability and strength improvement of the insulating film.

The content of the structural unit (a-3) may be 10 to 80 mol%, preferably 20 to 75 mol%, based on the total number of moles of the structural units constituting the copolymer. When it is within the above range, it may be more advantageous to maintain the storage stability of the colored photosensitive resin composition and improve the remaining film rate.

Examples of the copolymer having the above structural units (a-1) to (a-3) include (meth)acrylic acid/styrene copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/styrene /methyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / glyc Cydyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl (meth) acrylate / N-cyclohexyl maleimide copolymer, (meth) ) acrylic acid / styrene / n-butyl (meth) acrylate / glycidyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / glycidyl (meth) acrylate / N-phenyl A maleimide copolymer, a (meth)acrylic acid/styrene/4-hydroxybutyl (meth)acrylate glycidyl ether/N-phenyl maleimide copolymer, etc. are mentioned.

The copolymer may be contained in one type or two or more types in the colored photosensitive resin composition.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (elution solvent: tetrahydrofuran, etc.) of the copolymer may be 3,000 to 50,000, preferably 5,000 to 40,000. When it is within the above range, it may be better in terms of adhesion to the substrate, physical/chemical properties, and viscosity.

The content of the copolymer in the total colored photosensitive resin composition may be 1 to 70 wt%, preferably 5 to 50 wt%, based on the total solid weight of the colored photosensitive resin composition (that is, the weight excluding the solvent). When it is within the above range, the pattern development after development may be good and properties such as chemical resistance may be improved.

The copolymer according to the present invention can be prepared by adding a molecular weight modifier, a radical polymerization initiator, a solvent, and the structural units (a-1) to (a-3), adding nitrogen, and then polymerization while slowly stirring.

The molecular weight modifier is not particularly limited, but may be a mercaptan compound such as butyl mercaptan or octyl mercaptan or α-methylstyrene dimer.

The radical polymerization initiator is not particularly limited, but 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- azo compounds such as methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, etc. have. These radical polymerization initiators can be used individually or in mixture of 2 or more types.

In addition, any solvent may be used as long as the solvent is used for the preparation of the copolymer, and for example, propylene glycol monomethyl ether acetate (PGMEA) may be used.

(b) an epoxy resin compound or a compound derived therefrom

The colored photosensitive resin composition of the present invention includes an epoxy resin compound or a compound derived therefrom, and preferably, an epoxy resin compound having a xanthene-based skeleton structure or a compound derived therefrom.

As the epoxy resin compound, a compound having a polystyrene equivalent weight average molecular weight (Mw) of 400 to 10,000 measured by gel permeation chromatography may be used, and an epoxy having a xanthene (9H-xanthene) skeleton structure represented by the following Chemical Formula 4 It may be a resin compound:

[Formula 4]

In Formula 4,

,

,

또는

에 포함된 *로 라벨링된 탄소로 대체되고;Each carbon labeled with * is independently

,

,

or

replaced by the carbon labeled with * contained in ;

L ¹ is each independently a C _1-10 alkylene group, a C _3-20 cycloalkylene group, or a C _1-10 alkyleneoxy group;

R ₁ to R ₇ are each independently H, a C _1-10 alkyl group, a C _1-10 alkoxy group, a C _2-10 alkenyl group, or a C _6-14 aryl group;

R ₈ is H, a methyl group, an ethyl group, CH ₃ CHCl-, CH ₃ CHOH-, CH ₂ =CHCH ₂ - or a phenyl group;

n is an integer from 0 to 10;

Specific examples of the C _1-10 alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, t-butylene group, pentylene group, isopentylene group, t- Pentylene group, hexylene group, heptylene group, octylene group, isooctylene group, t-octylene group, 2-ethylhexylene group, nonylene group, isononylene group, decylene group, isodecylene group, etc. are mentioned. Specific examples of the C _3-20 cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a decalinylene group, and an adamantylene group. Specific examples of the C _1-10 alkyleneoxy group include methyleneoxy group, ethyleneoxy group, propyleneoxy group, butyleneoxy group, sec-butyleneoxy group, t-butyleneoxy group, pentyleneoxy group, hexyleneoxy group, heptyl group A lenoxy group, an octyleneoxy group, 2-ethyl- hexyleneoxy group, etc. are mentioned. Specific examples of the C _1-10 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a t-pentyl group, A hexyl group, a heptyl group, an octyl group, an isooctyl group, t-octyl group, 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, isodecyl group, etc. are mentioned. Specific examples of the C _1-10 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butyloxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexyloxy group, a heptoxy group, an octyloxy group, 2 -ethyl-hexyloxy group etc. are mentioned. Specific examples of the C _2-10 alkenyl group include a vinyl group, an allyl group, a butenyl group, and a propenyl group. Specific examples of the C _6-14 aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

A compound derived from an epoxy resin having a xanthene-based skeleton structure of Formula 4 is obtained by reacting an epoxy resin having a xanthene-based skeleton structure of Formula 4 with an unsaturated basic acid to obtain an epoxy adduct, and then reacting it with a polybasic acid anhydride It may be a compound or a compound obtained by further reacting it with a monofunctional or polyfunctional epoxy compound. As said unsaturated basic acid, well-known things, such as acrylic acid, methacrylic acid, a crotonic acid, cinnamic acid, and sorbic acid, can be used. Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, hexa A well-known thing, such as a hydrophthalic anhydride (hexahydrophthalic anhydride), can be used. The monofunctional or polyfunctional epoxy compound is glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether Well-known things, such as cidyl ether and bisphenol Z glycidyl ether, can be used.

When a compound derived from an epoxy resin having a xanthene-based skeleton structure of Formula 4 is used, the xanthene-based skeleton structure further improves adhesion between the cured product and the substrate, alkali resistance, workability, strength, etc., and the non-cured portion after development It is possible to form an image more precisely in a fine pattern when removing .

The epoxy resin compound or a compound derived therefrom may be 1 to 70% by weight, preferably 5 to 50% by weight, based on the total weight (ie, based on solid content) of the colored photosensitive resin composition excluding the solvent. When it is within the above range, it may be more advantageous to implement a constant step difference between patterns with a desired margin width (allowable width) while maintaining the pattern shape as well as more improved resolution and chemical resistance.

(c) photopolymerizable compounds

The photopolymerizable compound used in the present invention is a compound that can be polymerized by the action of a photopolymerization initiator, and a polyfunctional monomer, oligomer or polymer generally used in the colored photosensitive resin composition may be used.

More specifically, the photopolymerizable compound may include a first acrylic photopolymerizable unsaturated compound of Formula 1 below, and a second acrylic photopolymerizable unsaturated compound different from the first acrylic photopolymerizable unsaturated compound, and surface properties are improved In the second acrylic photopolymerizable unsaturated compound may be a compound represented by the following formula (3).

[Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, or a substituent represented by the following formula (2);

At least one of R ¹ to R ⁶ is a substituent represented by the following formula 2, wherein n is 1 or 2,

[Formula 2]

In Formula 2,

R ⁷ is an optionally substituted C _2-20 oxyalkylene group; More preferably, it is -C ₅ H ₁₀ O-.

R ⁸ is H, or a methyl group;

n is an integer from 0 to 2.

[Formula 3]

In Formula 3,

a is 3 to 4,

b is 0 to 1.

The first commercially available acrylic photopolymerizable unsaturated compound includes DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), and the second acrylic photopolymerizable unsaturated compound is KAYARAD HDDA, HX-220, R-604, DPHA-40H, TMPTA, DPHA, PET-30, TPA-330, RP-1040, T-1420 (manufactured by Nippon Kayaku Co., Ltd.), V-295, V- 300, V-360, V-GPT, V-3PA, V-400 and V-802 (product of Osaka Yuki Chemical High School), Aronix M-309, M-400, M-403, M-405 , copper M-450, copper M-7100, copper M-8030, copper M-8060, TO-1382 (manufactured by Toagosei Co., Ltd.), Laromer BDDA, HDDA, TPGDA, DPGDA (manufactured by BASF), etc. may be mentioned, but is not limited thereto.

The said photopolymerizable unsaturated compound can be used individually or in combination of 2 or more types.

The content of the first acrylic photopolymerizable unsaturated compound may be 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the total solid weight of the colored photosensitive resin composition (ie, the weight excluding the solvent).

The first acrylic photopolymerizable unsaturated compound and the second acrylic photopolymerizable unsaturated compound may have a weight ratio of 3: 100 to 24: 100, preferably 5: 100 to 22: 100 by weight.

(d) photopolymerization initiator

As the photopolymerization initiator used in the present invention, any known polymerization 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 diketone-based compound, α-diketone-based compound, a polynuclear quinone-based compound, and a thioxanthone-based compound. It may be selected from the group consisting of compounds, diazo compounds, imide sulfonate compounds, oxime compounds, carbazole compounds, sulfonium borate compounds, and mixtures thereof.

Among them, Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753, 2009 -0009991, 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467 and 2011-0015683, and International Patent Publication Nos. WO 2010/102502 and It is preferable from the viewpoint of high sensitivity to use at least one of the oxime compounds described in WO 2010/133077. As these brand names, commercial products such as OXE-01 (BASF), OXE-02 (BASF), N-1919 (Adecas), NCI-930 (Adecas), and NCI-831 (Adecas) have high sensitivity and resolution. is preferable in terms of

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.2 to 5% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the solvent). When it is within the above range, curing by exposure is sufficiently performed so that it can be sufficiently adhered to the substrate during excellent temporary development, and a spacer having an excellent elastic recovery rate can be obtained.

(e) colorants

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. In particular, it may be more advantageous to use a mixture of two or more organic colorants to prevent light leakage of the black matrix and secure transmittance for mask alignment.

In addition, the colorant includes a black colorant and a blue colorant, wherein the black colorant may be a black inorganic colorant and/or a black organic colorant.

According to one example, the colored photosensitive resin composition may include a black organic colorant as a colorant, and may optionally further include a black inorganic colorant and a blue colorant.

As the black inorganic colorant, black organic colorant, and blue colorant, any known colorant may be used, and for example, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colorists) may be included. 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. Among them, carbon black is preferred in terms of pattern characteristics and chemical resistance. preferred in terms of

In addition, 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, transmittance, etc. do.

Specific examples of the blue colorant include C.I Pigment Blue 15:6, C.I Pigment Blue 15:4, C.I Pigment Blue 60, and C.I Pigment Blue 16. Among them, it is preferable to use C.I Pigment Blue 15:6 to prevent light leakage.

The content of the black inorganic colorant, the black organic colorant, and the blue colorant is, with respect to the total weight of the colored photosensitive resin composition excluding the solvent (ie, based on the solid content), respectively greater than 0 and less than 20% by weight, greater than 10 and less than or equal to 40% by weight, and greater than 0 15% by weight or less, preferably more than 0 to 20% by weight, 10 to 40% by weight, and more than 0 to 15% by weight, more preferably more than 0 to 10% by weight or less, 10 to 40% by weight, respectively , and 1 to 15% by weight.

When in the above range, it is advantageous to achieve a high optical density capable of preventing light leakage, and it is possible to implement the transmittance required for mask alignment.

On the other hand, in order to disperse the colorant in the colored photosensitive resin composition of the present invention, a dispersing agent may be used. Examples of the dispersant include any known colorant dispersant, and specific examples include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, fluorine surfactants, etc. can be heard 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 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.

In addition, after mixing the colorant with a binder, it can be used in the production of a colored photosensitive resin composition. The binder used at this time may be the copolymer (a) described in the present invention, a known copolymer, or a mixture thereof.

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

(f) solvent

The colored photosensitive resin composition of the present invention may be preferably prepared as a liquid composition in which the above 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.

Although content of the said solvent is not specifically limited, From a viewpoint of applicability|paintability, stability, etc. of the final coloring photosensitive resin composition, the solid content concentration of the composition excluding a solvent may be an amount normally 5 to 70 weight%, Preferably it is 10 to 55% by weight.

(g) surfactant

The colored photosensitive resin composition of the present invention further includes a surfactant for improving coating properties and preventing 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.

Examples of commercially available silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, manufactured by Dow Corning Toray Silicone Co., Ltd. BYK's BYK 333, BYK 307, BYK3560, BYK UV 3535, BYK 361N, BYK 354, BYK 399, etc. are mentioned. These can be used individually or in combination of 2 or more types. Examples of commercially available fluorine-based surfactants include Megaface F-470, F-471, F-475, F-482, F-489, F-563, RS-55 and the like of Dainippon Ink Chemical Co., Ltd. (DIC). can be heard Among them, BYK 333, BYK 307 of BYK and F-563 of DIC, Megaface RS-55 of Dainippon Ink Chemical Co., Ltd. (DIC) may be preferably used in terms of coating properties.

The surfactant is added in an amount of 0.0001 to 10% by weight, more preferably 0.005 to 5% by weight, based on the total weight of the colored photosensitive resin composition. Here, the weight of the colored photosensitive resin composition serving as a basis for the content may be the total weight including the solvent. When within the above range, the coating of the colored photosensitive resin composition may be smooth.

(h) silane coupling agent

The colored photosensitive resin composition of the present invention is composed of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, an epoxy group, and combinations thereof, if necessary, in order to improve adhesion with the substrate. A silane coupling agent having a reactive substituent selected from the group may be further included.

The type of the silane coupling agent is not particularly limited, but trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltrie Toxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, phenylaminotrimethoxysilane and these It may be selected from the group consisting of a mixture of In addition, among them, γ-isocyanatopropyltriethoxysilane (eg, KBE-9007 from Shin-Etsu) or phenylaminotrimethoxysilane having an isocyanate group with good adhesion to the substrate while maintaining chemical resistance is preferable. .

The silane coupling agent may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the solid content of the colored photosensitive resin composition (ie, excluding the solvent). When within the above range, the adhesiveness of the colored photosensitive resin composition may be improved.

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 as described above has excellent resolution and surface properties when manufacturing a black column spacer having a complex structure such as a two-ton structure.

Method for producing a colored photosensitive resin composition

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 solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant reaches a desired level. At this time, a surfactant may be used, and some or all of the copolymer may be blended. To this dispersion, the remainder of the copolymer and surfactant, an epoxy resin compound or a compound derived therefrom, a photopolymerizable compound and a photoinitiator are added, and if necessary, an additive such as a silane coupling agent or an additional solvent is added to a predetermined concentration. After further mix|blending, it can fully stir and can obtain the target coloring photosensitive resin composition.

black column spacer

The present invention also provides a black column spacer prepared using the colored photosensitive resin composition.

In particular, the present invention provides a black column spacer (BCS) prepared by using the colored photosensitive resin composition and in which a column spacer and a black matrix are integrally formed. An example of the black column spacer pattern is shown in FIG. 1 .

The column spacer, black matrix, or black column spacer 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, for example, by using a method such as a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, etc. After coating to a thickness of 2 to 25 μm, a coating film may 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. In this case, in order to manufacture the integrated black column spacer, a mask having different transmittance patterns may be used so that the column spacer and the black matrix can be simultaneously implemented. 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, compounding 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 the image pattern obtained by development is cooled to room temperature, a desired final pattern can be obtained by post-bake at 180°C to 250°C for 10 to 60 minutes in a hot air circulation drying furnace.

The black column spacer prepared as described above may be usefully used in electronic components such as LCD and OLED displays due to excellent physical properties. Accordingly, the present invention provides an electronic component including the black column spacer.

The LCD, OLED display, etc. may include a configuration known to those skilled in the art, except for having the black column spacer of the present invention. That is, any LCD, OLED display, etc. to which the black column spacer of the present invention can be applied may 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.

Preparation Example 1: Preparation of copolymer

In a 500 ml round-bottom flask equipped with a reflux condenser and stirrer, 100 g of the monomer mixture in the content ratio shown in Table 1 below, 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and 2,2'-azobis as a radical polymerization initiator 2 g of (2,4-dimethylvaleronitrile) was added, and then the temperature was raised to 70° C. and stirred for 5 hours to polymerize a copolymer having a solid content of 31 wt %. The resulting copolymer had an acid value of 100 mgKOH/g, and a polystyrene reduced weight average molecular weight (Mw) measured by gel permeation chromatography was 20,000.

Monomer constituting the copolymer (mol%) N-phenylmaleimide styrene 4-hydroxybutyl acrylate
glycidyl ether methacrylic acid 51 4 10 35

Preparation Example 2: Compound derived from an epoxy resin having a xanthene-based skeleton structure

In a flask equipped with a stirrer, thermometer, nitrogen replacement device and reflux condenser, 160 g of propylene glycol monomethyl ether acetate (PGMEA) was placed as a solvent, and 3,3'-(spiro[fluorene-9,9'-xanthene] -3',6'-diylbis(oxy))bis(2-hydroxypropane-3,1-diyl)diacrylate (3,3'-(spiro[fluorene-9,9'-xanthene]-3 100 g of ',6'-diylbis(oxy))bis(2-hydroxypropane-3,1-diyl) diacrylate) and 0.1 g of chloroplatinic acid were added, and the temperature was raised to 80 °C. Here, 47.6 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was diluted in 80 g of PGMEA and slowly added dropwise, and then the temperature was raised to 100° C. and reacted for 2 hours. After cooling to room temperature (25° C.), 0.3 g of para-toluenesulfonic acid pyridinium salt was added. As a result, a polymer compound having a weight average molecular weight (Mw) of 6,000, an acid value of 107 mgKOH/g, and a solid content of 50% by weight was obtained.

Preparation Example 3: Preparation of colored dispersion

8 g of the copolymer prepared in Preparation Example 1, 8 g of a polymer dispersant (DISPERBYK-2000, BYK), 12 g of carbon black, 53 g of lactam black (Black 582, BASF) as organic black, 15:6 16 g of CI Pigment Blue, and As a solvent, 384 g of PGMEA was dispersed at 25 to 60° C. for 6 hours using a paint shaker. Dispersion was carried out using 0.3 mm zirconia beads, and after the dispersion was completed, the beads and the dispersion were separated with a filter to prepare a colored dispersion.

Example 1 to 8 and Comparative Examples 1 to 4: Preparation of colored photosensitive resin composition

By solid content weight ratio, the copolymer obtained in Preparation Example 1, the compound derived from the epoxy resin having a xanthene-based skeleton structure obtained in Preparation Example 2, DPCA-20 (Nippon Kayaku Corporation) as the first photopolymerizable compound, and the second light weight Any one of C-1 to C-8 described in Table 2 below as a synthetic compound, D-1 (NCI831, Adecas) which is an oxime-based photoinitiator as a photopolymerization initiator, and D-2 (T-Y, PHARMASYNTEHSE) which is a triazine-based photoinitiator, Megaface RS-55 (DIC) as a surfactant and the colored dispersion obtained in Preparation Example 3 as a colorant were used as shown in Table 3 below, and propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content was 19% by weight. By mixing according to a conventional method and stirring for 5 hours, a colored photosensitive resin composition was prepared.

product name manufacturing company C-1 PET-30 Nippon Kayaku Co., Ltd. C-2 DPHA Nippon Kayaku Co., Ltd. C-3 BDDA BASF C-4 TMPTA Nippon Kayaku Co., Ltd. C-5 TPA-330 Nippon Kayaku Co., Ltd. C-6 RP-1040 Nippon Kayaku Co., Ltd. C-7 T-1420 Nippon Kayaku Co., Ltd. C-8 M-403 Toagosei Co., Ltd.

division Preparation Example 1
copolymer Preparation Example 2 compound first photopolymerizable compound second photopolymerizable compound photoinitiator coloring
dispersion interface
activator Example 1 4.25 3.65 0.65 C-1 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 2 4.25 3.65 0.65 C-2 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 3 4.25 3.65 0.65 C-3 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 4 4.25 3.65 0.65 C-4 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 5 4.25 3.65 0.65 C-5 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 6 4.25 3.65 0.65 C-6 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 7 4.25 3.65 0.65 C-7 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Example 8 4.25 3.65 0.65 C-8 3.25 D-1 0.15 D-2 0.19 6.84 0.02 Comparative Example 1 4.25 3.65 1.95 C-1 1.95 D-1 0.15 D-2 0.19 6.84 0.02 Comparative Example 2 4.25 3.65 0.00 C-1 3.90 D-1 0.15 D-2 0.19 6.84 0.02 Comparative Example 3 4.25 3.65 0.00 C-2 3.90 D-1 0.15 D-2 0.19 6.84 0.02 Comparative Example 4 4.25 3.65 3.90 C-1 0.00 D-1 0.15 D-2 0.19 6.84 0.02

test example 1: Evaluation of coating properties

Applicability was evaluated by spin-coating the colored photosensitive resin compositions of Examples and Comparative Examples while dropping them on a 10 cmx10 cm glass substrate in an amount of 3 g.

It can be said that it is favorable when a coating film with no Bernard cell or interference fringes is seen and non-uniformity is obtained.

test example 2: Black column of spacer thickness measurement

The colored 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 80° C. for 150 seconds to form a coating film. A pattern mask composed of a 100% full-tone column spacer (CS) pattern and a 20% half-tone black matrix pattern is applied to the obtained coating film, and a 150 μm gap between the coating film and the mask is applied. and irradiated with light of a wavelength of 365 nm at 45 mJ/cm 2 . Then, after confirming the break point (BP) time at 23° C. with an aqueous solution in which potassium hydroxide was diluted to 1% by weight, development was performed for an additional 15 seconds, followed by washing with pure water for 1 minute. The formed pattern was post-cured in an oven at 230° C. for 30 minutes to obtain a cured film.

As a result, a black column spacer pattern (see FIG. 1) in which the black matrix and the column spacer are integrally formed was obtained, and then the thickness (A) of the column spacer and the black matrix part were obtained using a step measuring device (SIS-2000, manufactured by SNU Precision). The thickness (B) was measured. In this case, when the thickness (B) of the black matrix part is 2.0±0.2 μm, excellent light blocking properties can be expected.

Test Example 3: CD size measurement of black column spacer

A cured film was prepared according to the procedure of Test Example 2, but a 100% full-tone column spacer (CS) pattern (thickness after heat curing: 3.0 (± 0.2) μm) and 20% half-tone black A cured film composed of a matrix pattern (thickness after thermal curing: 2.0 (±0.2) μm) was prepared.

In this case, a full-tone (F/T) region size (D) (see FIG. 2 ) of a mask for forming a 100% full-tone column spacer (CS) pattern was 10 μm.

The CD size of the black column spacer was measured using a three-dimensional surface measuring instrument (trade name: SIS 2000, manufacturer: SNU precision).

When the CD size (C) (refer to FIG. 1) of the 100% full-tone column spacer (CS) pattern is 35 μm or less after thermal curing, it can be said to be good, and when it is 30 μm or less, it can be said to be excellent.

Test Example 4: Evaluation of black mattress surface properties

In the preparation of the colored photosensitive resin composition, when the composition content is not correct, the roughness of the surface of the black matrix is greatly increased due to excessive development of the resin composition during the development, so that the surface tearing phenomenon may be seen even after thermal curing.

When such a surface tearing phenomenon is not seen when viewed with an optical microscope, it can be said that it is good.

The above measurement results are summarized in Table 4 below.

division Application characteristics black column spacer CD size
(μm) black mattress surface Column spacer thickness
(μm) black matrix thickness
(μm) Example 1 Good 3.00 2.05 28 Good Example 2 Good 3.04 2.07 33 Good Example 3 Good 2.98 1.97 32 Good Example 4 Good 3.00 1.98 34 Good Example 5 Good 3.02 1.94 33 Good Example 6 Good 2.99 2.03 32 Good Example 7 Good 3.02 2.02 32 Good Example 8 Good 3.02 2.00 29 Good Comparative Example 1 Good 2.97 2.07 38 error Comparative Example 2 Good 2.98 1.96 38 Good Comparative Example 3 Good 3.00 1.99 36 Good Comparative Example 4 Good 3.01 2.03 37 error

As shown in Table 4, the colored photosensitive resin compositions of Examples 1 to 8 and cured films prepared therefrom, for example, column spacers and black matrices, were uniformly excellent in application characteristics, thickness, CD size, and surface characteristics. . Therefore, the colored photosensitive resin composition according to the present invention can be usefully used in the manufacture of various electronic components including LCD and OLED displays.

On the other hand, it can be seen that the colored photosensitive resin compositions of Comparative Examples 1 to 4 and the cured film prepared therefrom had poorly measured properties of at least one of them. In particular, the CD sizes of Comparative Examples 1 to 4 were all greater than the reference value (35 μm or less).

A: the thickness of the column spacer,
B: the thickness of the black matrix part,
C: line width (CD) of the column spacer,
D: The size of the full-tone (F/T) area of the mask

Claims (6)

(a) copolymers;
(b) an epoxy resin compound or a compound derived therefrom;
(c) photopolymerizable compounds;
(d) a photopolymerization initiator; and
(e) a colorant;
The photopolymerizable compound is a first acrylic photopolymerizable unsaturated compound of Formula 1, and a second acrylic photopolymerizable unsaturated compound represented by Formula 3 below in a weight ratio of 3: 100 to 24: 100, a colored photosensitive resin composition comprising:
[Formula 1]

In Formula 1, R ¹ to R ⁶ are each independently hydrogen, or a substituent represented by Formula 2 below; At least one of R ¹ to R ⁶ is a substituent represented by the following formula 2, wherein n is 1 or 2,
[Formula 2]

In Formula 2, R ⁷ is an optionally substituted C _2-20 oxyalkylene group; R ⁸ is H, or a methyl group; n is an integer from 0 to 2,
[Formula 3]

In Formula 3, a is 3 to 4, and b is 0 to 1.
delete The method of claim 1,
The first acrylic photopolymerizable unsaturated compound of Formula 1 is contained in an amount of 0.5 to 15% by weight based on the total weight of the solid content of the colored photosensitive resin composition, the colored photosensitive resin composition.
4. The method of claim 3,
The first acrylic photopolymerizable unsaturated compound and the second acrylic photopolymerizable unsaturated compound have a weight ratio of 5: 100 to 22: 100, the colored photosensitive resin composition.
The method of claim 1,
The colored photosensitive resin composition in which the said epoxy resin compound has a xanthene system frame|skeleton structure.
The method of claim 1,
The colorant contains more than 0 and not more than 20% by weight of a black inorganic colorant, more than 10 and not more than 40% by weight of a black organic colorant and not more than 0% by weight of a blue colorant, based on the total solids content of the colored photosensitive resin composition. A photosensitive resin composition.

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