KR101861067B1 - Black photosensitive resin composition - Google Patents

Abstract

More particularly, the present invention relates to a black photosensitive resin composition, which comprises a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a leveling agent, And the polar surface free energy is 0.1 to 4.5 mN / m, the storage stability is very excellent, and even when the coating film is formed after leaving for a long time, the change in line width is small and the adhesion of the pattern is excellent To a black photosensitive resin composition capable of forming a pattern.

Description

BLACK PHOTOSENSITIVE RESIN COMPOSITION [0001]

The present invention relates to a black photosensitive resin composition.

A color filter may be embedded in a color imaging device of an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), etc., and may be used to actually obtain a color image . In addition, the color filter is widely used for a photographing element, a plasma display panel (PDP), a liquid crystal display (LCD), a field emission display (FEL), a light emitting display (LED) and the like. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.

Color filters are widely used in imaging elements, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a colorant corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

The black matrix serves to distinguish the colors of red, green and blue. It is important that the black matrix is formed in a precise pattern in order to prevent lowering of the transmittance and deterioration of the visibility of the pixel portion, and the adhesion to the substrate should be excellent.

This is usually done with a black photosensitive resin composition. However, when a coating film such as a black matrix is formed with a composition that is just produced, there is no particular problem. However, the composition has problems such as transportation time, There is a problem in that foreign matter or the like is generated during the period of time and the precision and adhesion of the pattern are deteriorated at the time of forming the coating film.

Korean Patent Publication No. 2010-66197 discloses a black photosensitive resin composition, and a light-shielding layer and a column spacer using the same.

Korea Patent Publication No. 2010-66197

It is an object of the present invention to provide a black photosensitive resin composition excellent in storage stability.

1. A coating film comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a leveling agent, wherein the coating film has a polar surface free energy of 0.1 to 4.5 mN / m, Black photosensitive resin composition.

2. The black photosensitive resin composition according to 1 above, wherein the leveling agent is a silicone leveling agent.

3. The black photosensitive resin composition according to 1 above, wherein the leveling agent is represented by the following general formula (1)

[Chemical Formula 1]

(Wherein l, m and n are each independently an integer of 1 to 30, Z 'is an alkyl group having 1 to 20 carbon atoms, and Z is one of substituents represented by the following general formulas (2) to (4)

(2)

(Wherein R ₁ and R ₂ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₃ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)

(3)

(Wherein R ₁ to R ₃ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₄ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)

[Chemical Formula 4]

(Wherein R ₁ is a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₂ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, and n is an integer of 1 to 10).

4. The black photosensitive resin composition according to 1 above, wherein the leveling agent is contained in an amount of 0.1 to 5% by weight based on the total weight of the black photosensitive resin composition.

5. The black photosensitive resin composition according to item 1 above, wherein the substrate has a water contact angle of 10 DEG to 50 DEG.

6. The photosensitive resin composition according to item 1 above, wherein, in the total amount of the black photosensitive resin composition, 3 to 20 wt% of a black pigment, 0.5 to 50 wt% of an alkali soluble resin, 1 to 10 wt% of a photopolymerizable compound, 0.01 to 15 wt% of a photopolymerization initiator, To 90% by weight of the black photosensitive resin composition.

7. An optical laminate comprising a base material and a coating film formed from the black photosensitive resin composition of any one of items 1 to 6 on one surface of the base material, wherein the coating film has a polar surface free energy of 0.1 to 4.5 mN / m.

8. The optical laminate according to 7 above, wherein said substrate has a water contact angle of 10 DEG to 50 DEG.

9. The optical laminate according to 7 above, wherein said coating film is a light shielding layer.

The black photosensitive resin composition of the present invention is excellent in storage stability. Thus, even when the coating film is formed after leaving for a long time, the pattern line width is less changed and the pattern adhesion is excellent, compared with the case where the coating film is not formed.

The present invention relates to a coloring composition comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a leveling agent, wherein the coating film has a polar surface free energy of 0.1 to 4.5 mN / m The present invention provides a black photosensitive resin composition which is excellent in storage stability and capable of forming a pattern having a small line width change and excellent in pattern adhesion even when a coating film is formed after leaving for a long time, will be.

Hereinafter, the present invention will be described in detail.

<Black Photosensitive Resin Composition>

The black photosensitive resin composition of the present invention comprises a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and has a polar surface free energy of 0.1 to 4.5 mN / m after curing of the coating film prepared therefrom.

The present invention is excellent in storage stability when the polar surface free energy after curing of a coating film formed of a black photosensitive resin composition has a value within the above range, and even when a coating film is formed with a composition after standing for a long time at a high temperature condition, And the difference between the line width and the adhesion of the pattern is small.

The polar surface free energy is the surface free energy due to the polar group interactions and can be derived by the "Owen, Wendt, Rabel and Kaelble (OWRK) method" of equations (1) to have.

[Equation 1]

&Quot; (2) &quot;

&Quot; (3) &quot;

&Quot; (4) &quot;

&Quot; (5) &quot;

(P: Polar, D: Dispersive, σ _l : Surface Tension of the liquid, σ _s : Surface Tension of the solid, γ _sl The interfacial tension between the phases (theta: the contact angle).

An interfacial tension between the above Equation 1 to 4 σ _l is the surface tension of the liquid dropped on the coated film (surface free energy), σ _s is the surface tension of the coating film (the surface free energy), γ is these, equation (1) to (5) can be derived from Equation (4), and the polarity surface free energy (?) Of the coating film can be obtained by substituting each value into Equation (5).

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

Black pigment

The black pigment according to the present invention is not particularly limited as long as it has a polar surface free energy after curing of the coating film so as to have the above-mentioned range, for example, carbon black; Organic black pigments; Titanium black; And pigments in which red, green and blue are blended to give a black color. These may be used alone or in combination of two or more.

The carbon black is not particularly limited as long as it has shading properties, and known carbon black can be used. For example, channel black, furnace black, thermal black, lamp black black).

The carbon black according to the present invention may be coated with a nonconductive resin. In such a case, it is used in the production of a black matrix, a black column spacer and the like, and excellent electrical insulation can be imparted.

Examples of commercial products that can be used as carbon black include CISTO 5HIISAF-HS, CISTO KH, CISTO 3HHAF-HS, CISTO NH, CISTO 3M, CISTO 300HAF-LS, CISTO 116HMMAF -HS, Cysto 116MAF, Cysto FMFEF-HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Diagram Black, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, CF9, # 95, # 3030, # 3050, MA-7, MA-77, MA-8, MA-11, MA-100, MA-40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN- 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- But are not limited to, 2500 ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA and RAVEN-1170. These may be used alone or in combination of two or more.

The black pigment according to the present invention can be used by mixing a color pigment with carbon black.

The coloring pigment is not particularly limited and a known coloring pigment can be used. Examples thereof include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086) Cyanine black, lino yellow (CI 21090), lino yellow yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI 42595), CI Pigment Red 97, 122, 149, 168, 177, 180, 192, 215, C.I. Pigment Green 7, 36, C.I. Pigment 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. Pigment 83, 139; C.I. Pigment Violet 23, etc. In addition, a white pigment, a fluorescent pigment and the like may be used.

The black pigment according to the present invention preferably uses a pigment dispersion in which the particle size of the black pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment by adding the pigment dispersant and the like, and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by the above method.

The pigment dispersant may be any of those generally used in the art. Preferably an acrylate-based dispersant comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate); Polycarboxylic acid esters; Unsaturated polyamides; Polycarboxylic acids; (Partial) amine salts of polycarboxylic acids; Ammonium salts of polycarboxylic acids; Alkylamine salts of polycarboxylic acids; Polysiloxanes; Long chain polyaminoamide phosphate salts; Esters of hydroxyl group-containing polycarboxylic acids and their modification products; An amide formed by the reaction of a polyester having a free carboxyl group with a poly (lower alkyleneimine) or a salt thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; Phosphate esters and the like. These may be used alone or in combination of two or more.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK- DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 (BYK KEMISA); EFKA-44, EFKA-44, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA- 4400, EFKA-4406, EFKA-4510, EFKA-4800 (BASF); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (Lubirzol); Hinoact T-6000, Hinoact T-7000, Hinoact T-8000 (Kawaken Fine Chemicals); AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 (Ajinomoto); FLORENE DOPA-17HF, Florene DOPA-15BHF, Florene DOPA-33 and Florene DOPA-44 (Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The content of the pigment dispersant is not particularly limited and may be, for example, 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the black pigment. When the content of the dispersing agent is within the above range, the pigment can be finely atomized and have an appropriate viscosity.

The content of the black pigment in the pigment dispersion is not particularly limited and may be, for example, 20 to 90% by weight, preferably 30 to 75% by weight, based on the total weight of the solid dispersion pigment dispersion. When the content of the black pigment is 20 to 90% by weight, it can have an appropriate viscosity, is excellent in storage stability, and is highly effective in improving the contrast ratio because of high dispersion efficiency.

The content of the pigment dispersion is not particularly limited and may be, for example, 20 to 70% by weight of the total weight of the black photosensitive resin composition.

The black pigment may be contained in an amount of 3 to 20% by weight based on the total weight of the black photosensitive resin composition.

Alkali-soluble resin

The alkali-soluble resin is polymerized including an ethylenically unsaturated monomer having a carboxyl group. The ethylenically unsaturated monomer having a carboxyl group is a component that imparts solubility to an alkali developing solution used in a developing treatment process for forming a pattern.

The ethylenically unsaturated monomer having a carboxyl group is not particularly limited as long as it has a polar surface free energy after curing of the prepared coating film within the above range, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, preferably acrylic acid and methacrylic acid. These may be used alone or in combination of two or more.

The acid value of the alkali-soluble resin is not particularly limited, and may be, for example, 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mg / KOH / g, the developing speed may be lowered. When the acid value is more than 150 mg / KOH / g, the compatibility and storage stability may be lowered, And the pattern may be short-circuited.

The method of imparting a hydroxyl group to the alkali-soluble resin is not particularly limited and includes, for example, a method of further polymerizing an ethylenically unsaturated monomer having a hydroxyl group, a method of reacting with a compound having a glycidyl group, A method of reacting a polymerized copolymer further including a monomer with a compound having a glycidyl group, and the like.

The ethylenically unsaturated monomer having a hydroxyl group is not particularly limited. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl acrylamide, and N-hydroxyethyl acrylamide. Of these, 2-hydroxyethyl (meth) acrylate is preferable. These may be used alone or in combination of two or more.

The compound having a glycidyl group is not particularly limited and includes, for example, butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl Methyl ethyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Diallyl ether, and methacrylic acid glycidyl ester. Of these, butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester may be preferably used. These may be used alone or in combination of two or more.

The alkali-soluble resin according to the present invention may further comprise at least one other monomer copolymerizable with the monomer. Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p- Aromatic vinyl compounds such as vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like. These may be used alone or in combination of two or more.

The content of the alkali-soluble resin is not particularly limited and may be, for example, 0.5 to 50% by weight, preferably 1 to 35% by weight, based on the total weight of the black photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, solubility in a developing solution is sufficient and pattern formation is easy, and reduction of the film of the pixel portion of the exposed portion is prevented during development, so that the missing property of the non-pixel portion is improved.

Photopolymerization  compound

The photopolymerizable compound is a component for enhancing the strength of the pattern and is not particularly limited as long as it is within a range such that the polar surface free energy after curing of the prepared coating film has the above range. For example, 1 to 6 functional monomers have. Specific examples of the monofunctional compounds such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Monomers; (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di 3-methylpentanediol di (meth) acrylate, 3- (acryloyloxy) -2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, Bifunctional monomers such as 2-hydroxy-1-acryloxy-3-methacryloxypropane; Trifunctional monomers such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

The photopolymerizable compound may preferably be a bifunctional or higher functional monomer and, more preferably, a pentafunctional or higher functional monomer in view of enhancement of pattern strength and improvement in smoothness.

Examples of commercially available photopolymerizable compounds include 701 (NK ESTER), 701A (NK ESTER), ATMM-3L (NK ESTER) and KAYARAD DPHA (Nippon Kayaku).

The content of the photopolymerizable compound is not particularly limited and may be, for example, 1 to 10% by weight, preferably 3 to 8% by weight, of the total weight of the black photosensitive resin composition. When the photopolymerizable compound is contained in an amount of 1 to 10% by weight, the strength of the pixel portion is excellent and the smoothness of the pattern can be improved.

Light curing Initiator

The type of the photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the photopolymerizable compound, and may be a photopolymerization initiator commonly used in the art. Examples thereof include acetophenone, benzophenone, triazine, A thiol compound, a thiol compound, a thiol compound, a hydrazide compound, an oxime compound, and a thioxanthone compound. These may be used alone or in combination of two or more.

The acetophenone compound is not particularly limited and includes, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan- ] Propane-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

The benzophenone compound is not particularly limited, and examples thereof include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- methyldiphenylsulfide, 3,3 ' -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The triazine compound is not particularly limited, and examples thereof include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2 , 2,4-bis (trichloromethyl) -6- [2- (5-methylpiperazin-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The imidazole compound is not particularly limited, and examples thereof include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted with a carboalkoxy group And preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl- And the like.

The oxime-based compound is not particularly limited and may be, for example, o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one. OXE01 and OXE02 of BASF Co. are commercially available.

The thioxanthone compound is not particularly limited and includes, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Oakstone, and the like.

The content of the photopolymerization initiator is not particularly limited and may be, for example, 0.01 to 15% by weight, preferably 0.1 to 7% by weight, based on the total weight of the black photosensitive resin composition. When the photopolymerization initiator is contained in an amount of 0.01 to 15% by weight, the black photosensitive resin composition has a high sensitivity and shortens the exposure time, thereby improving the productivity and maintaining the high resolution. The strength of the formed pixel portion and the smoothness Can be improved.

Light curing  Initiator

The colored photosensitive resin composition of the present invention may further include a photopolymerization initiation auxiliary agent for improving the sensitivity.

The photopolymerization initiation auxiliary is not particularly limited, and examples thereof include an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group. These may be used alone or in combination of two or more.

The amine compound is not particularly limited, and examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is not particularly limited and includes, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, And aromatic heteroacetic acids such as phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is not particularly limited and examples thereof include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (1H, 3H, 5H) -triene, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis Phonate), and the like.

The content of the photopolymerization initiation auxiliary agent is not particularly limited and may be, for example, 0.01 to 15% by weight, preferably 0.1 to 7% by weight, based on the total weight of the black photosensitive resin composition. When the photopolymerization initiator is contained in an amount of 0.01 to 15% by weight, the sensitivity of the black photosensitive resin composition is further improved and the productivity of the pattern formed therefrom can be improved.

solvent

The solvent is capable of dissolving the above components and is not particularly limited as long as it has a polar surface free energy after curing of the prepared coating film within the above range, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters And the like. These may be used alone or in combination of two or more.

For example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Ethers such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; And esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone. Of these, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent is preferably an organic solvent having a boiling point of 100 占 폚 to 200 占 폚 in view of coatability and dryness. Specific examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These may be used alone or in combination of two or more.

The content of the solvent is not particularly limited and may be, for example, 10 to 90% by weight, preferably 60 to 85% by weight, of the total weight of the colored photosensitive resin composition. When the content of the solvent is within the above range, the coating property may be good.

Leveling agent

The black photosensitive resin composition of the present invention can be adjusted so that the polar surface free energy after curing of the prepared coating film has the above range by mixing the components in an appropriate amount and including a leveling agent.

The leveling agent according to the present invention is not particularly limited as long as the surface free energy of the polar surface after curing of the prepared coating film has the above range, and may be, for example, a silicon leveling agent.

The silicone leveling agent according to the present invention is not particularly limited and may be a silicone leveling agent conventionally used in the art, but it may preferably be a silicon leveling agent represented by the following formula (1)

[Chemical Formula 1]

(Wherein l, m and n are each independently an integer of 1 to 30,

Z 'is an alkyl group having 1 to 20 carbon atoms,

Z is one of substituents represented by the following formulas (2) to (4)

(2)

(Wherein R ₁ and R ₂ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₃ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)

(3)

(Wherein R ₁ to R ₃ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₄ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)

[Chemical Formula 4]

(Wherein R ₁ is a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₂ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, and n is an integer of 1 to 10).

Examples of commercially available products include Silsurf A008 of Siltech, BYK-UV 3505, BYK-371, BYK-UV 3570, BYK-377, BYK-333 and BYK- But is not limited thereto. These may be used alone or in combination of two or more.

The content of the leveling agent is not particularly limited within a range such that the polar surface free energy after curing of the prepared coating film has the above range. For example, the leveling agent may be contained in an amount of 0.1 to 5% by weight based on the total weight of the black photosensitive resin composition, Preferably 0.1 to 1% by weight. 0.1 to 5% by weight, the storage stability of the composition can be maximized.

materials

The black photosensitive resin composition of the present invention is applied onto a substrate.

The substrate according to the present invention may be a substrate commonly used in the art, but it is preferable that the water contact angle is 10 to 50 degrees. In such a case, adhesion with a coating film having a polar surface free energy of 0.1 to 4.5 mN / m is excellent.

The substrate according to the present invention can be, for example, glass, silicon (Si), silicon oxide (SiO _x ), or a substrate made of a polymer.

The polymer may be polyethersulfone, polycarbonate, polyimide, polyethylene naphthalate, or the like. These may be used alone or in combination of two or more.

<Optical The laminate >

The present invention also provides a substrate and a coating film formed of the black photosensitive resin composition on one surface of the substrate, wherein the coating film has a polar surface free energy of 0.1 to 4.5 mN / m.

The substrate may be the above-described substrate and may preferably have a water contact angle of 10 DEG to 50 DEG from the viewpoint of maximizing improvement in adhesion with a coating film.

The coating film can be used as a light shielding layer. For example, it can be used as a black matrix for forming a non-display portion in which an image is not driven in an image display device, or for distinguishing patterns of red, green and blue in a color filter.

The thickness of the coating film is not particularly limited, and may be, for example, 0.5 to 10 占 퐉.

The coating film may be obtained by coating the black photosensitive resin composition on a substrate, and then curing and developing the photocurable resin.

The method of applying the black photosensitive resin composition is not particularly limited, and examples thereof include spin coating, flexible coating, roll coating, slit and spin coating, slit coating and the like.

After application of the composition, a drying process may be further applied if necessary. The drying temperature is not particularly limited and may be, for example, 70 to 200 占 폚, preferably 80 to 130 占 폚.

Thereafter, ultraviolet rays are irradiated to the obtained coating film using a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto.

When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method is not particularly limited, and examples thereof include a liquid addition method, a dipping method, and a spray method. Further, the substrate may be inclined at an arbitrary angle during development.

The developer may be an aqueous solution containing an alkaline compound and a surfactant conventionally used in the art.

The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like. The inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The concentration of the alkaline compound in the alkaline developer is not particularly limited and may be, for example, 0.01 to 10% by weight, preferably 0.03 to 5% by weight.

The surfactant may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium naphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts and the like. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developing solution is not particularly limited and may be, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

After development, it may be rinsed, and if necessary, post-baking may be performed at 150 to 230 ° C for 10 to 60 minutes.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example . Preparation of pigment dispersion

, 12.0 parts by weight of carbon black (MA-8, Mitsubishi) as a black pigment, 4.0 parts by weight of DISPERBYK-2001 (BYK) as a pigment dispersant, 44 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 40 parts by weight of propylene glycol monomethyl ether Were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A).

Synthetic example . Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 84.7 parts of benzyl methacrylate, 15.3 parts of methacrylic acid , and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 97 mgKOH / g, and a weight average molecular weight measured by GPC of the following specifications was about 15,000.

Device: HLC-8120GPC (Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-

Example  And Comparative Example

A black photosensitive resin composition having the composition and content shown in Table 1 below was prepared.

division Pigment
Dispersion
(A) Alkali-soluble resin
(B) Photopolymerizable compound
(C) Photopolymerization initiator
(D) Photopolymerization initiator
(E) solvent
(F) Leveling agent
(G) Weight portion Weight portion Weight portion ingredient Weight portion Weight portion Weight portion ingredient Weight portion Example 1 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-2 0.3 /
0.1 Example 2 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-3 0.3 /
0.1 Example 3 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-4 0.3 /
0.1 Example 4 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-5 0.3 /
0.1 Example 5 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-6 0.3 /
0.1 Example 6 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-7 0.3 /
0.1 Comparative Example 1 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-8 0.3 /
0.1 Comparative Example 2 50 9.5 1.98 D-1 /
D-2 /
D-3 0.21 /
0.4 /
0.4 0.1 37.41 G-1 /
G-9 0.3 /
0.1 A: A pigment dispersion
B: Copolymer of methacrylic acid and benzyl methacrylate (molar ratio 27:73, acid value 97 mg / KOH / g, weight average molecular weight 15,000)
C: KAYARAD DPHA (Nippon Kayakaji)
D-1: IGACURE 369 (Shiba)
D-2: IGACURE OXE01 (Shiba)
D-3: IGACURE OXE02 (Ciba)
E: 4,4'-di (N, N'-dimethylamino) -benzophenone
F: Propylene glycol monomethyl ether acetate
G-1: Silsurf A008 (Sil Tec)
G-2: BYK-UV 3505 (BYKKEMASA)
G-3: BYK-371 (BYK-KIMASA)
G-4: BYK-UV 3570 (BYK-KIMASA)
G-5: BYK-377 (BYK-KIMASA)
G-6: BYK-333 (BYK-KIMASA)
G-7: BYK-UV 3500 (BYK KEMISA)
G-8: BYK-UV 3530 (BYK-KIMASA)
G-9: aF60-C (Daikinsha)

Experimental Example

(1) Polar surface free energy measurement of coating film

The black photosensitive resin compositions of Examples and Comparative Examples were applied on a glass substrate having a water contact angle of 30 DEG by spin coating, and then placed on a heating plate and maintained at a temperature of 100 DEG C for 2 minutes to form a thin film and then irradiated with ultraviolet rays. At this time, an ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high-pressure mercury lamp containing g, h, and i lines to prepare an evaluation substrate.

Using a DSA100 water contact angle measuring instrument (Yokokawa), the contact angles of water of the deionized water and the diiodomethane on the substrates of the examples and comparative examples were measured, and then the polar surface free energy was calculated according to the above formulas 1 to 5 . The results are shown in Table 2 below.

(2) Evaluation of storage stability

The storage stability was evaluated by a color filter prepared therefrom immediately after the black photosensitive resin compositions of the Examples and Comparative Examples were prepared and a color filter prepared therefrom after each of the resin compositions was allowed to stand at 40 DEG C for 2 days, And then the line width and the pattern adhesion of the color filter fabricated therefrom were compared and evaluated.

The manufacturing method of each color filter is as follows.

The black photosensitive resin compositions of Examples and Comparative Examples were applied to a glass substrate having a water contact angle of 30 DEG by spin coating, and then placed on a heating plate and maintained at a temperature of 100 DEG C for 2 minutes to form a thin film.

A test photomask having a pattern of 20 mu m was placed thereon and irradiated with ultraviolet rays at an interval of 50 mu m from the test photomask. At this time, the ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used.

The ultraviolet irradiated thin film was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate on which the thin film was coated was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter.

The line width of a pattern formed on a mask having a line width of 20 mu m in the manufactured color filter was measured, and the change amount ([Delta] CD) of the line width according to the length of time allowed to stand was measured. The results are shown in Table 2 below.

&Quot; (6) &quot;

? CD = line width of a pattern evaluated with the resin composition produced on the same day - line width of a pattern evaluated with a resin composition left at 40 占

?:? CD is 0.5 占 퐉 or less

DELTA: CD is in the range of more than 0.5 mu m to 1.0 mu m or less

X:? CD exceeds 1.0 占 퐉

The adhesion of the pattern was evaluated by observing whether the pattern was peeled off to a pattern of several 탆 with an optical microscope.

division Water contact angle (°) Surface free energy
(mN / m) Pattern linewidth change Pattern adhesion (탆) Deionized water Diiodo
methane Sum Dispersibility polarity Leave for 2 days Leave for 3 days Immediately after manufacture Leave for 2 days Leave for 3 days Example 1 101.87 70.67 23.40 22.50 0.90 ○ ○ 5 5 5 Example 2 103.21 67.76 24.65 24.13 0.52 ○ ○ 5 5 5 Example 3 97.68 68.01 25.47 23.99 1.47 ○ △ 5 5 5 Example 4 98.84 67.09 25.67 24.51 1.16 ○ △ 5 5 6 Example 5 97.98 66.93 25.92 24.60 1.31 ○ △ 5 6 6 Example 6 98.69 66.07 26.20 25.09 1.11 ○ △ 5 6 8 Comparative Example 1 80.65 52.97 37.41 32.60 4.80 X X 5 11 - Comparative Example 2 104.5 50 19.1 19.03 0.07 △ X 5 8 10

Referring to Table 2, the coating films formed from the compositions of Examples 1 to 6 had a polar surface free energy of 0.90 to 1.47 mN / m, and even when a coating film was formed after these compositions were left for 2 or 3 days, It was confirmed that the change in line width was small, the pattern adhesion was excellent, and the storage stability was excellent.

However, when the coating film formed by the composition of Comparative Example 1 had a polar surface free energy of 4.80 mN / m and was allowed to stand for 2 or 3 days, the line width of the pattern was greatly changed, The pattern formed by the neglected composition was lost. As a result, the storage stability is remarkably decreased.

The coating film formed of the composition of Comparative Example 2 had a polar surface free energy of 0.07 mN / m, and it was confirmed that the pattern width after the same standing was changed greatly, the adhesion was decreased, and the storage stability was lowered.

Claims (9)

A black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a leveling agent,
Wherein the coating film has a polar surface free energy of 0.1 to 4.5 mN / m when applied on a substrate to form a coated film.
The black photosensitive resin composition according to claim 1, wherein the leveling agent is a silicone leveling agent.
The blacking photosensitive resin composition according to claim 1, wherein the leveling agent is represented by the following formula (1)
[Chemical Formula 1]

(Wherein l, m and n are each independently an integer of 1 to 30,
Z 'is an alkyl group having 1 to 20 carbon atoms,
Z is one of substituents represented by the following formulas (2) to (4)
(2)

(Wherein R ₁ and R ₂ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₃ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)
(3)

(Wherein R ₁ to R ₃ are independently of each other a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₄ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, To 10)
[Chemical Formula 4]

(Wherein R ₁ is a hydrogen atom, an acryl group, a carboxyl group or a hydroxy group, R ₂ is an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an acryl group, a carboxyl group or a hydroxy group, and n is an integer of 1 to 10).
The black photosensitive resin composition according to claim 1, wherein the leveling agent is contained in an amount of 0.1 to 5% by weight based on the total weight of the black photosensitive resin composition.
The black photosensitive resin composition according to claim 1, wherein the substrate has a water contact angle of 10 ° to 50 °.
The photosensitive resin composition according to claim 1, which comprises 3 to 20% by weight of a black pigment, 0.5 to 50% by weight of an alkali soluble resin, 1 to 10% by weight of a photopolymerizable compound, 0.01 to 15% by weight of a photopolymerization initiator, By weight based on the total weight of the black photosensitive resin composition.
And a coating film formed from the black photosensitive resin composition of any one of claims 1 to 6 on one side of the base material,
And the polar surface free energy of the coating film is 0.1 to 4.5 mN / m.
The optical laminate according to claim 7, wherein the substrate has a water contact angle of 10 to 50 °.
The optical laminate according to claim 7, wherein the coating film is a light shielding layer.