KR101970325B1 - Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same - Google Patents

Abstract

The black photosensitive resin composition which concerns on this invention is alkali-soluble resin containing an alicyclic cyclic epoxy group; And a thermal acid generator.

Description

BLACK PHOTOSENSITIVE RESIN COMPOSITION, BLACK MATRIX, COLUMN SAPCER AND COLUMN SPACER COMBINED WITH BLACK MATRIX FOR IMAGE DISPLAY DEVICE PRODUCED USING THE SAME }

The present invention relates to a black photosensitive resin composition, a black matrix, a column spacer and a black matrix integrated column spacer for an image display device manufactured therefrom.

The black photosensitive resin composition is an essential material such as a color filter, a liquid crystal display material, an organic light emitting element, and a display. As an example, a light blocking layer may be formed in a color filter of a color liquid crystal display in a boundary portion between colored layers such as red, green, and blue to increase display contrast and color development effects.

Specifically, in a pixel composed of red (R), green (G), and blue (B), a black matrix is formed at the boundary between the colored layers of each pixel in order to prevent mixing with other colors or to hide the pattern of the electrode. May be formed or a column spacer may be formed in a portion in contact with the liquid crystal.

Recently, a technology for allowing a single material used in a display to simultaneously perform various roles has been developed. As a result, a black photosensitive resin composition is required to form a black matrix and a cell gap maintaining spacer on an array substrate. . Accordingly, there is a demand for the development of a black photosensitive resin composition which is excellent in reliability such as chemical resistance and secures a uniform optical density (OD, optical density) to form a uniform coating film and can provide excellent surface roughness and elastic modulus. .

Korean Patent Laid-Open Publication No. 2007-0094460 relates to a black photosensitive composition, which discloses a black photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator, and a black pigment, and a black photosensitive composition containing an organic pigment as a shape stabilizer. have.

In addition, the Republic of Korea Patent Publication No. 2012-0033893 relates to a photosensitive resin composition, (A) binder resin; (B) polyfunctional monomers; (C) photoinitiator or photosensitizer; (D) a black pigment; And (E) a solvent, wherein the black pigment discloses a content of at least one photosensitive resin composition selected from aniline black, perylene black, and metal oxides.

However, it does not suggest that the black photosensitive resin composition of the said document needs improvement of surface roughness and elastic recovery rate.

Republic of Korea Patent Publication No. 2007-0094460 (2007.09.20.) Republic of Korea Patent Publication No. 2012-0033893 (2012.04.09.)

The present invention has been made to solve the above problems, and an object thereof is to provide a black photosensitive resin composition having excellent reliability such as chemical resistance through sufficient curing.

Another object of the present invention is to provide a black matrix, a column spacer, or a black matrix integrated column spacer having excellent surface roughness or elastic recovery rate prepared using the black photosensitive resin composition described above.

The black photosensitive resin composition according to the present invention for achieving the above object is an alkali-soluble resin containing an alicyclic cyclic epoxy group; And a thermal acid generator.

The present invention also provides a black matrix, column spacer, or black matrix integrated column spacer comprising the cured product of the black photosensitive resin composition described above.

The black photosensitive resin composition according to the present invention has an advantage of being excellent in reliability, such as chemical resistance, by providing a specific alkali-soluble resin and a thermal acid generator together with excellent elastic modulus by curing with light and heat.

In addition, the black matrix, the column spacer or the black matrix integrated column spacer prepared using the black photosensitive resin composition according to the present invention has excellent surface roughness and excellent elastic recovery.

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

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

<Black photosensitive resin composition>

The black photosensitive resin composition which concerns on this invention is alkali-soluble resin containing an alicyclic cyclic epoxy group; And a thermal acid generator.

Furthermore, the black photosensitive resin composition which concerns on this invention is a coloring agent containing a black pigment; Photopolymerization initiator; solvent; And it may further include one or more selected from the group consisting of additives.

One aspect of this invention is alkali-soluble resin containing an alicyclic cyclic epoxy group; And it relates to a black photosensitive resin composition comprising a thermal acid generator.

Alicyclic  Alkali-soluble resin containing cyclic epoxy group

Alkali-soluble resins according to the present invention include alicyclic cyclic epoxy groups. Specifically, the alkali-soluble resin according to the present invention may include an alicyclic cyclic epoxy group in the compound.

Alkali-soluble resin containing an alicyclic cyclic epoxy group according to the present invention makes the non-exposed portion of the black photosensitive resin layer formed by using the black photosensitive resin composition is alkali-soluble and has reactivity to the action of light or heat.

In one embodiment of the present invention, the alkali-soluble resin may include a moiety represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R 1 is hydrogen or a methyl group,

a is an integer of 1-20.

The term "including the moiety represented by the formula (1)" refers to a case where a part of the compound included in the alkali-soluble resin includes the moiety represented by the formula (1).

When the alkali-soluble resin includes the moiety represented by the formula (1), it is preferable in view of reliability such as chemical resistance.

The part represented by Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2.

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

R 1 is hydrogen or a methyl group,

a is an integer of 1-20.

The alkali-soluble resin according to the present invention may be in the form of a copolymer including a moiety represented by Chemical Formula 1-1 and a moiety represented by Chemical Formula 1-2 in one molecule. For example, the alkali-soluble resin according to the present invention may be in the form of a copolymer including the moiety represented by Formula 1-1 and Formula 1-2 in a molar ratio of 50:50 relative to 100 mole% of the total repeating units in the copolymer. It may be.

In another embodiment of the present invention, the alkali-soluble resin may further include a portion represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R 4 is hydrogen or a methyl group,

b is an integer of 1-20.

Specifically, the alkali-soluble resin according to the present invention may include a part represented by Formula 1 and a part represented by Formula 3, and more specifically, the alkali-soluble resin according to the present invention is a part represented by Formula 1 And it may include a copolymer comprising a moiety represented by the formula (3). Specifically, the alkali-soluble resin according to the present invention may include a copolymer including a moiety represented by Chemical Formula 1-1 and Chemical Formula 1-2 and a moiety represented by Chemical Formula 3.

The form of the copolymer is not limited in the present invention, for example, the copolymer may be a block copolymer, a cross copolymer or a random copolymer.

The molecular weight of the alkali-soluble resin is not particularly limited in the present invention. For example, the polystyrene reduced weight average molecular weight (hereinafter referred to as weight average molecular weight) may be 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 20,000.

In still another embodiment of the present invention, the alkali-soluble resin may be included in an amount of 5 to 80 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin and 100 parts by weight of the photopolymerizable compound. When the alkali-soluble resin is included in the above range, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable.

Thermal acid generator

The black photosensitive resin composition which concerns on this invention contains a thermal acid generator. The thermal acid generator refers to a component that generates acid by heat, and generates components by heat treatment (for example, post-baking) applied in the process of curing the black photosensitive resin composition to promote curing of the pattern.

In another embodiment of the present invention, the thermal acid generator may be represented by the following formula (2).

 [Formula 2]

In Chemical Formula 2,

R2 is a C3-8 cycloalkyl group,

R3 is a C1-C8 alkyl group or a C6-C10 aryl group.

In the present invention, the alkyl group is not particularly limited, but may be linear or branched, and preferably has 1 to 8 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl , tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n- Octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2 -Methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present invention, the cycloalkyl group is preferably 3 to 8 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

The cycloalkyl group may be substituted or unsubstituted with a hydroxy group, but is not limited thereto.

In the present invention, the aryl group is not particularly limited, but preferably has 6 to 8 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

The aryl group may be substituted or unsubstituted with an alkyl group, specifically a methyl group.

Specifically, the thermal acid generator represented by Chemical Formula 2 may be represented by the following Chemical Formulas 2-1 to 2-3, and each may be used alone or in combination of two or more thereof.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In still another embodiment of the present invention, the thermal acid generator may be included in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin and 100 parts by weight of the total photopolymerizable compound solids. Can be.

When the thermal acid generator is included in the above range, the solution uniformity to the solvent is secured, solubility is improved, and the black photosensitive resin composition is highly sensitive, so that the strength of the pattern portion formed using the black photosensitive resin composition or the surface of the pattern portion It is preferable because the smoothness of tends to be good.

If the thermal acid generator is included in less than the above range may be a weak effect of solvent resistance, if exceeding the above range is preferable to be included in the above range because there is a problem of developability of the peeling type is faster. .

In another embodiment of this invention, the said black photosensitive resin composition contains a photopolymerizable compound further.

Moreover, in another embodiment of this invention, the said black photosensitive resin composition is a coloring agent containing a black pigment; Photopolymerization initiator; solvent; And it may further include one or more selected from the group consisting of additives.

Photopolymerizable  compound

When the photopolymerizable compound is included in the black photosensitive resin composition, the crosslinking density may be increased during the manufacturing process, and the mechanical properties of the pattern to be manufactured may be enhanced.

The photopolymerizable compound is not limited as long as it contains an unsaturated group and is photosensitive, and those commonly used in the art can be used, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone Etc. can be mentioned.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol Bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound is preferably included in an amount of 5 to 50 parts by weight, and more preferably in an amount of 7 to 45 parts by weight, based on 100 parts by weight of the total solid in the black photosensitive resin composition. When the content of the photopolymerizable compound is included within the above range, the intensity or smoothness of the pixel portion may be improved.

coloring agent

The black photosensitive resin composition which concerns on this invention contains the coloring agent containing a black pigment.

The black pigment may be, for example, aniline black, perylene black, titanium black, carbon black, and may be used without particular limitation as long as it has a light shielding property.

Carbon blacks which can be used include CHBK-17 from Mikuni; Sisto 5HIISAF-HS, Sisto KH, Sisto 3HHAF-HS, Sisto NH, Sisto 3M, Sisto 300HAF-LS, Sisto 116HMMAF-HS, Sisto 116MAF, Sisto FMFEF- HS, cysto SOFEF, cysto VGPF, cysto SVHSRF-HS, and cysto SSRF; Mitsubishi Chemical Corporation Diagram Black II, 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, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; Daegu Co., Ltd. PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN- 2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

The carbon black is not particularly limited as long as it is a pigment having light blocking properties, and known carbon black can be used. Specifically, the black pigment, carbon black, may be a channel black, a furnace black, a thermal black, a lamp black, or the like.

In addition, the carbon black which is the said black pigment can also use the carbon black coated with resin. Since the carbon black coated with the resin has lower conductivity than the carbon black coated with the resin, it is possible to impart excellent electrical insulation when forming the black matrix or the black column spacer.

In another embodiment of the present invention, the colorant may further include one or more selected from the group consisting of organic pigments and dyes.

Specifically, the colorant may include one or two or more organic pigments and dyes that are light-shielding in visible light.

The organic pigment is, for example, a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colourists), specifically the color index (CI) as described below. Names may be given, but is not limited thereto.

Specifically, the organic pigment is C.I. Pigment Yellow No. 1, C.I. Pigment Yellow No. 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 55, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow No. 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow No. 173, C.I. Pigment Yellow No. 180, C.I. Pigment yellow 211;

C.I. Pigment Orange No. 5, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 14, C.I. Pigment Orange No. 24, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 34, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 46, C.I. Pigment Orange 49, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange No. 68, C.I. Pigment Orange No. 70, C.I. Pigment Orange 71, C.I. Pigment Orange No. 72, C.I. Pigment Orange No. 73, C.I. Pigment orange 74;

C.I. Pigment Red No. 1, C.I. Pigment Red No. 2, C.I. Pigment Red No. 5, C.I. Pigment Red No. 9, C.I. Pigment Red No. 17, C.I. Pigment Red No. 31, C.I. Pigment Red No. 32, C.I. Pigment Red No. 41, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red No. 170, C.I. Pigment Red 171, C.I. Pigment Red No. 175, C.I. Pigment Red 176, C.I. Pigment Red No. 177, C.I. Pigment Red 178, C.I. Pigment Red No. 179, C.I. Pigment Red No. 180, C.I. Pigment Red No. 185, C.I. Pigment Red 192, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red No. 208, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red No. 220, C.I. Pigment Red No. 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red No. 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment red 272;

C.I. Pigment Blue No. 16, C.I. Pigment Blue No. 60, C.I. Pigment blue 80;

C.I. Pigment Purple No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38;

C.I. Pigment Brown No. 23, C.I. Pigment brown 25;

C.I. Pigment Black No. 1, C.I. Pigment Black No. 7. And the like, and, optionally, rosin treatment, surface treatment with a pigment derivative having an acidic group or basic group introduced therein, surface graft treatment with a polymer compound, etc., fine granulation treatment with sulfuric acid, or an organic solvent or water. The cleaning treatment may be performed.

In addition, pigments used in printing inks and ink jets, and water-soluble azo, insoluble azo, phthalocyanine, quinacryton, isoindolinone, isoindolin, perylene, perinone, dioxyzin, anthraquinone, dianine Traquinonyl, anthrapyrimidine, ananthrone, indanthrone, pravantron, pyrantrone-based pigments and the like may be used, but is not limited thereto.

The dye is for example C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent orange 63; C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91: 1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent red 197; C.I. Solvent Purple No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent purple 59; C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent blue 70; C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent green 7 and the like.

In another embodiment of the present invention, the colorant may further include a blue pigment. Specifically, in the present invention, the organic pigment may be a blue pigment.

When the colorant further comprises a blue pigment, there is an advantage of more effectively blocking the transmission of light in the 700 ~ 750nm region.

The colorant according to the present invention may include 25 to 55 parts by weight, preferably 25 to 40 parts by weight, more preferably 27 to 37 parts by weight based on 100 parts by weight of the total black solid photosensitive resin composition. When the content of the colorant is less than the above range, the optical density (OD) may be somewhat lowered. If the colorant exceeds the above range, the relative dielectric constant is slightly increased, which may cause problems in driving the display device. It is preferable.

The black pigment may be included in an amount of 40 to 60 parts by weight, more preferably 45 to 50 parts by weight, based on 100 parts by weight of the total colorant. When the black pigment satisfies the above range, there is an advantage that O.D / μm satisfies 1.33 or more. When the black pigment is included in the range below the OD is low, there may be a problem that light leakage occurs in short and long wavelengths, and if the black pigment exceeds the range there may be a problem that the dielectric constant increases, so the black pigment It is preferable to be included in the said range.

Photopolymerization Initiator

The photopolymerization initiator included in the present invention can be applied to those commonly used in the photosensitive resin composition, for example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based Compounds and the like can be used.

Acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl- Oligomers of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one are possible. Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

As the benzophenone compound, benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (Diethyl amino) benzophenone and the like are possible.

Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4' '-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2 -Biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro methyl (Piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available products such as OXE-01 and OXE-02 from Ciba.

As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like can be used.

Biimidazole type compounds include 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-chlorophenyl) -4,4', 5,5 ''-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' '-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 '' position The imidazole compound etc. which are substituted by the carboalkoxy group are possible.

The photopolymerization initiator may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the black photosensitive resin composition. This content range takes into account the photopolymerization rate of the photopolymerizable compound and the physical properties of the final obtained coating film, and if it is less than the above range, the overall polymerization time may be low due to the low polymerization rate. Since the physical property of a coating film may fall rather, it is preferable to use suitably within the said range.

In addition, a photopolymerization initiation aid may be used together with the photopolymerization initiator. When the photopolymerization initiation aid is used together with the photopolymerization initiator, the photosensitive resin composition is more sensitive, and thus productivity is preferable. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

Such photopolymerization initiation adjuvant is preferably used in the range of usually 10 mol or less, preferably 0.01 to 5 mol per mol of the photopolymerization initiator. When using a photopolymerization start adjuvant within the said range, it can anticipate the effect of improving productivity by increasing a polymerization efficiency.

solvent

The solvent may be used as long as the solvent has compatibility with the above-described components and does not react. Various organic solvents generally used can be used, and the solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in view of applicability and dryness.

For example, the solvent may include alkylene glycol alkyl ether acetates, ketones, esters such as 3-ethoxypropionate ethyl and 3-methoxypropionate methyl, and more preferably propylene glycol monomethyl ether acetate and propylene. Glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents can be used individually or in mixture of 2 or more types, respectively.

It is preferable to be contained in 60-90 weight part with respect to 100 weight part of said whole black photosensitive resin compositions, and, as for content of the solvent in the black photosensitive resin composition of this invention, it is more preferable that it is included in 65-85 weight part. If the solvent content is included within the above range, the coating property may be improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet. .

additive

The black photosensitive resin composition according to the present invention may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, and the like, as necessary.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of the other high molecular compound include thermosetting resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

 The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like. Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned. Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like. The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent.

As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example. As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Japan Ewha Co., Ltd.) is mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.

As said leveling agent, commercially available surfactants can be used, For example, surfactants, such as a silicone type, a fluorine type, ester type, a cation type, an anion type, a nonionic type, an amphoteric, etc., are mentioned, These are each independently, either You may use in combination of 2 or more type. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), MegaPac (Dainippon Ink Chemical Co., Ltd.) Corporation), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahigaras Co., Ltd.), Soap Sparse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKACHEMICALS ), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

 As the adhesion promoter, a silane compound is preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

The additive may be used as appropriate in the range that does not impair the object of the present invention, for example, 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably based on 100 parts by weight of the total black photosensitive resin composition May be included in an amount of 0.01 to 3 parts by weight, but is not limited thereto.

<Black matrix, column Spacer , Black matrix integrated column Spacer >

Another aspect of the present invention relates to a black matrix, column spacer, or black matrix integrated column spacer comprising the cured product of the black photosensitive resin composition described above.

Since the black photosensitive resin composition according to the present invention includes a specific alkali-soluble resin and a thermal acid generator, sufficient curing is possible in a thermosetting process such as post-baking, and thus, there is an advantage of excellent reliability such as chemical resistance. Therefore, the black matrix, the column spacer or the black matrix according to the present invention prepared using the same have excellent solvent resistance, excellent elastic modulus and excellent surface roughness.

In the present invention, the black matrix integrated column spacer does not form the black matrix and the column spacer, respectively, but means that the black matrix and the column spacer can be performed in one pattern.

The introduction of the black matrix, the column spacer or the black matrix integrated column spacer may be formed by patterning through a photolithography method after coating. The photolithographic method is not particularly limited in the present invention, and any known method using the photosensitive resin composition can be applied. As an example, the following steps may be included:

a) applying a black photosensitive resin composition to the substrate;

b) a prebaking step of drying the solvent;

c) applying a photo mask to the obtained film to irradiate actinic rays to cure the exposed portion;

d) dissolving the unexposed portion using an aqueous alkali solution to perform a developing process; And

e) drying and post-baking steps

The substrate is a glass substrate or a polymer plate. Especially as a glass substrate, soda-lime glass, barium or strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be used preferably. Moreover, a polycarbonate, an acryl, a polyethylene terephthalate, a polyether sulfide, a poly sulfone, etc. are mentioned as a polymer board.

In this case, the coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, and the like to obtain a desired thickness.

The prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

Moreover, exposure performed after a prebaking is performed by an exposure machine, and it exposes only the part corresponding to a pattern by exposing through a photomask. At this time, the light to be irradiated may be visible light, ultraviolet light, X-ray, electron beam, or the like.

It is performed for the purpose of removing the photosensitive resin composition of the part which is not removed of the alkali image development unexposed part after exposure, and a desired pattern is formed by this phenomenon. As a developer suitable for this alkali image development, the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, etc. can be used, for example. In particular, using a developer or an ultrasonic cleaner in a temperature of 10 to 50 ° C., preferably 20 to 40 ° C., using a less alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate. Do it.

The post bake is performed to increase the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220 ° C. for 10 to 120 minutes. Like post-baking prebaking, it is carried out using an oven, hot plate and the like.

The black matrix, column spacer, and black matrix integrated column spacer manufactured using the black photosensitive resin composition according to the present invention may be applied to various image display devices such as liquid crystal displays, OLEDs, flexible displays, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Production Example  1: Alkali Soluble Resin (B) Synthesis

277 g of methoxybutyl acetate was added to a 1-liter separate-type flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and heated to 80 ° C., followed by 3,4-epoxytricyclo [5.2.1.0 ³⁰¹ g of a mixture of ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate [50:50 (molar ratio)], methacrylic acid 49 g and a mixed solution obtained by dissolving 23 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate were added dropwise over 5 hours, and further aged for 3 hours to obtain a copolymer solution [solid content (NV) 35.0 wt%]. The dry value of the obtained copolymer was 69.8 KOH mg / g, the weight average molecular weight (Mw) was 12300, and the dispersion degree (Mw / Mn) was 2.1.

Production Example  2: colored dispersion preparation

As a pigment, C.I. Pigment Red (PR208) 30.0 parts by weight, organic black 44.0 parts by weight, C.I. 53.0 parts by weight of Pimentation Blue (PB60), 27.0 parts by weight of carbon black, and 65.0 parts by weight of an alkali-soluble resin synthesized under the above conditions [solid content (NV) 35.0% by weight], and the dispersant are an acrylic polymer dispersant (DISPERBYK-2000). 94.0 parts by weight [solid content (NV) 40.0% by weight] and a composition consisting of 687 parts by weight of propylene glycol monomethyl ether acetate as a solvent and a rigid milling medium (zirconia beads) having an average particle size of 0.1mm in a weight ratio of 50:50 After the addition and co-dispersion of four pigments for 4-6 hours by using a bead mill to prepare a colored dispersion.

Preparation of the black photosensitive resin composition: Example  1 to 5 and Comparative example  1 to 2

 Black photosensitive resin compositions according to Examples and Comparative Examples were prepared, including the compositions described in Table 1 and the colored dispersions according to Preparation Example 2.

division Example Comparative example One 2 3 4 5 One 2 Thermal acid generator A-1 0.31 - - - 0.61 - - A-2 - 0.31 - 0.61 - - - A-3 - - 0.31 - - - - A-4 - - - - - - 0.31 Alkali soluble resin B 17.65 17.65 17.65 17.10 17.10 18.24 17.65 Photopolymerizable compound 3.34 3.34 3.34 3.25 3.25 3.44 3.34 Photopolymerization Initiator 0.42 0.42 0.42 0.41 0.41 0.43 0.42 additive 0.02 0.02 0.02 0.02 0.02 0.02 0.02 solvent 37.55 37.55 37.55 37.90 37.90 37.16 37.55 Coloring dispersion 40.71 40.71 40.71 40.71 40.71 40.71 40.71 Alkali-soluble resin: Copolymer solution of alkali-soluble resin according to manufacture example 1 (solid content 35%)
Photopolymerizable compound: DPHA, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
Photoinitiator: Irgacure 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, product of Ciba Specialty Chemicals
Solvent: PGMEA (Propylene glycol monomethyl ether acetate)
Additive: DiperBYK-163 (by KK)
Colored dispersion liquid: The colored dispersion liquid according to manufacture example 2

[A-1]

[A-2]

[A-3]

[A-4]

Experimental Example

(One) Surface roughness  evaluation

The board | substrate was manufactured using the black photosensitive resin composition manufactured according to the Example and the comparative example. The substrate was used by washing a 5 × 5 cm glass substrate (Corning Corporation, # 1737) with a neutral detergent and water, followed by drying. The black photosensitive resin composition was apply | coated by this spin coating method on this glass substrate, and it puts on a heating plate, and dried at the temperature of 80-120 degreeC for 1-2 minutes, and removed the solvent. And the thin film from which the solvent was removed was immersed in a KOH aqueous solution developing solution of pH 10.5 at 20 ℃ to observe the development behavior of the coating film. The time when the coating film was developed completely was measured and the experiment was conducted based on the measured time. The development was carried out for each hour, and the glass substrate having the thin film was immersed in distilled water for 5 seconds, dried by blowing nitrogen gas, and heated in a heating oven at 220 to 250 ° C. for 20 to 30 minutes to prepare a substrate. The surface roughness of the surface of the produced coating film was measured in Ra and Rq values using Dektak 6M (Veeco), and are shown in Table 2 below. In the measurement method, the measurement scan range of Dektak was set to 500 μm, the measurement point was set to the front part of the manufactured substrate, and the measurement range point of the result value was set to 50 μm and 450 μm respectively within the entire scan range.

division Developing speed Developing Type Surface Roughness (Rq / Ra) Example 1 40 Dissolution 2.00nm / 1.59nm Example 2 42 Dissolution 1.97nm / 1.50nm Example 3 42 Dissolution 2.24nm / 1.73nm Example 4 35 Dissolution 1.80nm / 1.49nm Example 5 33 Dissolution 1.93nm / 1.52nm Comparative Example 1 55 Dissolution 7.95nm / 6.21nm Comparative Example 2 30 Peeling 2.49nm / 1.94nm

The roughness of the surface was determined by measuring the surface roughness of the coating film produced according to Examples 1-5 and Comparative Examples 1-2 of the black photosensitive resin composition. Referring to Table 2, it can be seen that the coating film prepared using the black photosensitive resin composition of Examples 1 to 5 has excellent surface roughness. On the other hand, the coating film prepared according to Comparative Example 1 was not excellent in the surface roughness, in the case of Comparative Example 2 showed a developability of the peeling form was confirmed that the use is restricted.

(2) Solvent resistance  evaluation

Reliability was determined by measuring solvent resistance using a coating film prepared from the black photosensitive resin composition prepared according to Examples 1 to 5 and Comparative Examples 1 to 2, and the manufacturing method of the coating film was the same as in Experimental Example (1).

Solvent resistance was measured by immersing the coating film (3 × 3) in NMP 18g solution at room temperature for 60 minutes, extracting the NMP solvent, and measuring the absorbance at the visible light wavelength of the NMP solvent after immersion using a UV-2600 device from Shimadzu. Peak absorbance of the solvent is shown in Table 3 below.

peak absorbance @ 520nm (abs) Example 1 0.0015 Example 2 0.0013 Example 3 0.0016 Example 4 0.0012 Example 5 0.0012 Comparative Example 1 0.0259 Comparative Example 2 0.0007

Referring to Table 3, in the experimental results of measuring the wavelength of the NMP solvent, the coating films of Comparative Examples 1 to 2 exhibited high detectability due to the high dissolution of pigments and dyes in the NMP solvent, whereas Examples 1 to 5 The coating film of showed low detectability because there was little elution of pigment or dye in NMP solvent. That is, it turned out that solvent resistance is excellent in the coating film formation of the composition of Examples 1-5.

(3) elastic recovery rate of CS pattern of coating film

Using the coating films prepared according to Examples and Comparative Examples, the change in height before and after the compression property was measured to confirm the elastic recovery rate, and the results are shown in Table 4 below. At this time, the measurement conditions were fixed D1 (compression displacement) = 1.0㎛, Force = max 500mN (at 2mN / sec), the indenter confirmed the compression characteristics in a flat type.

Elastic recovery Example 1 99.2% Example 2 99.7% Example 3 98.3% Example 4 99.8% Example 5 99.7% Comparative Example 1 93.3% Comparative Example 2 95.9%

As a result of confirming the elastic recovery rate of the coating films prepared according to Examples 1 to 5 and Comparative Examples 1 to 2, when the photoinitiator and the thermal acid generator are mixed, an IPN (Interpenetraiting polymer network) structure is formed by photocrosslinking and thermal crosslinking. It can be seen that the elastic recovery rate is improved.

Claims (13)

Alkali-soluble resin containing an alicyclic cyclic epoxy group;
Colorants including black pigments; And
In the black photosensitive resin composition comprising: a thermal acid generator represented by the formula (2);
The black photosensitive resin composition of the cured product of the black photosensitive resin composition has a compressive displacement D1 of 1.0 μm and an elastic recovery rate of 98.3% or more measured with a flat type indenter at 500 mN at 2 mN / sec:
[Formula 2]

In Chemical Formula 2,
R2 is a cycloalkyl group having 3 to 8 carbon atoms,
R 3 is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms. The method of claim 1,
The black photosensitive resin composition wherein the alkali-soluble resin comprises a part represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R 1 is hydrogen or a methyl group,
a is an integer of 1-20. delete The method of claim 2,
The black photosensitive resin composition wherein the alkali-soluble resin further comprises a portion represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R 4 is hydrogen or a methyl group,
b is an integer of 1-20. The method of claim 1,
The black photosensitive resin composition which further contains a photopolymerizable compound. The method of claim 5,
The black photosensitive resin composition of the said alkali-soluble resin is contained in 5 to 85 weight part with respect to 100 weight part of said alkali-soluble resin and the said total photopolymerizable compound. The method of claim 5,
The thermal photo-acid generator is a black photosensitive resin composition which is contained in 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin and 100 parts by weight of the total photopolymerizable compound solids. The method of claim 1,
Photopolymerization initiator; solvent; And at least one selected from the group consisting of additives. The method of claim 1,
The colorant is a black photosensitive resin composition further comprises one or more selected from the group consisting of organic pigments and dyes. The method of claim 9,
The color photosensitive resin composition wherein the colorant further comprises a blue pigment. The black matrix containing the hardened | cured material of the black photosensitive resin composition of any one of Claims 1, 2, and 4-10. The column spacer containing the hardened | cured material of the black photosensitive resin composition of any one of Claims 1, 2, and 4-10. A black matrix integrated column spacer comprising the cured product of the black photosensitive resin composition according to any one of claims 1, 2, and 4 to 10.