KR102202344B1 - 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 according to the present invention comprises a monomer having a functional group of 5 to 12 and an acid value of 10 to 60 mgKOH/g.

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 for an image display device prepared therefrom, a column spacer, and a black matrix integrated column spacer.

The black photosensitive resin composition is an essential material such as a color filter, a liquid crystal display material, an organic light emitting device, and a display. For example, in a color filter of a color liquid crystal display, a light-shielding layer is formed at a boundary between colored layers such as red, green, and blue, thereby enhancing display contrast or color development effect.

Recently, a technology that allows one material used inside the display to play various roles at the same time has been developed, and for this reason, a black photosensitive resin composition is also required to form a spacer for maintaining a black matrix and cell gap on an array substrate. The demand for black photosensitive resin compositions is further increasing.

Republic of Korea Patent Publication No. 2007-0094460 relates to a black photosensitive composition, a black photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator, and a black pigment, and discloses the contents of a black photosensitive composition containing an organic pigment as a shape stabilizer. have.

In addition, Korean Patent Application Publication No. 2012-0033893 relates to a photosensitive resin composition, (A) a binder resin; (B) polyfunctional monomer; (C) a photoinitiator or a photosensitizer; (D) black pigment; And (E) a solvent, wherein the black pigment is at least one selected from aniline black, perylene black, and metal oxide.

However, the black photosensitive resin composition of the document has a problem in that the margin on the process is low due to the limitation of the exposure transmittance due to the black expression and the disadvantage to the development process.

Therefore, there is a demand for the development of a black photosensitive resin composition with improved manufacturing yield by improving the margin on the process.

Republic of Korea Patent Publication No. 2007-0094460 (2007.02.06.) Republic of Korea Patent Publication No. 2012-0033893 (2012.04.09.)

The present invention is to solve the above problems, and an object thereof is to provide a black photosensitive resin composition capable of increasing a margin in a process.

In addition, an object of the present invention is to provide a black matrix, a column spacer, or a black matrix-integrated column spacer prepared using the above-described black photosensitive resin composition.

The black photosensitive resin composition according to the present invention for achieving the above object comprises a functional group of 5 to 12, and a monomer having an acid value of 10 to 60 mgKOH/g; characterized in that it comprises.

In addition, the present invention provides a black matrix, a column spacer, or a black matrix-integrated column spacer including the cured product of the black photosensitive resin composition described above.

Since the black photosensitive resin composition according to the present invention contains a specific monomer, it has excellent developability, reliability, or processability, and has an advantage of improving a process margin.

In addition, a black matrix, a column spacer, or a black matrix-integrated column spacer manufactured using the black photosensitive resin composition according to the present invention has advantages of excellent reliability and ease of manufacture.

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

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

In the present invention, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise specified.

<Black photosensitive resin composition>

The black photosensitive resin composition according to the present invention comprises a monomer having a functional group of 5 to 12 and an acid value of 10 to 60 mgKOH/g.

In addition, the black photosensitive resin composition according to the present invention includes a colorant including a black pigment; Binder resin; Photopolymerization initiator; It may further include one or more selected from the group consisting of solvents and additives.

One aspect of the present invention relates to a black photosensitive resin composition comprising a monomer having a functional group of 5 to 12 and an acid value of 10 to 60 mgKOH/g.

In the present invention, the “monomer” may be used interchangeably with “monomer”, and may be distinguished from “oligomer” and “polymer”.

The monomer according to the present invention may include a functional group of 5 to 12, preferably a functional group of 5 to 9, more preferably a functional group of 6 to 8, and the functional group contains an unsaturated group or What has photosensitivity can be used.

When the monomer according to the present invention includes a functional group within the above range, it may have better sensitivity, and thus, it may be easier to manufacture a black matrix, a column spacer, or a black matrix integrated column spacer.

In one embodiment of the present invention, the monomer may further contain a hydroxyl group. Although not wishing to be bound by theory, in the case of a colored photosensitive resin composition for manufacturing a general color filter, if the monomer contains a hydroxyl group, it is advantageous for developability, but it may have a somewhat adverse effect on reliability and process margin. . However, when a hydroxyl group is included in the monomer included in the black photosensitive composition according to the present invention, developability, reliability, and fairness are excellent. Specifically, when a hydroxyl group is included in the monomer, there is an advantage that reliability can be improved as the degree of crosslinking increases due to a crosslinking reaction with a photoinitiator and a binder resin to be described later.

The monomer according to the present invention may have an acid value of 10 to 60 mgKOH/g, preferably 10 to 50 mgKOH/g, and more preferably 20 to 40 mgKOH/g. When the acid value of the monomer is within the above range, there is an advantage of increasing the process margin. When the acid value of the monomer is less than the above range, there is a problem that developability may be slightly lowered, and when the acid value of the monomer exceeds the above range, there is a problem that the margin on the process may be reduced due to too high an acid value in the monomer, so it is included within the above range. It is desirable to be.

In the present invention, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution.

In another embodiment of the present invention, the functional group may include an ethylenically unsaturated double bond. When the functional group contains the ethylenically unsaturated double bond, it reacts with the photopolymerized alkaline resin to be described later, thereby increasing the degree of crosslinking, and has an advantage of being easy to handle in the process.

In another embodiment of the present invention, the monomer may be included in 1.7 to 4.2 parts by weight, preferably 1.8 to 4.0 parts by weight, more preferably 2.0 to 3.8 parts by weight, based on the total 100 parts by weight of the black photosensitive resin composition. have.

When the monomer is included within the above range, it is possible to provide a black photosensitive resin composition having excellent process margin because developability, reliability, or processability is excellent. If the monomer is included below the above range, it may be difficult to form a pattern because developability may be slightly lowered, and if it exceeds the above range, the margin value of developability and fairness may be slightly lowered, thus satisfying the above range. It is preferable to be included so as to.

The monomer may be directly synthesized and used, or commercially available ones may be purchased and used. The commercially available monomers include, for example, Viscoat#802-A, Viscoat#802-B, Viscoat#802-C, Viscoat#802-D, etc. of Osaka Organic Chemical, but are not limited thereto, and according to the present invention What satisfies the monomer can be used.

In yet another embodiment of the present invention, the black photosensitive resin composition comprises a black colorant; Binder resin; Photopolymerization initiator; It may further include one or more selected from the group consisting of solvents and additives.

The black photosensitive resin composition according to the present invention includes a black colorant.

In another embodiment of the present invention, the colorant relates to a black photosensitive resin composition comprising at least one selected from the group consisting of red, blue and black pigments.

The black (black) pigment may be, for example, aniline black, perylene black, titanium black, or carbon black, and may be used without particular limitation as long as it has light-shielding properties.

Examples of usable carbon black include CHBK-17 from Mikuni Saxophone; Donghae Carbon Co., Ltd.'s Systo 5HIISAF-HS, Systo KH, Systo 3HHAF-HS, Systo NH, Systo 3M, Systo 300HAF-LS, Systo 116HMMAF-HS, Systo 116MAF, Systo FMFEF- HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Mitsubishi Chemical Corporation's 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 Corporation's 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; Columbia Carbon Co., Ltd.'s 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 light-shielding pigment, and a known carbon black may be used. Specific examples of carbon black as the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

In addition, as the carbon black as the black pigment, carbon black coated with a resin may be used. Since the carbon black coated with the resin has a lower conductivity than the carbon black not coated with the resin, excellent electrical insulation can be provided when forming a black matrix or a black column spacer.

The colorant may further include at least one 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 capable of blocking light from 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 Colorists), specifically, the following color index (CI) The name 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 No. 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 No. 137, C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow No. 153, C.I. Pigment Yellow No. 154, C.I. Pigment Yellow No. 155, C.I. Pigment Yellow No. 166, C.I. Pigment Yellow No. 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 No. 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 No. 64, C.I. Pigment Orange No. 65, C.I. Pigment Orange No. 68, C.I. Pigment Orange No. 70, C.I. Pigment Orange No. 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 No. 123, C.I. Pigment Red No. 144, C.I. Pigment Red No. 149, C.I. Pigment Red No. 166, C.I. Pigment Red No. 168, C.I. Pigment Red No. 170, C.I. Pigment Red No. 171, C.I. Pigment Red No. 175, C.I. Pigment Red No. 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 178, C.I. Pigment Red No. 179, C.I. Pigment Red No. 180, C.I. Pigment Red No. 185, C.I. Pigment Red No. 192, C.I. Pigment Red No. 194, C.I. Pigment Red No. 202, C.I. Pigment Red No. 206, C.I. Pigment Red No. 207, C.I. Pigment Red No. 208, C.I. Pigment Red No. 209, C.I. Pigment Red No. 214, C.I. Pigment Red No. 215, C.I. Pigment Red No. 216, C.I. Pigment Red No. 220, C.I. Pigment Red No. 221, C.I. Pigment Red No. 224, C.I. Pigment Red No. 242, C.I. Pigment Red No. 243, C.I. Pigment Red No. 254, C.I. Pigment Red No. 255, C.I. Pigment Red No. 262, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment red No. 272;

C.I. Pigment Blue No. 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, 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 Green No. 7, C.I. Pigment Green No. 36, C.I. Pigment Green No. 58, C.I. Pigment Green No. 59, C.I. Pigment Green No. 62, C.I. Pigment green 63;

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

C.I. Pigment Black No. 1, C.I. Pigment Black No. 7. May be used, and in some cases, rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group is introduced, surface graft treatment using a polymer compound, etc., fine particle treatment using sulfuric acid, or an organic solvent or water It may be that the washing treatment or the like has been performed.

In addition, pigments and water-soluble azo-based, insoluble azo-based, phthalocyanine-based, quinacrytone-based, isoindolinone-based, isoindolin, perylene, perinone, dioxygen, anthraquinone, dian Traquinonyl, anthrapyrimidine, antantron, indanthrone, pravantrone, pyrantrone pigments, etc. may be used, but the present invention is not limited thereto.

Such dyes are, 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 No. 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 No. 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 No. 7 and the like.

In still another embodiment of the present invention, the black photosensitive resin composition according to the present invention includes at least one colorant selected from the group consisting of red, blue, and black among the above-described colorants in order to facilitate the implementation of black.

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

When the colorant further includes a blue pigment, the effect in the exposure process may be excellent as the transmittance in the near-infrared region becomes excellent, and reliability may be improved due to improvement in chemical resistance to an organic solvent.

The colorant according to the present invention may include, for example, 25 to 55 parts by weight, preferably 27 to 40 parts by weight, more preferably 28 to 33 parts by weight, based on 100 parts by weight of the total solid content of the black photosensitive resin composition, but limited thereto. It doesn't work. If the content of the colorant is less than the above range, the optical density (OD) may be slightly lowered, and if the content of the colorant exceeds the above range, the relative dielectric constant may be slightly increased, which may cause some problems in driving the display device. It is desirable.

The black pigment may be included in, for example, 1 to 17 parts by weight, more preferably 2 to 17 parts by weight based on the total 100 parts by weight of the colorant, but is not limited thereto. When the black pigment satisfies the above range, there is an advantage in that the optical density can be excellent. If the black pigment is included below the above range, there may be a problem that the optical density may be slightly lowered, and if the black pigment exceeds the above range, there may be a problem that the transmittance in the near infrared region may be slightly lowered. It is preferable that the black pigment is included within the above range.

The black photosensitive resin composition according to the present invention includes a binder resin. The binder resin generally makes the non-exposed portion of the black photosensitive resin layer formed using the black photosensitive resin composition alkali-soluble, and acts as a dispersion medium for the pigment. The binder resin is not particularly limited in the present invention, and may be selected from various polymers used in the applicable technical field.

The weight average molecular weight of the binder resin is preferably 3000 to 30000, more preferably 5000 to 20000, and the acid value of the binder resin is preferably in the range of 50 to 200 mgKOH/g based on solid content.

When the acid value satisfies the above range, it is preferable because developability against alkali development is excellent, the occurrence of residues is suppressed, and adhesion of the pattern can be improved.

The binder resin may be included in an amount of 5 to 85 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, based on 100 parts by weight of the total solid content of the black photosensitive resin composition. When the binder resin is contained within the above range, the solubility in the developer solution is sufficient, so that the non-pixel portion is unlikely to be left behind on the substrate, and it is difficult to reduce the film of the pixel portion of the exposed portion during development, so that the non-pixel portion is omitted. This tends to be good.

The photopolymerization initiator included in the present invention can be applied to those generally 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, benzyldimethylketal, and 2-hydroxy-1-[4-(2-hydroxyethoxy) Phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- Oligomers of 2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. are possible And, among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one can be preferably used.

Benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis (Diethyl amino) benzophenone and the like are possible.

Triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4''-dime Toxic 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-triazine)-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(trichloromethyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl (Piperonyl)-6-triazine, 2,4-trichloromethyl (4'-methoxy styryl)-6-triazine, etc. are possible.

As the thioxanthone compound, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like are possible.

Examples of oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include Ciba's OXE-01 and OXE-02.

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

Biimidazole 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, the phenyl group at the 4,4',5,5'' position An imidazole compound substituted by a carboalkoxy group, etc. 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 is in consideration of the photopolymerization rate of the monomer and the physical properties of the finally obtained coating film.If it is less than the above range, the polymerization rate is low and the overall process time may be lengthened, and if it exceeds the above range, the crosslinking reaction will pass due to excessive reaction and the coating film Since the physical properties of may rather deteriorate, it is preferable to use appropriately within the above range.

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

It is preferable to use such a photopolymerization initiation aid within the range of usually 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, it is possible to increase the polymerization efficiency and improve productivity.

The solvent has compatibility with the above-described configurations, but may be used without limitation as long as it does not react. Various organic solvents generally used may be used, and the solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coating and drying properties.

For example, the solvent includes esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene. Glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents can be used alone or in combination of two or more.

The content of the solvent in the black photosensitive resin composition of the present invention is preferably contained in an amount of 60 to 90 parts by weight, and more preferably 65 to 85 parts by weight, based on 100 parts by weight of the total black photosensitive resin composition. When the content of the solvent is within the above range, coating properties 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), or inkjet. .

The black photosensitive resin composition according to the present invention may further include additives commonly used in the art to improve dispersibility, coating properties, or adhesion.

As the dispersant, suitable dispersants such as cationic, anionic, and nonionic can be used, but polymer dispersants are preferred. Specifically, acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be mentioned. Such dispersants can be obtained commercially, for example, as acrylic copolymers DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol) ), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol) ), as polyethyleneimine, Solsperse 24000 (manufactured by Lubrizol), and polyester such as Azisper PB821, Azisper PB822, Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

In addition, the additive may include, for example, a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof in order to increase adhesion to the substrate, but is limited thereto. It doesn't work. Specifically, the silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidok Cypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, may be used alone or in combination of two or more, but are not limited thereto.

In order to improve coatability, a surfactant may be further added. For example, fluorine-based surfactants such as M-1000, BM-1100 (BM Chemie), and Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M) may be used, but are not limited thereto. Surfactants commonly used in the industry can be used.

In the present invention, the content of the additive is not limited, and may be appropriately added and used within a range not impairing the object of the present invention. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total black photosensitive resin composition, 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, a column spacer, or a black matrix-integrated column spacer comprising a cured product of the black photosensitive resin composition described above.

The black photosensitive resin composition according to the present invention has an advantage of excellent production yield of a black matrix, a column spacer, or a black matrix integrated column spacer as the margins of the developing process and the exposure process are increased.

In the present invention, the black matrix-integrated column spacer does not mean that a black matrix and a column spacer are formed respectively, but a black matrix and a column spacer can serve as a single pattern.

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

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

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

d) performing a developing process by dissolving the unexposed part using an aqueous alkali solution; And

e) Drying and post-baking steps

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Moreover, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned as a polymer plate.

In this case, the coating may be performed by a wet coating method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet so as 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 heating time in the pre-baking are appropriately selected according to the solvent used, and are performed for 1 to 30 minutes at a temperature of, for example, 80 to 150°C.

Further, the exposure performed after prebaking is performed by an exposure machine and exposed through a photomask to cause only the portion corresponding to the pattern to be exposed. The light to be irradiated at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

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

The post-baking 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 and pre-baking, it is carried out using an oven, hot plate, or the like.

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

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art. In addition, "%" and "parts" indicating content hereinafter are based on weight unless otherwise noted.

Synthesis example : Synthesis of binder resin

A flask equipped with a stirrer, thermometer, reflux condenser, dropping lot, and nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9-yl (meth)acrylate in a molar ratio of 50:50 40 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared by adding. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to prepare stirring. Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Thereafter, dropping of the monomer and the chain transfer agent was started from the dropping lot. Dropping was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH/g.

Measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin was measured under the following conditions by the GPC method.

An HLC-8120GPC (manufactured by Tosoh Corporation) apparatus was used. The TSK-GELG4000HXL and TSK-GELG2000HXL columns were connected in series and used, and the temperature of the column was set to 40°C. Tetrahydrofuran was used as a mobile phase solvent, and it was measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 µl, and analyzed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Corporation) were used as standard materials for calibration, and the weight average molecular weight and number of alkali-soluble resins obtained under the above conditions The average molecular weight was measured.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Preparation of black photosensitive resin composition: Example 1 to 4 and Comparative example 1 to 4

A black photosensitive resin composition according to Examples and Comparative Examples was prepared with the composition and composition according to Table 1 below.

Configuration Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 coloring agent R194 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 B15:6 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 CB 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Binder resin B 8.27 8.27 8.27 8.27 8.27 8.27 8.27 8.27 Monomer M1 3.54 - - - - - - - M2 - 3.54 - - - - - - M3 - - 3.54 - - - - - M4 - - - 3.54 - - - - M5 - - - - 3.54 - - - M6 - - - - - 3.54 - - M7 - - - - - - 3.54 - M8 - - - - - - - 3.54 Photopolymerization initiator PI 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 additive D1 1.92 1.92 1.92 1.92 1.92 1.92 1.92 1.92 D2 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 solvent S1 3 3 3 3 3 3 3 3 S2 77 77 77 77 77 77 77 77 R194: Red Pigment 194 (Wonil Trade)
B15:6: Pigment Blue 15:6 (EP-193, manufactured by DIC)
CB: PBk7 (Carbon Black, MA-8, manufactured by Mitsubishi Corporation)
Binder Resin (B): Binder Resin according to Synthesis Example
Monomer (M1): Viscoat#802-A (8 functional, acid value 20, Osaka Organic Chemical)
Monomer (M2): Viscoat#802-B (8 functional, acid value 30, Osaka Organic Chemical)
Monomer (M3): Viscoat#802-C (8-functional, acid value 40, Osaka Organic Chemical)
Monomer (M4): Viscoat#802-D (8-functional, acid value 60, Osaka Organic Chemical)
Monomer (M5): Viscoat#802 (8 functional, acid value 0, Osaka Organic Chemical)
Monomer (M6): M520 (4-functional, acid value 30, Teagosei)
Monomer (M7): Viscoat#802-F (8 functional, acid value 80, Osaka Organic Chemical)
Monomer (M8): BTD-1006 (Dendric Acrylate, DYMAX)
Photopolymerization initiator (PI): 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime) (Irgacure OXE-02: Ciba four)
Additive 1 (D1): Solspurs 5000 (manufactured by Lubrisol)
Additive 2 (D2): DiperBYK-163 (manufactured by BYK)
Solvent 1 (S1): n-butanol
Solvent 2 (S2): Propylene glycol monomethyl ether acetate

Experimental example

(One) Fabrication of patterned substrate

A 5cm×5cm glass substrate (Corning) was washed with neutral detergent and water, and then dried. On the glass substrate, each of the black photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated to a final film thickness of 3.0 μm, pre-baked at 80 to 120°C, and dried for 1 to 2 minutes to remove the solvent. I did. Thereafter, a pattern was formed by exposure with an exposure amount of 40 to 100 mJ/cm ^2, and the non-exposed portion was removed using an aqueous alkali solution. Then, after firing at 200 to 250°C for 10 to 30 minutes, a patterned substrate was prepared.

(2) Exposure margin

Table 2 shows the margin results for three substrates (reference exposure amount, reference exposure amount -10mJ, reference exposure amount +10mJ) by manufacturing a substrate at -10mJ from the reference exposure amount and +10mJ from the reference exposure amount. By measuring and comparing the line widths of the patterns formed on the three substrates produced above, the results for the exposure margin among the process margins were confirmed.

The line width was evaluated after manufacturing the substrate using a line pattern mask. The evaluation was performed using SNU's SIS-2000, and pattern measurement was performed.

Therefore, among the process margins, the exposure margin was evaluated with the resultant value within the exposure range of 20mJ, and the evaluation result range is as follows.

Excellent ◎=±0.5 or less, good ○=±1.0 or less, insufficient △=±1.0 or less

(3) Development margin

The substrate was prepared by making the substrate 10 seconds shorter than the reference development time, and the substrate was manufactured by adding 10 seconds to the reference development time, and the characteristics of a total of three substrates were evaluated.

The line width of the formed pattern was measured, and the process margin (exposure margin) was measured, and the line width was evaluated after manufacturing the substrate using a line pattern mask. The evaluation was performed using SNU's SIS-2000, and pattern measurement was performed.

The development margin was evaluated using the numerical values in the 20sec development process, and the evaluation result range is as follows.

Excellent ◎=±1.0 or less, good ○=±1.5 or less, insufficient △=±1.5 or less

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Exposure margin ◎ ◎ ◎ ○ △ △ △ △ Developing margin ◎ ○ ○ ○ △ △ △ △

Referring to Table 2, the pattern substrate formed using the black photosensitive resin composition according to the present invention has excellent exposure margin or development margin, but the pattern substrate formed using the black photosensitive resin composition according to the comparative example has exposure margin and development margin. You can see that none of these are excellent.

Claims (8)

It contains a functional group of 8,
A monomer having an acid value of 20 to 40 mgKOH/g;
A binder resin containing a repeating unit derived from 3,4-epoxytricyclodecane-8-yl (meth)acrylate; And
A black photosensitive resin composition for a black matrix-integrated column spacer comprising a colorant comprising a blue pigment. The method of claim 1,
The monomer is a black photosensitive resin composition for a black matrix-integrated column spacer further comprising a hydroxyl group. The method of claim 1,
Black photosensitive resin composition for a black matrix-integrated column spacer, wherein the functional group contains an ethylenically unsaturated double bond. The method of claim 1,
The monomer is a black photosensitive resin composition for a black matrix-integrated column spacer contained in 1.7 to 4.2 parts by weight based on the total 100 parts by weight of the black photosensitive resin composition. The method of claim 1,
Black colorant; Photopolymerization initiator; A black photosensitive resin composition for a black matrix integrated column spacer further comprising at least one selected from the group consisting of a solvent and an additive. The method of claim 1,
The colorant is a black photosensitive resin composition for a black matrix-integrated column spacer further comprising at least one selected from the group consisting of red and black pigments. delete A black matrix-integrated column spacer comprising a cured product of the black photosensitive resin composition according to any one of claims 1 to 6.