JP7063614B2 - Black photosensitive resin composition, black matrix for image display device, column spacer and black matrix integrated column spacer manufactured from this. - Google Patents

Description

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

The black photosensitive resin composition is an essential material for color filters, liquid crystal display materials, organic light emitting elements, displays and the like. As an 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 to enhance display contrast and color development effect. Can be done.

Recently, techniques have been developed that allow a single material used inside a display to perform a variety of roles at the same time, which allows a black photosensitive resin composition to form a black matrix and cell gap maintenance on an array substrate. The role of forming a spacer is also required, and the demand for a black photosensitive resin composition is further increasing.

Republic of Korea Publication No. 2007-0094460 relates to a black photosensitive composition, which is a black photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator and a black pigment, and contains an organic pigment as a shape stabilizer. The contents relating to the black photosensitive composition are disclosed.

In addition, Republic of Korea Publication No. 2012-0033893 relates to a photosensitive resin composition, wherein (A) a binder resin; (B) a polyfunctional monomer; (C) a photopolymerization initiator or a photoreducer; (D) black. Pigments; and (E) the solvent are included, and the black pigment discloses the content relating to one or more photosensitive resin compositions selected from aniline black, perylene black, and metal oxide.

However, the black photosensitive resin composition of the above-mentioned document has a problem that the margin in the process is low due to the limit of the exposure transmittance due to the development of black color and the disadvantage to the developing process due to the limitation.

Therefore, the actual situation is that the development of a black photosensitive resin composition in which the production yield is improved by improving the margin in the process is required.

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

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

Another object of the present invention is to provide a black matrix, a column spacer or a black matrix integrated column spacer manufactured by using the above-mentioned black photosensitive resin composition.

The black photosensitive resin composition according to the present invention for achieving the above object is characterized by containing a monomer containing 5 to 12 functional groups and an acid value of 10 to 60 mgKOH / g;

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

The black photosensitive resin composition according to the present invention has an advantage that it is excellent in developability, reliability, or processability by containing a specific monomer, and can improve the process margin.

Further, the black matrix, the column spacer or the black matrix integrated column spacer manufactured by using the black photosensitive resin composition according to the present invention has an advantage that it is excellent in reliability and easy to manufacture.

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

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

In the present invention, when a component is referred to as "contains" a component, this means that the other component may be further included without excluding the other component unless otherwise specified. do.

<Black photosensitive resin composition>
The black photosensitive resin composition according to the present invention is characterized by containing 5 to 12 functional groups and a monomer having an acid value of 10 to 60 mgKOH / g;

Further, the black photosensitive resin composition according to the present invention may further contain one or more selected from the group consisting of a colorant containing a black pigment; a binder resin; a photopolymerization initiator; a solvent and an additive.

One aspect of the present invention relates to a black photosensitive resin composition containing a monomer containing 5 to 12 functional groups and an acid value of 10 to 60 mgKOH / g;

In the present invention, the "monomer" can be mixed with a "monomer" and can be distinguished from an "oligomer" and a "polymer".

The monomer according to the present invention contains 5 to 12 functional groups, preferably 5 to 9 functional groups, more preferably 6 to 8 functional groups, and the functional groups contain unsaturated groups. Alternatively, one having photosensitivity can be used.

When the monomer according to the present invention contains a functional group within the above range, it can have better sensitivity, so that the production of a black matrix, a column spacer or a black matrix integrated column spacer can be facilitated.

In one embodiment of the invention, the monomer may further contain a hydroxyl group. Although not bound by theory, if the monomer contains a hydroxyl group in the case of a colored photosensitive resin composition for producing a general color filter, it is advantageous for developability, but reliability and process. It can adversely affect the margin. However, when the monomer contained in the black photosensitive composition according to the present invention contains a hydroxyl group, it is characterized by being excellent in developability, reliability and processability. Specifically, when the monomer contains a hydroxyl group, there is an advantage that the degree of cross-linking is increased by the cross-linking reaction with the photoinitiator and the binder resin described later, so that the reliability can be excellent.

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 that the process margin can be increased. If the acid value of the monomer is less than the above range, there is a problem that the developability may be slightly lowered, and if it exceeds the above range, the acid value in the monomer becomes excessively high, so that a margin in the process is obtained. Since there is a problem that there is a possibility that the amount of the substance may decrease, it is preferable that the substance is contained within the above range.

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

In yet another embodiment of the invention, the functional group may contain an ethylenically unsaturated double bond. When the functional group contains the ethylenically unsaturated double bond, it reacts with a photopolymerizable alkaline resin described later to increase the degree of cross-linking, which has an advantage of being easy to handle in the process.

In still another embodiment of the invention, the monomer is 1.7 to 4.2 parts by weight, preferably 1.8 to 4.0 parts by weight, based on 100 parts by weight of the entire black photosensitive resin composition. It may preferably be contained in an amount of 2.0 to 3.8 parts by weight.

When the monomer is contained within the above range, it is excellent in developability, reliability or processability, and therefore, there is an advantage that a black photosensitive resin composition having an excellent process margin can be provided. If the monomer is contained in the range below the range, it may be difficult to form a pattern because the developability may be slightly lowered, and if the monomer is contained in the range, the margin values of the developability and the processability are slightly lowered. Since there is a possibility, it is preferable that it is included so as to satisfy the above range.

The monomer may be directly synthesized and used, or a commercially available product may be purchased and used. Examples of the commercially available monomers include, but are not limited to, Viscoat # 802-A, Viscoat # 802-B, Viscoat # 802-C, Viscoat # 802-D of Osaka Organic Chemistry, and the present invention. Those satisfying the above-mentioned monomers can be used.

In yet another embodiment of the invention, the black photosensitive resin composition may further comprise one or more selected from the group consisting of black colorants; binder resins; photopolymerization initiators; solvents and additives. ..

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

Yet another embodiment of the invention relates to a black photosensitive resin composition comprising one or more of the colorants selected from the group consisting of red, blue and black pigments.

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

As carbon black that can be used, CHBK-17 of Gokoku Dye Co., Ltd .; Seest 5HIISAF-HS, Seest KH, Seest 3HHAF-HS, Seest NH, Seest 3M, Seest 300HAF-LS, Seest 116HMMAF-HS of Tokai Carbon Co., Ltd. , Seest 116MAF, Seest FMFEF-HS, Seest SOFEF, Seest VGPF, Seest SVHSRF-HS, and Seest SSRF; , 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; PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRITEX-140V, PRITEX-95, PRITEX-85, PRITEX-75, PRITEX-55, PRITEX-45, PRITEX-300, PRODUCTX- of degusa Co., Ltd. 35, PRITEX-25, PRITEX-200, PRITEX-40, PRITEX-30, PRITEX-3, PRITEX-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 of Columbia Carbon Co., Ltd. 860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RA VEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN- Included are 1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 and the like.

The carbon black is not particularly limited as long as it is a pigment having a light-shielding property, and a known carbon black can be used. Specific examples of the carbon black, which is the black pigment, include channel black, furnace black, thermal black, and lamp black.

Further, as the carbon black which is the black pigment, carbon black coated with a resin can also be used. Since the carbon black coated with the resin has lower conductivity than the carbon black not coated with the resin, excellent electrical insulation can be imparted when the black matrix or the black column spacer is formed.

The colorant may further include one or more selected from the group consisting of organic pigments and dyes. Specifically, the colorant may contain one or more organic pigments and dyes having a light-shielding property in visible light.

The organic pigment is, for example, a compound classified as a pigment by a color index (CI; The Society of Dyers and Colorists), specifically, a color index (CI) name as described below. Can be mentioned, but is not limited to this.

Specifically, the organic pigment is C.I. I. Pigment Yellow No. 1, C.I. I. Pigment Yellow No. 12, C.I. I. Pigment Yellow No. 13, C.I. I. Pigment Yellow No. 14, C.I. I. Pigment Yellow No. 15, C.I. I. Pigment Yellow No. 16, C.I. I. Pigment Yellow No. 17, C.I. I. Pigment Yellow No. 20, C.I. I. Pigment Yellow No. 24, C.I. I. Pigment Yellow No. 31, C.I. I. Pigment Yellow No. 53, C.I. I. Pigment Yellow No. 55, C.I. I. Pigment Yellow No. 83, C.I. I. Pigment Yellow No. 86, C.I. I. Pigment Yellow No. 93, C.I. I. Pigment Yellow No. 94, C.I. I. Pigment Yellow No. 109, C.I. I. Pigment Yellow No. 110, C.I. I. Pigment Yellow No. 117, C.I. I. Pigment Yellow No. 125, C.I. I. Pigment Yellow No. 128, C.I. I. Pigment Yellow No. 137, C.I. I. Pigment Yellow No. 138, C.I. I. Pigment Yellow No. 139, C.I. I. Pigment Yellow No. 147, C.I. I. Pigment Yellow No. 148, C.I. I. Pigment Yellow No. 150, C.I. I. Pigment Yellow No. 153, C.I. I. Pigment Yellow No. 154, C.I. I. Pigment Yellow No. 155, C.I. I. Pigment Yellow No. 166, C.I. I. Pigment Yellow No. 168, C.I. I. Pigment Yellow No. 173, C.I. I. Pigment Yellow No. 180, C.I. I. Pigment Yellow No. 211;
C. I. Pigment Orange No. 5, C.I. I. Pigment Orange No. 13, C.I. I. Pigment Orange No. 14, C.I. I. Pigment Orange No. 24, C.I. I. Pigment Orange No. 31, C.I. I. Pigment Orange No. 34, C.I. I. Pigment Orange No. 36, C.I. I. Pigment Orange No. 38, C.I. I. Pigment Orange No. 40, C.I. I. Pigment Orange No. 42, C.I. I. Pigment Orange No. 43, C.I. I. Pigment Orange No. 46, C.I. I. Pigment Orange No. 49, C.I. I. Pigment Orange No. 51, C.I. I. Pigment Orange No. 55, C.I. I. Pigment Orange No. 59, C.I. I. Pigment Orange No. 61, C.I. I. Pigment Orange No. 64, C.I. I. Pigment Orange No. 65, C.I. I. Pigment Orange No. 68, C.I. I. Pigment Orange No. 70, C.I. I. Pigment Orange No. 71, C.I. I. Pigment Orange No. 72, C.I. I. Pigment Orange No. 73, C.I. I. Pigment orange No. 74;
C. I. Pigment Red No. 1, C.I. I. Pigment Red No. 2, C.I. I. Pigment Red No. 5, C.I. I. Pigment Red No. 9, C.I. I. Pigment Red No. 17, C.I. I. Pigment Red No. 31, C.I. I. Pigment Red No. 32, C.I. I. Pigment Red No. 41, C.I. I. Pigment Red No. 97, C.I. I. Pigment Red No. 105, C.I. I. Pigment Red No. 122, C.I. I. Pigment Red No. 123, C.I. I. Pigment Red No. 144, C.I. I. Pigment Red No. 149, C.I. I. Pigment Red No. 166, C.I. I. Pigment Red No. 168, C.I. I. Pigment Red No. 170, C.I. I. Pigment Red No. 171 and C.I. I. Pigment Red No. 175, C.I. I. Pigment Red No. 176, C.I. I. Pigment Red No. 177, C.I. I. Pigment Red No. 178, C.I. I. Pigment Red No. 179, C.I. I. Pigment Red No. 180, C.I. I. Pigment Red No. 185, C.I. I. Pigment Red No. 192, C.I. I. Pigment Red No. 194, C.I. I. Pigment Red No. 202, C.I. I. Pigment Red No. 206, C.I. I. Pigment Red No. 207, C.I. I. Pigment Red No. 208, C.I. I. Pigment Red No. 209, C.I. I. Pigment Red No. 214, C.I. I. Pigment Red No. 215, C.I. I. Pigment Red No. 216, C.I. I. Pigment Red No. 220, C.I. I. Pigment Red No. 221 and C.I. I. Pigment Red No. 224, C.I. I. Pigment Red No. 242, C.I. I. Pigment Red No. 243, C.I. I. Pigment Red No. 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red No. 262, C.I. I. Pigment Red No. 264, C.I. I. Pigment Red No. 265, C.I. I. Pigment Red No. 272;
C. I. Pigment Blue No. 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue No. 16, C.I. I. Pigment Blue No. 60, C.I. I. Pigment blue No. 80;
C. I. Pigment Purple No. 1, C.I. I. Pigment Purple No. 19, C.I. I. Pigment Purple No. 23, C.I. I Pigment Purple No. 29, C.I. I Pigment Purple No. 32, C.I. I Pigment Purple No. 36, C.I. I Pigment Purple No. 38;
C. I. Pigment Green No. 7, C.I. I. Pigment Green No. 36, C.I. I. Pigment Green No. 58, C.I. I. Pigment Green No. 59, C.I. I. Pigment Green No. 62, C.I. I. Pigment green No. 63;
C. I. Pigment Brown No. 23, C.I. I. Pigment brown No. 25;
C. I. Pigment Black No. 1, C.I. I. Pigment Black No. 7 or the like can be used, and in some cases, rosin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced, surface graft treatment using a polymer compound, etc., and sulfuric acid are used. It may have been subjected to a fine particle treatment, a cleaning treatment using an organic solvent or water, or the like.

In addition to this, pigments used in printing inks, inkjets, etc. and water-soluble azo-based, insoluble azo-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, isoindoline, perylene, perinone, dioxydine, anthraquinone, dianthraquinonyl, Anthraquinone, anthrantron, indantron, flavantron, pyranthron-based pigments, etc. can also be used, but are not limited to this.

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

In still another embodiment of the present invention, the black photosensitive resin composition according to the present invention is selected from the group consisting of red, blue and black among the above-mentioned colorants in order to facilitate the realization of black color1. Contains the above colorants.

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

When the colorant further contains a blue pigment, there is an advantage that the effect on the exposure process can be excellent as the transmittance in the near infrared region becomes excellent, and the reliability can be excellent due to the improvement of the chemical resistance to the organic solvent. ..

The colorant according to the present invention is contained, for example, in an amount of 25 to 55 parts by weight, preferably 27 to 40 parts by weight, and more preferably 28 to 33 parts by weight with respect to 100 parts by weight of the total solid content of the black photosensitive resin composition. However, it is not limited to this. If the content of the colorant is less than the above range, the optical density (OD) may be slightly low, and if it exceeds the above range, the relative permittivity may be slightly high, which causes a problem in driving the display device. Is likely to occur to some extent, and therefore, it is preferably contained within the above range.

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

The black photosensitive resin composition according to the present invention contains a binder resin. The binder resin makes the non-exposed portion of the black photosensitive resin layer, which is usually formed by using the black photosensitive resin composition, alkaline-soluble, and acts as a dispersion medium for the pigment. The binder resin is not particularly limited in the present invention, and can be selected from various polymers used in the art of application.

The weight average molecular weight of the binder resin is preferably 3000 to 30,000, more preferably 5000 to 20000, and the acid value of the binder resin has a range of 50 to 200 mgKOH / g on a solid content basis. Is preferable.

When the acid value satisfies the above range, the developability for alkaline development is excellent, the generation of residues can be suppressed, and the adhesion of the pattern can be improved, which is preferable.

The binder resin may be contained 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 non-pixel portion is difficult to generate a residue on the substrate because the solubility in the developing solution is sufficient, and the film reduction of the pixel portion of the exposed portion is unlikely to occur during development. Therefore, the non-pixel portion tends to have good dropout.

As the photopolymerization initiator contained in the present invention, those generally used for photosensitive resin compositions can be applied, for example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, non-imidazole-based. System compounds can be used.

The acetophenone compounds are diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-. Methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-) Morphorinophenyl) butane-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one oligomers, etc. are possible, of which 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butane-1-one is preferably used.

Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino). Benzophenone etc. are possible.

Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3', 4 "-dimethoxystyryl) -4. , 6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like are possible.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, and Ciba's OXE-01 and OXE-02 are typical commercially available products.

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.

Examples of the biimidazole compound 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) biimidazole, 2,2'-bis (2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5 "-tetra (trialkoxyphenyl) biimidazole, imidazole compounds in which the phenyl group at the 4,4', 5,5" position is replaced by a carboalkoxy group, etc. It is possible.

The photopolymerization initiator can 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. Such a content range takes into consideration the photopolymerization rate of the monomer and the physical properties of the finally obtained coating film, and if it is less than the above range, the polymerization rate is low and the entire process time may be long. On the contrary, when the above range is exceeded, the cross-linking reaction may be excessively generated due to the excessive reaction and the physical properties of the coating film may be deteriorated. Therefore, it is preferable to use the coating appropriately within the above range.

Further, a photopolymerization initiator can be used together with the photopolymerization initiator, but when the photopolymerization initiator is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and the productivity is improved. It is preferable to do so. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amines and carboxylic acid compounds can be preferably used.

Such a photopolymerization initiator is preferably used in an amount of usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When a photopolymerization initiation aid is used within the above range, the polymerization efficiency can be increased and the effect of improving productivity can be expected.

Although the solvent has compatibility with each of the above-mentioned configurations, it can be used without limitation as long as it does not react. Various commonly used organic solvents can be used, and the solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coatability and drying property.

For example, examples of the solvent include esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate and propylene glycol monoethyl. Examples thereof include ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like. Each of these solvents can be used alone or in admixture of two or more.

The content of the solvent in the black photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, and 65 to 85 parts by weight, based on 100 parts by weight of the entire black photosensitive resin composition. Is more preferable. When the content of the solvent is within the above range, the coatability may be good when applied by 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. ..

The black photosensitive resin composition according to the present invention may further contain additives commonly used in the art for enhancing dispersibility, coating properties, adhesion and the like.

As the dispersant, for example, an appropriate dispersant such as a cationic system, an anionic system, or a nonionic system can be used, but a polymer dispersant is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines and polyallylamines. Such dispersants are commercially available, for example, as acrylic copolymers such as DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (all manufactured by Big Chemie (BYK)). Solsperse 5000 (manufactured by Lubrizol), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-170, DisperBYK-182 (manufactured by SpperBYK-172) Examples thereof include 76500 (manufactured by Lubrizol), Solsperse 24000 (manufactured by Lubrizol) as polyethyleneimin, and Ajispo PB821, Ajispo PB822, and Ajispo PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as polyesters.

Further, the additive is, for example, a silane coupling agent having a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, and a reactive substituent selected from the group consisting of a combination thereof in order to enhance the adhesiveness to the substrate. Can include, but is not limited to. Specifically, the silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyl. Examples thereof include trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, which can be used alone or in combination of two or more, but are not limited thereto.

Further surfactants can be added to improve the coating property. For example, fluorine-based surfactants such as M-1000, BM-1100 (BM Chemie), and Florard FC-135 / FC-170C / FC-430 (Sumitomo 3M Ltd.) can be used. Without limitation, surfactants commonly used in the industry can be used.

In the present invention, the content of the additive is not limited, and it can be appropriately added and used as long as the object of the present invention is not impaired. For example, the additive may be contained 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 entire 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 containing a cured product of the black photosensitive resin composition described above.

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

In the present invention, the black matrix integrated column spacer means one that can perform both the roles of the black matrix and the column spacer in one pattern, instead of forming the black matrix and the column spacer respectively.

The introduction of the black matrix, column spacer or black matrix integrated column spacer can 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, the following steps can be included:
a) The stage of applying the black photosensitive resin composition to the substrate;
b) Pre-baking stage to dry the solvent;
c) A step of applying a photomask on the obtained film and irradiating it with active light to cure the exposed part;
d) The step of dissolving the unexposed part using an alkaline aqueous solution to carry out the developing step; and e) the step of carrying out the drying and post-baking.

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium-borosilicate glass, quartz and the like can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.

At this time, the coating can be carried out 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 that a desired thickness can be obtained. ..

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 prebake are appropriately selected depending on the solvent used, and are performed at a temperature of 80 to 150 ° C. for 1 to 30 minutes, for example.

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

Alkaline development after exposure This is performed for the purpose of removing the photosensitive resin composition of the unexposed portion of the unexposed portion, and the desired pattern is formed by this development. As a developing solution suitable for this alkaline development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used.

The post-baking is carried out in order to enhance the adhesion between the patterned film and the substrate, and is carried out through heat treatment at 80 to 220 ° C. for 10 to 120 minutes. Like pre-baking, post-baking is also performed using an oven, hot plate, etc.

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. Is.

Hereinafter, in order to specifically explain the present specification, examples will be given and described in detail. However, the embodiments according to the present specification can be transformed into various different forms, and the scope of the present specification is not construed to be limited to the examples detailed below. The examples herein are provided to provide a more complete description of the specification to those with average knowledge in the art. In addition, "%" and "part" indicating the content below are based on weight unless otherwise specified.

Synthesis example: Synthesis of binder resin A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was prepared. As a monomer dropping funnel, 40 weights of 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. 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). Was added to prepare stirring. As a chain transfer agent dropping tank, 6 parts by weight of n-todecanethiol and 24 parts by weight of PGMEA were added to prepare stirring. Then, 395 parts by weight of PGMEA was added to the flask to change the atmosphere in the flask from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. by stirring. Then, the monomer and the chain transfer agent were dropped from the dropping funnel. The 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.

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

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

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

Production of Black Photosensitive Resin Compositions: Examples 1 to 4 and Comparative Examples 1 to 4
The black photosensitive resin compositions according to Examples and Comparative Examples were produced with the configurations and compositions shown in Table 1 below.

Experimental example

(1) Production of Pattern Substrate A 5 cm × 5 cm glass substrate (Corning Inc.) was washed with a neutral detergent and water, and then dried. The black photosensitive resin compositions produced in the Examples and Comparative Examples were spin-coated on the glass substrate so as to have a final film thickness of 3.0 μm, and pre-baked at 80 to 120 ° C. to 1 to 2 The solvent was removed by drying for a minute. Then, it was exposed at an exposure amount of 40 to 100 mJ / cm ² to form a pattern, and the unexposed portion was removed using an alkaline aqueous solution. Subsequently, the pattern substrate was manufactured by firing at 200 to 250 ° C. for 10 to 30 minutes.

(2) Exposure Margin A substrate is manufactured by -10 mJ from the standard exposure amount, and a substrate is manufactured by +10 mJ from the standard exposure amount, and three types of substrates (standard exposure amount, standard exposure amount -10 mJ, standard exposure amount + 10 mJ) are used. The margin results of are shown in Table 2. The line widths of the patterns formed on the three types of substrates manufactured above were measured and compared to confirm the results for the exposure margin during the process margin.

The line width was evaluated after the substrate was manufactured using a line pattern mask. For the evaluation, pattern measurement was advanced using SIS-2000 manufactured by SNU.

Therefore, among the process margins, the exposure margin is evaluated using the numerical value on the result within the exposure range of 20 mJ, and the result of the evaluation, the range is as follows.

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

(3) Development Margin A substrate was manufactured 10 seconds shorter than the standard development time, and a substrate was manufactured 10 seconds longer than the standard development time, and the characteristics of a total of three types of substrates were evaluated.

The line width of the formed pattern was measured, the process margin (exposure margin) was measured, and the line width was evaluated after the substrate was manufactured using the line pattern mask. For the evaluation, pattern measurement was advanced using SIS-2000 manufactured by SNU.

The development margin is evaluated using the numerical value on the result in the 20 sec development process, and the range as a result of the evaluation is as follows.

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

Referring to Table 2, the pattern substrate formed by using the black photosensitive resin composition according to the present invention has an excellent exposure margin or development margin, but the black photosensitive resin composition according to the comparative example is used. It can be seen that the pattern substrate formed in the above-mentioned manner does not have excellent exposure margin and development margin.

Claims (9)

Contains 8 functional groups
Monomers with an acid value of 10-60 mgKOH / g; and
Contains binder resin,
The binder resin comprises a repeating unit of 3,4-epoxytricyclodecane-8-yl (meth) acrylate and derived from 3,4-epoxytricyclodecane-9-yl (meth) acrylate , which is black photosensitive. Sex resin composition. The black photosensitive resin composition according to claim 1, wherein the monomer further contains a hydroxyl group. The black photosensitive resin composition according to claim 1, wherein the monomer has an acid value of 20 to 40 mgKOH / g. The black photosensitive resin composition according to claim 1, wherein the functional group contains an ethylenically unsaturated double bond. The black photosensitive resin composition according to claim 1, wherein the monomer is contained in an amount of 1.7 to 4.2 parts by weight with respect to 100 parts by weight of the entire black photosensitive resin composition. The black photosensitive resin composition according to claim 1, further comprising one or more selected from the group consisting of a black colorant; a photopolymerization initiator; a solvent and an additive. The black photosensitive resin composition according to claim 6, further comprising one or more selected from the group consisting of a red pigment and a blue pigment. The black photosensitive resin composition according to claim 7, which comprises the blue pigment. A black matrix, a column spacer, or a black matrix integrated column spacer containing a cured product of the black photosensitive resin composition according to any one of claims 1 to 8.