TW200912526A - Photo-sensitive resin composition for black resist and light-shielding film and color filter using the same - Google Patents

Abstract

Provided is a photo-sensitive resin composition for black resist capable of forming a pattern with excellent pattern dimension stability, pattern adhesiveness and sharpness in edge even in a case of large thickness, without resulting deterioration of surface roughness due to thermal-curing shrinkage in thermal calcination process, and without reduced volume resistance even using conductive materials such as carbon as light-shielding material. The photo-sensitive resin composition for black resist of the present invention contains (a) photo-curing resin and/or photo-curing monomer, (b) at least one light-shielding pigment selected from black organic pigment, mixed color organic pigment and light-shielding material, and (c) granular silica, wherein the averaged primary particle diameter of the granular silica of component (c) is 10 to 50nm, and the ratio of the averaged primary particle diameter of the granular silica (c) to the light-shielding pigment (b) ((c)/(b)) is 0.1 to 1.0.

Description

In the invention, the present invention relates to a photosensitive resin composition for a photosensitive resist aqueous solution development type black resist, and a light-shielding film formed using the composition of the sensor. In order to collect the color n, in particular, there is a photosensitive resin composition for a black resist which forms a fine light-shielding film on the plate, and a light-shielding film and a color filter. [Prior Art] The color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially forms three or more different hue of red, green, and blue into stripes or mosaics (mosaic). ) The color pattern of the shape. The size of the pattern varies with the purpose of the color filter and the color, and is about 5 to 7 〇 0 #m. At the same time, the positional accuracy of the overlap is several to several tens of meters, and is manufactured by a microfabrication technique with high dimensional accuracy. Representative production methods of the color filter include a dyeing method, a printing method dispersion method, and an electrodeposition method. Among them, a pigment 77 φ which is formed by coating a photopolymerizable composition containing a color material on a transparent substrate and forming a color filter image by repeating an image exposure method and hardening according to demand The precision of the position and film thickness of the filter, the color of the pigment, etc. is still: The durability such as heat is excellent, and the defects such as pinholes are few. Therefore, the black matrix of the color of the bran which is widely used is generally arranged in a grid shape in red, green, and . , striped or mosaic, 圩 achieve color mixing between the colors to improve the contrast effect, or to prevent the effect of TFT failure caused by & light. Therefore, the black matrix is required to be high, and the formation of a black matrix by using a metal film such as chrome is a commonly used method. 32〇2°5 200912526 The method is to deposit a metal such as chromium on a transparent substrate and pass a photolithography process. Since the chrome layer is etched, a thin film thickness and high high-definition light-shielding property can be obtained. On the contrary, since it is a long manufacturing process and a productive (four) method, there are problems such as high cost, waste liquid, etc., which cause environmental problems and the like. Here, in order to solve such a problem, in the patent document i, a photolithography method H containing a photosensitive resin is proposed. The resin light-shielding film obtained by this method is blackened by a metal film such as chromium. The substrate has the same light-shielding property (optical density), and the content of the matte pigment or the like must be increased. However, when the light-shielding ability is required in the full-wavelength region of the light as in the case of the resin black matrix, the light-hardening is performed on the riding purple light (four). Miscellaneous towels, because the light-shielding pigment will absorb the material, and there will be a lower material: the exposed portion will also produce a difference in cross-link density in the film thickness direction, even in the film table = light hardening, the base wire is still It is not easy to harden the light; 2) it is obvious that the difference between the exposed portion and the unexposed portion is different; 3) because the image is mixed with the light-insoluble pigment, which is insoluble in the coating, which significantly reduces the imaging properties, etc. ^ There is still a problem in the characteristics of light sensitivity, resolution, adhesion, imaging, and sharpness of the edge of the black resist, and it is necessary to develop a light-shielding property = or with a close pattern (in pattern) The edge shape is clear black in recent years, in order to reach Gaoming color, high-definition, color filter equipment left:: Resin black matrix is based on the use of film thickness of about 1 / / m film is required to be higher than the previous shading, but also more than more than / / m Film thickness resin black matrix. 320205 4 200912526 In addition, recently, a flat panel incorporating the "color filter on array" technology has attracted attention. This technology integrates the color filter substrate and the TFT array substrate, and does not require precise positional matching of the two substrates, so that the red, blue, and green elements of the color filter can be miniaturized to the limit. Therefore, the high definition of the flat panel can be achieved. Such a resin color black matrix for a color filter array requires a high light-shielding property, and therefore requires a film thickness of 2 // m or more. However, as the film thickness of the resin black matrix increases, the difference in the crosslinking density in the film thickness direction of the exposed portion (4) is enlarged, so (4) it is more difficult to achieve a black pattern which is more sensitive to the south and more difficult to obtain a good shape. Furthermore, in the subsequent hot calcination, the crosslink density in the film thickness direction of the exposed portion is different because of the difference, so the thermal hardening shrinkage of the surface of the coating film and the substrate is generated. Roughness, surface roughness will deteriorate and wrinkles will appear on the surface. After m and green, the formation of each element will be changed. The condition of the wire and the hot calcination can prevent the surface from increasing, but the pattern characteristics and reliability. It is not good. (4) (9) The increase in the amount of miscellaneous impurities is reported in Patent Document 2, and the reaction of the specific: acrylic acid is further reacted with the polybasic (four) or hydrazine to the compound containing the unsaturated group to obtain the main component of the resin. Resist system; =: a compound of a saturated base is easy to form a fine pattern, and, two: two light, can be used: a light-shielding thinness that is excellent in stability and stability, and a: ", and the patent document 2 also has black Based on: things. However, 320205 5 200912526: The use of black resists in thin enamel 'but if it exceeds ·, and related light hardenability, imaging characteristics. , factory--, thick film as a feature; the case of the color-receiver-related material is shown in the 3 to 5, etc. in the patent text is about the content of the patent document 3, not only the content of the method, the hot calcination step The color filter under the printing method forms the same color A. Regarding the resin black matrix, it is related to the formation method of red, blue, and green ochre soil. The method of specializing in thick film is not the same as „ 糸 4 The characteristics of the light-shielding property of the back surface are not sufficient, and the second one is ΓίΓ光, so there is still a problem in terms of productivity and yield. Patent Document 5 is a content of a protective film for a color filter. Preventing the surface roughness after hot forging is large - = The heat-hardening shrinkage is small, and the adhesive resin is added: the method of sub-two-two, photohardenability, image-forming properties, image, etc. Because the image margin is sufficiently wide to get the tree (the shape of the pattern, and the surface roughness of the coating film does not increase is the weight 2 (= _, in the thick _ fat black base f In the case of very difficult: both are established, so in the pigment dispersion method, the black matrix film is thick, and the related report of the light-shielding film formed by the use of the black matrix film In the past, the method of high light-shielding has been tried, and when a large amount of light-shielding material is used as a light-shielding material, the volume resistance of the black base is lowered, and a display device or the like is used. [Patent Document 1] Japanese Patent Laid-Open No. Hei 8-278629 (Patent Document 1) Japanese Patent Laid-Open No. Hei 8-278629 (Patent Document 1) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 5-181000 [Patent Document 1] Japanese Patent Application Laid-Open No. Hei No. 5-288926 (Claim of the Invention) (Problems to be Solved by the Invention) The present invention is directed to a precursor resin composition for a black resist agent, which solves the above problems even if When the thickness of the crucible exceeds 15 or 2, the dimensional stability of the pattern is also excellent, and the image margin and the sharpness of the edge shape of the pattern of the water are formed, and in the subsequent calcination step. The surface of the coating film is also smooth and does not deteriorate in surface roughness due to thermal curing shrinkage. Even when a conductive material such as carbon is used as the light shielding material, the volume resistance does not decrease. Further, the object of the present invention is to provide use. The black resist is a light-shielding enamel and a color filter formed by using a sensible resin composition. (The means for solving the problem) That is, the present invention provides a photosensitive resin composition for a black resist, which contains (a a photocurable resin and/or a photocurable monomer, wherein: a light-blocking pigment selected from at least one of a black organic pigment, a mixed color organic pigment, and a light-shielding material, and ((a granular cerium oxide; Special The average particle size of the granular cerium oxide of (4) is -% and the average particle size of the opaque pigment (b) and the particulate SiO2 (4) is 320205 7 200912526. The ratio of the ratio ((c)/(b)) to the value ((c)/(b)) is in the range of 0.2 to 5.0, and the weight of the particulate cerium oxide (c) and the light-shielding pigment (b) Further, the present invention provides a light-shielding film which is coated on a transparent substrate by the above-mentioned photosensitive resin composition, and dried (I) by an ultraviolet exposure apparatus. The light-shielding film obtained by exposure, (11) development by alkaline water-soluble two, and (III) heat treatment is characterized by a taper angle of 60. the above. Furthermore, the present invention provides a color filter suitable as a color filter of an inkjet process, wherein a light-shielding partition as a black matrix is composed of the above-described light-shielding film, and The film thickness is 15 to 4 " m. (Effects of the Invention) The photosensitive tree composition for a black resist of the present invention, for example, even when a black matrix having a film thickness of more than 1.5/zm is obtained, the pattern size stability is excellent. A pattern having a sufficient margin of image development, pattern adhesion, and a sharp edge shape of the pattern is formed. Further, in the subsequent calcination step, the surface of the coating film is smooth and the surface roughness is not deteriorated by the thermosetting shrinkage, and even when a carbon 4 conductive material is used as the light shielding material, the volume resistance can be lowered. Try to reduce as much as possible. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention contains (a) component i(c) as an essential component. Here, the photocurable resin of the component (a) is preferably a compound containing an unsaturated group as described below. That is, for the epoxidized oxime having two glycidyl groups derived from bisphenols 320205 200912526, (mercapto)acrylic acid (this means "acrylic acid and/or methacrylic acid" The reaction is carried out to obtain a compound which has been recorded, and the compound having a (4) group is reacted with a polybasic citric acid or an anhydride thereof (methyl sulphuric acid hydrate adduct. Here, the epoxy derived from the double sided layer) The term "compound" means an epoxy compound obtained by reacting double lysine with epoxy = epihdohydrin. The ring = compound and the unsaturated oxygen-containing compound (methyl) which is touched by the epoxy compound. The acryl-adducts are based on the aforementioned Patent Document 2 and the like, and Ma Baizhi 'is widely used. Sexuality is not described in the case where the photocurable resin of the component (8) has a vinyl compound possessing a bond and a wire, so that the black resistance _ photosensitive tree wax can be made into a special cleavage property and good development. And improve the physical properties of the given pattern. The graded resin of the component (8) is preferably a gasified compound derived from the epoxy compound represented by the formula (1). This ring can be derived from the duality of the people. Therefore, by explaining the double-seeking class, there are two compounds having an unsaturated group, so a preferred specific example is used by

Cf>CH, CtU〇. r Ri

u h %

〇Cfi,-Cfl-CB«〇 U OH

Ri (1) (wherein, and the Han 2 series each independently represent a hydrogen atom, a carbon number i to 320205 9 200912526 , a burnt group, a phenyl group or a halogen atom, and X represents -CO-, -S 〇2-, . -C(CF3)2-, -Si(CH3)2-, -CH2_, -C(CH3)2-,-0-, 9,9-fluorenyl, or not presence,

η is an integer from 0 to 10). The bisphenol which can impart a preferred compound containing an unsaturated group can be exemplified as follows. For example, it contains bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimercaptophenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, Bis(4-octylphenyl), bis(4-lightyl-3,5-dimethylphenyl), bis(4-lightyl-3,5-dichlorophenyl)sulfone, bis ( 4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, double (4-hydroxyphenyl)didecyldecane, bis(4-hydroxy-3,5-diamidinophenyl)dimethylnonane, bis(4-hydroxy-3,5-dichlorophenyl)difluorene Base decane, bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3,5-didecylphenyl)decane, bis(4-hydroxy-3,5-dichlorophenyl)decane , 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4.hydroxy-3,5-dianonylphenyl)propane, 2,2-bis(4-hydroxy-3,5 -dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-ylmercaptophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyl a compound such as phenyl)ether, bis(4-hydroxy-3,5-dimercaptophenyl)ether or bis(4-hydroxy-3,5-dichlorophenyl)ether, or X is the aforementioned 9, 9-mercapto 9,9-bis (4-hydroxyl Phenyl) 9,9,9-bis(4-hydroxy-3-indolylphenyl), 9,9-bis(4-hydroxy-3-chlorophenyl), 9,9·bis (4- Hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3-methyl 10 320205 200912526 oxyphenyl)anthracene, 9,9-bis (4-menu, hydroxy-3,5-diphenyl), 9,9t., :methylphenyl), 9,9-bis (4_ • or 4, 4, - Photo-curing property of the component (8), (i), (i), (4, 4, -biphen〇1), 3, 1, 3, 5-diylphenyl), etc. Obtained from the compound, but in the epoxidation of the double ray = raw epoxy novolac) epoxy compound or phenolic phenolic varnish (phenol can be meaningfully included with 2: Junqing lacquer epoxy compound, etc. In addition, when the compound of the double glycerin, that is, the polymer unit, is to be entangled in the water, the average value of the range of 0 to 2 is 0 to 1 〇 ( In addition, there is no problem with the performance such as *11. The epoxy f-methyl, *% oxygen compound and (mercapto)acrylic acid or acid acid thereof are obtained. The basic reaction of the polybasic reaction can be exemplified by: maleic acid, succinic acid, itaconic acid, tetra: phthalic acid: formic acid, hexanitrobenzene, methyl endomethylene acid, Stupid three f _ = (chlG1: endie Aeid), methyltetrahydrobenzene diphenyl 1 tetracarboxylic acid, such acid anhydride, material, such as tacrotic acid or its acid bis-acid, bis (tetra) W acid The family of diversified families chooses the appropriate person's funeral, ..., and the 'relevant ratio of acid or acid dianhydride' rate. 0 is formed by exposure, alkaline imaging operation The ratio of the pattern may be as follows: a photocurable resin of the component (a2) may be a mixture of only one of the 'anti-reservoirs of the acrylic acid. In addition, the epoxy compound and the (indenyl) polybasic acid or retanning compound ^ Further, the reaction of the epoxy (meth) acrylate obtained by the reaction with the mono- phthalic anhydride is carried out by the method of the above-mentioned Patent Document 2, which is known from the above-mentioned Patent Publication No. 320205 11 200912526, but is not particularly limited.

I. Since the component (a) in the present invention is hardened (polymerized) by light, when the photosensitive resin composition is in an uncured state, it includes only an unresinized component ( The case of monomer). In other words, the photocurable monomer used as the (&) component is a polymerizable monomer having at least one ethylenically unsaturated bond, and examples thereof include (meth)acrylic acid 2_light. a monomer having a hydroxyl group such as ethyl ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl acrylate (hydroxy) acrylate, or ethylene glycol di(meth)acrylate, diethylene glycol-one (Methyl)propionic acid S, diethyl-alcohol 'mono(indenyl)propionate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(methyl) Acrylic vinegar, trimethylolpropane tri(decyl) acrylate, trishydroxy ethane tri(meth) acrylate, pentaerythritol di(decyl) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol IV (meth) acrylates such as (meth) acrylate, dipentaerythritol tetrakis(meth) acrylate, dipentaerythritol 'hexa(methyl) acrylate, glycerol (meth) acrylate, etc. These compounds may be used alone or in combination of two or more. The photosensitive resin composition for a black resist of the present invention contains a photopolymerizable compound of the component (a), but it is preferred to contain a photopolymerization initiator in order to cure the light. The photopolymerization initiator generates a free radical by irradiation with ultraviolet light, and is added to a photopolymerizable compound to initiate radical polymerization to harden the resin composition. The photopolymerization initiator may, for example, be benzophenone, Michler's ketone, hydrazine, Ν'_tetradecyl-4,4'-diaminodibenzophenone, 4-decyloxy group. -4,-dimethylaminobiphenyl, 4,4,-diethylaminodiphenyl hydrazine 12 320205 200912526 ketone, 2-ethyl hydrazine, phenanthrene quinone

Pt Temple Fangxiangzu _; benzoin 曱 gene ethyl ether, benzoin phenyl _ and other benzoin oxime; A 1 benzene benzoate and other benzoin; 2 Qinqi phenyl (4)-diphenyl taste Saliva 2 body gas please: 4,5 · di (m-methoxyphenyl) imipenem, 2- (o-i-based) _4,5_ a base taste saliva 2, 2 Qin methoxy Phenyl phenyl (4) _ fine 2, 2, 4, 5, _ triaryl taste saliva 2, 2 _ base... amide small (4- fluorenyl phenyl) _ _, 2 _ trichloro Methyl·5_styrenetrichloromethyl_5_(p-cyanostyryl)], 3,4•oxadiazole, 2-tertungyl-5-5-methoxyphenylethyl (4), 4_曙二唾, etc. Tetramethyl-slope compound, 2,4,6-parade (trichloromethyl)_u, 5_triterpene, 2_methyl ♦ bis (trichloroindenyl hydrazine #三哄, 2_phenyl_4,6_bis(trichloromethyl)-1,3,5-trioxo, 2-(4-chlorophenyl)_4,6-bis(trichloromethyl)_1,3 , 5_three tillage, 2-(4. methoxyphenyl)_4,6_bis(trimethylmethyl)_u, 5_trimorphine, 2 methoxynaphthyl)-4,6-double ( Trichloromethyl h,3,5_trisole, 2♦methoxystyryl)-4,6-bis(trichloroindenyl)_1,3,5_three tillage, 4,5-three Vinyl M,6-bis(trichloromethyl h,3,5_trisole, 2♦methylmonothiobenzene乙土妇基)-4,6-bis (trichloroindenyl hydrazine, 3,5_ morphine, etc. _methyl each three tillage compounds '2,2-methoxy-l,2-diphenyl phenyl] _ketone, 2_mercaptomethylthio)phenyl]·2·morpholinylpropane, 2_pyramidyl-2-dimethylaminopyroxypyrrolylphenyl]butanone-U-hydroxy- A photopolymerization initiator such as cyclohexyl-phenyl ketone; and an oxime ester (〇xime) as a starter described in 曰本特表 2004-534794. _ These photopolymerization initiators may be used alone or in combination of two or more. Further, it may be added as a photopolymerization initiator or a sensitizer 320205 13 200912526, but it can increase the photopolymerization initiator or sensitizer by using it in combination with the above compounds. The ability of the compound. Such a compound may, for example, be a triethanolamine quinone di-t-amine which is effective when used in combination with dicuminone. The amount of the photopolymerization initiator to be used is preferably 7 to 20 parts by weight based on 100 parts by weight of the total of the components (a). When the compounding ratio of the photopolymerization initiator is less than 7 parts by weight, the rate of photopolymerization becomes slow and the sensitivity decreases. On the other hand, when it exceeds 20 parts by weight, the sensitivity is too strong, and the pattern line width is relative to the pattern mask. ) becomes a rough state, and the line width can no longer be faithfully presented relative to the mask. In addition, there is a problem that the edge of the pattern is prepared to be mineral-shaped and not clear. The black organic pigment of the component (b), the light-shielding pigment such as a mixed organic pigment or a light-shielding material, is preferably one having excellent heat resistance, light resistance and solvent resistance. Here, the black organic pigment is, for example, black, cyan black or the like (cya"nine black). The mixed organic pigment may be, for example, a mixture of at least two kinds of pigments selected from the group consisting of red, blue, green, purple, yellow, cyanine, and magenta to form a black color. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Although two or more types can be appropriately selected, the light-shielding property, surface smoothness, sub-stability, and resin are used. From the standpoint of good compatibility, it is particularly preferable to hinder black. The blending ratio of the component (b) is preferably 50 to 15 parts by weight based on 100 parts by weight of the total of the component (a) and the photopolymerization initiator component. When the amount is less than 50 parts by weight, the light shielding property may become insufficient. When the amount is more than 15 parts by weight, the content of the photosensitive resin which is originally an adhesive is reduced, and 14 320205 200912526 is detrimental to the development characteristics, and at the same time, the film formation is caused by the granular oxidized hair of the component (4). No limit = question generated. The production method of the liquid phase reaction or the shape (spherical, aspherical reaction or non-spherical reaction, and excellent dispersibility) is preferably in the form of granulated granules (second). The value is appropriately selected according to the type of rabbit black ^ = within the range 'better... (4) Range: When the value is =, the value of the dioxide + 4 in the resin composition is less than 10 Cong exceeds ^, (4) === Fully rotated, and further, the color filter. The surface roughness of the crucible becomes larger, * can be formed well, and the ratio of the average value of the sub-particle diameter of the opacifying pigment (b) to the granular dioxide (4) ( (b)/(4)) must be in the range of 〇2 to 5 ,, in the range of 〇3 to ((4) ―. If the ratio is less than Q2, it will not be able to maintain long-term distraction and exceed 5.G day After being applied to a substrate and dried, exposure by an ultraviolet exposure apparatus, development of an aqueous solution, and heat treatment: the substrate adhesion in the mask of each step is deteriorated, and in the photolithography system It is necessary to become effective (four) into the ability. Further, the weight ratio of the particulate cerium oxide (c) to the light-shielding pigment ((^ /(b)) must be The range of 0.1 illusion 〇 is preferably in the range of 〇 2 to G 9 . When the ratio is less than 0.1, it is applied to a substrate, dried, and exposed to an ultraviolet ray exposure apparatus, and the water is dissolved and the heat (4) is used. The volume resistivity of the light-shielding film obtained in the step is lowered, and the taper angle becomes less than 60. Significant wrinkles occur, and the surface roughness becomes large, and the results of the present invention are not sufficiently exhibited. Further, when it exceeds 1 G, In the practical film thickness, it becomes 15 320205 200912526 which is less than the shading effect of the black matrix. • In addition, the total weight of the light-shielding pigment (b) and the particulate cerium oxide (c) and the resin in the photosensitive resin composition The weight ratio of the weight of the solid (R) ([(b) + (c)) / (R)) is preferably in the range of 〇. 4 to 2.2. However, the resin solids herein refers to the photoresist. When all the solid matter (the solid residue after hardening) is removed from the particles dispersed in the photoresist such as the pigment and the particulate cerium oxide component, the occurrence of crepe becomes remarkable, and Surface roughness becomes larger, on the contrary, when it exceeds 2.2, in light micro In the photosensitive resin composition for a black resist of the present invention, a solvent is preferably used in addition to the above-mentioned components. Examples of the solvent include methanol, ethanol, n-propanol, and the like. Alcohols such as propanol, ethylene glycol, and propylene glycol; or terpene such as terpinenol; acetone, mercaptoethyl ketone, cyclohexanone, and N-methyl-2-pyrrole Ketones such as ketone; aromatic hydrocarbons such as toluene, xylene, tetradecylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, sulfhydryl Carbitol, ethyl carbitol, butyl carbitol, propylene glycol monodecyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl Ether ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve, carbitol Acid ester, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monodecyl ether acetate, propylene glycol single B An acetate or the like such as an ether acetate can be obtained by dissolving and mixing it to obtain a homogeneous solution. 16 320205 200912526 Further, in the photosensitive resin composition for a black resist of the present invention, a curing accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a solvent, a leveling agent, and the like may be blended as necessary. Additives such as foaming agents. The heat polymerization inhibitor may, for example, be hydroquinone, hydroquinone monomethyl ether, pyrogallol, tributyl catechin, phenothiazine or the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, triplesyl, and the like, and examples of the antifoaming agent or smoothing agent include lanthanide, fluorine, and propionate. a compound of the system. The photosensitive resin composition for a black resist of the present invention contains the above components (8) to (4) or these solvents and a solvent as a main component. In the solid matter from which the solvent is removed (the solid content includes a monomer which becomes a solid after hardening), the total of the components (a) to (c) is 70 wt% or more, preferably 80 wt% or more, more preferably It is desirable to contain 90 wt% or more. The content ratio of the solvent in the resin composition is such that the optimum viscosity range is changed with the coater used for coating, but it is desirably in the range of 5 Å to 90 wt%. Further, the color filter light-shielding film of the present invention is formed by photolithography using the above-mentioned photosensitive resin composition for a black resist of the present invention. The manufacturing steps may be as follows: first, 'the photosensitive tree residue is made into a solution and coated on the surface of the substrate, and then the _ crane (pre-(four)) is placed, and the film thus obtained is covered with a mask, and the (four) line is exposed. Partially hardened, and then the test water is dissolved and the unexposed portion is taken and developed and patterned, and then post bake is used as a method of post-drying. For the substrate on which the solution of the photosensitive resin composition is applied, it can be used on a glass or a permeable film (for example, poly (4), polyethylene terephthalate, poly 320205 17 200912526 ether stone, etc.) A transparent electrode such as IT 〇 or gold is formed by vapor deposition or patterning. A method of applying a solution of the photosensitive resin composition to a substrate, and in view of a conventional solution dipping method or a spraying method, a general-purpose tube coating machine or a surface coating machine (Land) can also be used. Any of the methods of a coater or a rotary machine. After coating to a predetermined thickness by such a method, a solvent is removed (prebaking) to form a film. Prebaking is carried out by heating in an oven, a hot plate or the like. The heating temperature and heating time in the prebaking are appropriately selected depending on the solvent to be used, for example, from 80 to 120. (The temperature is increased to 1 minute. The exposure of 仃1 after prebaking is performed by an exposure machine, and exposure is performed through the mask, and only the photoresist of the corresponding pattern portion is exposed. = The optomechanical and exposure conditions can be appropriately selected, using ultra-high pressure mercury lamps = high-pressure mercury lamps, halogenated metal lamps, far-ultraviolet lamps and other light sources for exposure, so that the black resist in the coating is photohardened with a photosensitive resin composition. "Alkaline imaging performed after exposure is carried out for the purpose of removing the photoresist of the unexposed portion, and the desired image can be formed by the development. Fu A's 'blade master' Fig. Q Examples of the imaging liquid for the test imaging include, for example, a metal gas test, an aqueous solution of a carbonate of a metal group, an aqueous solution of a hydroxide of an alkali metal, and the like, and particularly used at a temperature of 20 to 3 Torr. 〇.05 to 3 ^

%石石山缺 ^ K < anaerobic sodium, potassium carbonate, lithium carbonate and other carbonates of weak alkaline water If % < to 4 good 'can use a commercially available camera or ultrasonic cleaning machine Form a fine image. After the so-called development, the heat treatment (post-baking) is performed at iso to 25 (the temperature of rc and the temperature of 20 to i, τ, Wang υυ, min.) After baking, in order to improve the 遮光320205 18 200912526 This is carried out by the adhesion between the substrates, etc. This is carried out by heating in an oven, a hot plate or the like as in the prebaking: the mask of the present invention is subjected to the steps of the above photolithography method. The resin composition for a black resist of the present invention is suitable for forming a fine pattern by an operation such as exposure or alkaline development as described above, but the same pattern can be obtained by conventional screen printing. A light-shielding film excellent in light-shielding property, adhesiveness, electrical insulating property, heat resistance, and chemical resistance. The photosensitive resin composition for a black resist of the present invention can be suitably used as a coating material, particularly liquid crystal. The ink for color filter used in the display device or the photographic element, and the light-shielding film formed thereby can be used as a color filter, a black matrix for a liquid crystal projector, etc. Further, the photosensitivity of the black resist of the present invention The resin composition can be used as a color liquid crystal display device, a color fax machine, an image sensor, etc., in addition to the color filter ink of the above-mentioned color liquid liquid display. 'Bar shows the use of the body printing ink material. 菔 [Continuous example] <Production example of the dispersion containing the light-shielding material Α·1 to A-8 and 7 4-up to a-3> Resin-coated carbon black (MS18E manufactured by Mitsubishi Wind Co., Ltd.) and granular cerium oxide (manufactured by Aerosii Co., Ltd., so that the total concentration is 20% by weight, and then collapsed) ώ, knife dispersion shirt 5% by weight and propylene glycol monomethyl ether acetate together with a bead mill

Mill) Disperse to make a dispersion of 25% solids Α-1 to A eads, and use titanium black (manufactured by Mitsubishi Materials) or mixed black organic pigment (manufactured by Yutongsu) instead of carbon black to prepare dispersion A. -7 to A-8. ", color 320205 19 200912526 Table 1 ti w — 40eC 〇〇ooo .: 〇〇o 〇X o 柹〇〇〇〇〇〇〇〇〇x- noisy 0) α 0 〇CO 卜<dp 00 2 IO o CD inch CD o P 氡 氡 矽 / pigment ratio | 0.47 : 0.47 0.47 0.47 1_, __ 1,00 0.25 0.00 0.33 0.00 0.47 0.47 Solvent ID 卜 in it: JO in tn CO CO in in in take φή <ibil ψ*0! Μ m in ιο tr> in m to 卜 in in m IO Ί <〇5 <· to to O inch o in o sentence · <d inch cd t hemp 13.6 13.6 13.6 13.6 1_ o CD g in s 13.Θ 13.6 J 郏4 Dioxane/Pigment | s 2.00 0.60 1.20 I__:_:_ 1.20 1.20 1.00 1.00 II 0.20 2.80 Dioxide Dream | s in 〇CO I l〇oi in CM in CNi in CM IO CSl IO CM ID CM TO tn CM to CM IO 04 Pigment species carbon black broken black 嚷 black broken black broken black broken black titanium black mixed organic I pigment broken black disc black carbon black dispersion ft A-1 A -2 A-3 A-4 A-5 A-6 A-7 ! A-8 I <sa~2 a-3 . Manufacturing example 猇猇τ—CSJ Γ0 -'C to «〇r- CO a> o 20 320205 200912526 +0 sCi dispersion _ degree with E-type viscometer 2Q ah, 25·0 ±0.5 C 仃 仃 别 t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t f f In addition, 1G% (the average value in the table is Laihuamei-Oxygen-cutting-sub-grain size # I,, am, electron microscopic observation of the particle size, and the long axis length and the short axis length of 100 are randomly selected, and thus When the arithmetic mean y 'constitutes agglomerates or aggregates (which is egate), - the secondary particles; 5 Γ, the light-shielding color t ^ wire diameter described in Table 1, which is more than the method of expression The average value of the primary particle diameter. The dispersion a·1 of the first example is a dispersion containing no particulate oxidized ♦ 2 疋 The average particle diameter (average of the primary particle diameter) is 5 nm. In the case of granular dioxane (four), the viscosity change is above when it is maintained, and it is difficult to have a knife-and-scattering property (indicated by the parent in the table). The dispersion W is mixed with an average particle diameter (average of primary particle diameter) It is a granular red earth oxide of more than 5 〇 nm. <Preparation of photosensitive resin composition for black resists>, the ratio of each component described in Table 2 and Table 2 is shown in the table. Then, 0.23 parts of Shishiyuan coupling agent S-510 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the monomethyl ether acetate® were added to make the total amount 1GG parts by weight. The object/increase becomes 2G parts by weight. Add the Shishi system surfactant, 7 (Nahua), ο.οι重里伤', use 2#m polypropylene membrane filter to pressurize 0.2 kg/cm2 In the transition, a photosensitive resin composition for a black resist is prepared. Further, each component described in the table is disclosed as follows: B·1: Acetate polycondensate of an epoxy acrylate having an anthracene skeleton, C. 320205 21 200912526 Methyl ether acetate solution (resin solids concentration = 56.1% by weight - manufactured by Nippon Steel Chemical Co., Ltd., trade name V259ME) Β·2: N-ethyl malayan with an average molecular weight of 30,000 and an acid value of 100 Amine/mercaptoacrylic acid/benzyl methacrylate copolymer propylene glycol monodecyl ether acetate solution (resin solids concentration = 36.7 wt%) (Ν-ethyl maleimide: methacrylic acid: mercapto group Benzyl acrylate = 29 : 20 : 51 mol%) C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Chemical Co., Ltd., trade name DPHA) D-1: photopolymerization initiator, IRGACURE οχεο丨 (manufactured by Ciba Specialty Chemicals) D_2: photopolymerization initiator, IRGACURE 0XE02 (manufactured by Ciba Specialty Chemicals)

22 320205 200912526 挺挺ά 44.1 i 10.4 ol 0.96 I 0.47 I 0.78 0.30 〇XX 〇X 1 E12 I ±ί 44.1 L_ 10.41 CM 1 0.961 I— 0.47 1 0.78 I 0.30 X 〇〇X 〇C9 eg o 〇CO s 〇 ί leather ±3 c〇Γ5 i_imJ ΟΙ L 2.10JI 1.26 1 I 0.00 L_0.4_9 I 0.33 〇S 〇〇X csi s 〇I E12 i 擗±j CO C9 1__IMl I 2.621 1 1.26Ί I o.oo 1 0.49 I_ _〇33 〇S 〇〇X tr CNi |The occurrence of wrinkles o I E12 οι 44.11 CM 00 2-48 I o.oo! Γ 0.96 I 0.47 I 0.84 0.30 〇〇〇Csl oi 〇"EM r·· 1^· 44.1 C7 00 CM CO 2.00 1 CD 〇> d I 0.00 I 0,47 1 0.87 I 0.30 0 〇0 〇〇CO c>io 〇s Ο 44.1 LiMJ 2.00 I 0.48 ! 0.48 II 0.47 0.78 0.30 0 Si 〇〇〇 e*> oi s 〇 inch〇> 44.1 Ljm 1 2.00 1 I o.oo II 0.96 I 0.47 1 0.78 1 0.30 〇S 〇〇〇eo oi oo ω 00 44.1 i ml 1 2.00 1 0.96 II 0.47 1 0.78 0.30 0 B 0 〇0 oi so 1 £14 Bu 44.Π lm I 2.00 II 0. 96 II 0.47 0.78 i 1 0.30 0 〇〇〇CO so ω to 44.1 iJQ-iJ 1 zoo 1 0.96 I 0.25 ! 1 0.78 1 0.35 0 〇〇〇00 csi so 1 Ε13 \Λ 54.0 w • L9M s 1.16 0.27 0 S? 0 〇〇CM s 〇ID 守44.1 lIMJ 1 2.00 1 0.96 IMU LoJbJ Γ 0.30 0 〇0 〇〇p〇CsJ s 〇CO 44.1 10.4 2.00 0.96 Lp-17- I OJB I 0.30 0 〇0 〇〇eo csJ So ίΜ 44.1 104 2.00 0.96 J0.-47J I 0-78 | I 0.30 〇〇〇〇〇CO r4 s 〇ω ψ*" 44.1 IL ΪΜ I 2.001 I 0.961 1 0-47 ; I 0-78 I 1 0.30 0 1 40.00 0 〇〇1 2.30 s 〇5 A-2 I A-3 I A-4 i A 2 5 I A-6 I A-7 I A-8 1 (β C*4 (β n n ffl ; B-2 I 5 M__J l〇-2_I , 1 I [2 二 顾 顾 顾 顾 树 | | | | | | 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料Tw first (weight * share) composition weight ratio tearing m sleep «C t E : a \ Q 〇 * < u 4 > 4 Ipct 丨 volume resistance value 23 320205 200912526 will be the above-mentioned black resistance Composition using a spin coater, the photosensitive resin on a glass substrate to a film thickness of 125mmxl25mm after baking after coating became 2.1 # m manner, prebaked 8〇 arts 1 minute. After that, the exposure gap was adjusted to 80 /im 'the negative mask of the line/space = on the dry coating film, and the ultraviolet ray of 100 mj/cm 2 of the ultrahigh pressure mercury lamp with an illumination of 30 mW/cm 2 on the I line. A photohardening reaction of the photosensitive portion is carried out. Next, the exposed coated plate was subjected to a shower image of pressure lkgf/cm 2 at 23 ° C in a 0.05% potassium hydroxide aqueous solution to observe the time of the pattern as a development interruption time (BT, sec), and then After 2 seconds of development, the spray was washed with a pressure of 5 kgf/cm 2 , and the unexposed portion of the coating film was removed to form a halogen pattern on the glass substrate, followed by heat for 30 minutes at 230 C using a hot air dryer. After baking. The evaluation items and methods of the black matrix known in each of the examples and the comparative examples are as follows. Coating of foreign matter: The radial movement point of the coating film after spin coating was observed as x < bad>, and the time scale was not observed as <good>. Sensitivity: Using a step mask, the exposure amount of the residual film was measured as BT (break time) + 20 seconds). The image is squatting. In the BT+4G seconds, the 2G//m pattern remains as 〇, and the stripper is marked as X. Straightness of the pattern: The 2〇Am line (·) after post-baking was observed by a microscope, and the jagged time scale was observed as 乂, and the time scale was not observed. Film thickness and surface roughness were measured using a stylus type film thickness meter (manufactured by Tenc〇r Co., Ltd.). The surface roughness is on the surface of the black matrix separated by 2 sides. 320205 24 200912526

Ra(A). Taper shape. In the case of a fresh person, the daytime is interrupted by Nikko for 1 to 3 seconds, and the 20/zm line section after post-baking is observed by an electron microscope, and the substrate and the BM taper are The angle is usually 6 inches. ,,, u is 〇 from the top, △ is less than 60°, and 乂 is in the shape of an arc. Pattern adhesion: In the peeling test, it was not confirmed that the peeler of the m pattern was marked as 〇&lt;good&gt;, and it was confirmed that the peeler was marked as not wide PCT adhesiveness: the finished _ baked figure PCT (pressure cooker) test under conditions of 121〇C, 100%RH, 2atm, 24 hours, and less than the amount of soil, and then attach the cellophane tape to the peeling test in the 2〇 pattern. It was not confirmed that the 2 〇 pattern peeling was marked as 〇 &lt;good&gt;, and it was confirmed that the peeling person was marked as 乂 (bad) to evaluate. OD measurement: After baking, it is a coating film of 2 i&quot;m ★ a ' •i/zm, and measured by O D meter made by Dayuan Electronics Co., Ltd., every time! #m之〇 d value episode. Volume resistance value: On the glass substrate of the full-scale chrome-plated chrome, the coating film of 2.Um film thickness is formed in the same manner as above, and an A1 vapor film of l〇mm0 is formed on the coating film, and is added between Cr_Al and The electric dust of ι〇ν, the current value is measured, and the electric resistance is obtained. The taper angles of any of the examples r to 12 were all 6 〇. Above, no post-drying occurs, and the surface roughness (surface roughness Ra: JIS B〇60M994) does not exceed (10). On the other hand, the ratio of the ratio (4) i and the comparative example 2 which are not present in the granules is usually a circular arc shape. Further, Comparative Example 3 using a 5 nm particle size dioxo was found to have poor dispersion stability. When the black ink was applied, unevenness in radiation was observed. In Comparative Example 4 in which 320 nm 25 200912526 was used with a particle diameter of 70 nm, the pattern adhesion and PCT adhesion at the time of development were not good. <Examples 13 to 16, and Comparative Examples 5 and 6> In the photosensitive resin compositions used in Example 1, Comparative Example 1, and Comparative Example 2, when the exposure amount was increased to 50, 100, 150, and 200 mJ/cm 2 , The surface roughness and wrinkle condition of the exposed surface after baking were observed. The results are shown in Table 3. In the embodiment containing cerium oxide, no wrinkles occurred and the sensitivity may be improved. However, in the comparative example, the occurrence of wrinkles becomes remarkable when the exposure amount is increased, and if the sensitivity is increased, the surface roughness becomes large, and wrinkles are generated. Table 3 Examples 13 to 16, Comparative Examples 5 to 6 Composition. Exposure amount (mJ/cm2) Sensitivity. 100 150 200 Surface thick chain degree (A) Example 13 Composition of Example 1 74 67 95 47 Example 14 Composition of Example 9 75 66 89 13 Example 15 Composition of Example 10 110 100 110 23 Example 16 Composition of Example 11 82 86 71 20 Comparative Example 5 Composition of Comparative Example 1 700* 1200* 1900* 30 Comparative Example 6 Composition of Comparative Example 2 68 500* 1890* 60 * Wrinkles occurred 26 320205 200912526 &lt;Example 17&gt; Using the resin compositions used in Examples 13 to 16, the opening portion was formed to be 300 / / mxlOO # m and a matrix with a BM line of 30 // m and a film thickness of 2·1 // m of a light-shielding partition wall, after which it is treated with an oxygen atmosphere piezoelectric slurry for 3 seconds, and then subjected to CF4 atmospheric piezoelectric slurry for 3 seconds. Clock processing. When the static contact angle was measured using water or butyl carbitol acetate (BCA) on this opaque partition (shading film), it was 1 〇〇 °, 50 °, respectively. In this black matrix, a red, blue, and green ink having a viscosity of 9 mPa·sec and a solid concentration of 20% was injected using an inkjet head manufactured by Toshiba Technologies Co., Ltd., and post-baking was performed at 230 ° C to form a color filter. As a result, a good color filter can be obtained. [Simple description of the diagram] None [Key component symbol description] None . - 27 320205

Claims (1)

200912526 VII. Patent application scope: 1. A photosensitive resin composition for black resist, which contains (4) photohardenable, resin and/or photocurable monomer, (b) selected from black organic pigment, mixed color organic pigment And at least one or more of the light-shielding pigments and the (4) granular dioxide of the light-shielding material; wherein the average particle size of the particulate-rolled fossil of the (4) component is 1 〇 to 5 〇 nm, and the ratio of the average value of the sub-particle diameter of the opaque pigment (8) to the granulated dioxy-cut (e) ((4) / (8)) is in the range of 0.2 to 5. 并且, and in the above composition The weight ratio ((4) / (b))) of the particulate SiO2 (4) to the light-shielding pigment (b) is in the range of 0.1 to 1. 2. The photosensitive resin composition for a black resist according to the invention of claim i, wherein the total weight of the silk pigment (b) and the particulate gasified fossil (c) and the resin solid matter in the composition The weight ratio of (R) weight ([(b) + (c)] / (R))) is in the range of 0.4 to 2.2. 3. The black resist of claim 1 or 2 is composed of a photosensitive resin; 35, wherein the photocurable resin of the '(4) component is an epoxy compound represented by the following formula (1) and (methyl) The acrylic acid reactant is further composed of a compound containing an unsaturated group obtained by reacting a polybasic acid or its acid. Dcb9-ch-ch8d i OH 320205 28 200912526 】 (In the formula, Ri and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and χ represents CO ' -S〇 2-'-C(CF3)2-'-Si(CH3)2-^-CH2- &gt; -C(CH3)2-'-〇-, 9,9-diyl represented by the following formula, or Does not exist, 03⁄4 n represents an integer from 0 to 10). 4. The photosensitive resin composition for a black resist according to any one of claims 3 to 3, wherein the light-shielding material of the component (b) is carbon black. The photosensitive resin composition for a black resist according to any one of the items 1 to 4, wherein after being applied to a substrate and dried, it is necessary to expose the film to ultraviolet light (1). The surface roughness (Ra) of the light-shielding film obtained by the exposure of the apparatus, (II) the development by the alkaline water 'liquid mixture, and the heat treatment of (ΙΠ) heat treatment is 120 A or less. 6. The photosensitive resin composition for a black resist according to any one of claims 1 to 4, wherein after being applied to a substrate and dried, it is necessary to pass (I) by an ultraviolet exposure apparatus. The volume resistivity of the light-shielding film obtained by the exposure, (π) development by the alkaline water solution, and the heat treatment of (ΠΙ) heat treatment is not less than GQcm. 7. A light-shielding film which is obtained by applying a photosensitive resin composition for a black resist according to any one of claims 1 to 6 on a transparent substrate and drying it after passing through (I) by an ultraviolet exposure apparatus. Exposure, (η) development by an aqueous alkaline solution, and (III) heat treatment, 29 320205 200912526 «Η* obtained a light-shielding film having a taper angle of 60° or more. 8. A color filter suitable for use as an ink jet process color filter, wherein the light-shielding partition wall which is a black matrix is composed of a light-shielding film of the seventh application patent scope, and has a film thickness of 1.5 to 4//m. Provided is a photo-sensitive resin composition for black resist capable of ' forming a pattern with excellent pattern dimension stability, sharpness in edge even in a case of large thickness, without resulting The photo-sensitive resin composition for black resist of the present invention contains (a) Photo-curing resin and/or photo-curing monomer, (b) at least one light-shielding pigment selected from black organic pigment, mixed color organic pigment and light-shielding material, and (c) granular silica, wherein the averaged primary particle Diameter of the granular silica of component (c) is 10~50nm, and the ratio of the averaged primary particle diameter of the granular silica (c) to the Light-shielding pigment (b) ((c)/(b)) is IV. Designated representative map: There is no schema in this case (1) The representative representative figure in this case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. Γ 8ι Κι : negative DCBs-CJj-CH, h OH Ri R2 320205 2 .(1)