Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/201—Filters in the form of arrays

Definitions

• the present invention relates to a method for manufacturing a color filter used for a liquid crystal display device or a solid-state imaging device.
• the dyeing method has the feature that extremely fine color patterns can be freely formed, but the number of photolithographic steps, dyeing steps, and washing steps depends on the number of colors to be dyed. Manufacturing processes such as the fixing process and the anti-dyeing process are many and complicated, and there is also a risk that the yield may be reduced due to adhesion of debris during manufacturing. Also, since the coloring concentration is almost proportional to the thickness of the dyed resin film, the variation in the film thickness causes uneven color and lowers the quality of the product. Depending on the order of staining, color unevenness due to contamination or detachment of other colors may occur. In addition, there is a strong demand from liquid crystal display element manufacturers for a method of reducing the number of color filter manufacturing steps, improving the yield, and making the filter more inexpensive.
• the present inventors have conducted various studies to solve such a problem, and as a result, formed a photosensitive resin film having a specific dyeing property on a substrate, cured the cured resin film, and imprinted a photosensitive resin film on the cured photosensitive resin film.
• a predetermined dye solution By jetting a predetermined dye solution to a predetermined position by the jetting method to form a desired coloring pattern, it has a coloring pattern with high density and high accuracy, and has heat resistance, chemical resistance, It has been found that a color filter excellent in light resistance and the like can be manufactured, and the present invention has been completed.
• the present invention is a.
• a photosensitive resin thin film having the following dyeing properties (a) or (b) is formed on a substrate, and the thin film is cured by irradiation with energy rays.
• a method for producing a color filter which comprises jetting a dye solution to a predetermined position by a jetting method to form a desired colored pattern;
• the anion dye-dyeable polymer is a tertiary nitrogen or a quaternary nitrogen-containing anion dye-dyeable monomer of 20 to 70% by weight.
• a color filter according to the above (2) which is a polymer of a composition comprising 10 to 60% by weight of a hydrophilic monomer other than the monomer and 10 to 50% by weight of a hydrophobic monomer,
• the anionic dye-dyeable monomer is 3- (N, N-dimethylamino) propylamino or 3— (N, N-dimethylamino) propylmethacrylic Lua Mid (7)
• the method for producing a color filter according to the above (3) or (4), and (7) the anion dye-dyeable monomer is 3- (N, N-dimethylmethylamino) propyla Cryamide or 3 — (N, N-dimethylamino) propylmethacrylamide, which is a hydrophilic monomer other than the monomer 2 — Hydroxyshetti Lume acrylate, vinylpyrrolidone or dimethylamino acrylate, and the hydrophobic monomer is methyl methacrylate or methyl acrylate.
• the method for manufacturing a color filter according to the present invention may be implemented, for example, as follows. That is, a highly dyeable photosensitive resin is dissolved in a solvent such as methyl solvent, and the photosensitive resin solution is coated on a substrate by a method such as spin coating, and dried. Exposure is performed by irradiation with energy rays such as ultraviolet rays to cure the photosensitive resin. When curing the photosensitive resin thin film, a predetermined pattern may be exposed through a mask, or the entire surface may be exposed and cured without providing a pattern, or a black mat may be used. The back exposure may be performed through a liquid. Pattern If a pattern is provided, a partition may be formed in the gap between the patterns as black matrix.
• the thickness of the photocured film obtained is usually about 0.3 to 2 m, preferably about 0.3 to 1.5 ⁇ m, and more preferably about 0.3 to lzm. When a black pigment is used, it is better to increase the film thickness.
• the photocured film thus obtained is heat-treated at a temperature of 100 ° C. (: up to 160 ° C., if necessary.
• the heat treatment time is not particularly limited, but is usually 15 to 50 minutes.
• the heat treatment may be performed by a known method using a hot plate or an oven, etc. Then, the heat treatment is performed at a predetermined position on the photosensitive resin thin film which is heat-treated or not heat-treated.
• the jet method applies a predetermined amount of the dye solution from room temperature to 70 '(: preferably at room temperature.
• the ink jet method ejects ink droplets from the nozzle.
• the dyeing (coloring) by this method may be carried out for each color or for multiple colors simultaneously Hot plate at 70 to 180 ° C after dyeing Alternatively, heat drying in an oven for 3 to 15 minutes will give a colorless letter. After that, if necessary, in order to prevent elution of the dye, it may be subjected to a fixing treatment in tannic acid and an aqueous solution of tartar and washed, and if necessary, For the purpose of protecting one color filter, a transparent protective layer may be coated on the entire surface of the dyed thin film.
• the substrate used in the present invention is not particularly limited as long as it is a colorless and transparent plate.
• the substrate include glass, polyester, and polyester. Plates such as polycarbonate, polyacrylate, and polyethersulfone can be given. Its thickness is preferably about 0.5 to 1.5 mm.
• a photosensitive resin thin film having a thickness of 0.6 is added to a 4% aqueous solution of a dye having a molecular weight of 100 or more at room temperature.
• a dyeable photosensitive resin having a transmittance of 5% or less at the maximum absorption wavelength of the dye or
• a photosensitive resin thin film having a film thickness of 0.6 is converted to a molecular weight of 1
• a dye-sensitive photosensitive resin having a transmittance of 5% or less at the maximum absorption wavelength of the dye is preferred.
• New Examples of the dye having a molecular weight of 1000 or more include PCGreen F0P (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of the highly dyeable photosensitive resin satisfying the above conditions (a) or (b) include those containing anionic dye-dyeable polymer and a photosensitive compound as essential components. Is received.
• the anion dye-dyeable polymer is composed of an anion dye-dyeable monomer and a hydrophilic monomer other than the anion dye-dyeable monomer (hereinafter simply referred to as “hydrophilic monomer”). .
• the anion dye-dyeable polymer can be prepared by using a conventionally known solution polymerization method.
• the anion dye-dyeable monomer is, for example, a monomer having tertiary nitrogen or quaternary nitrogen in its molecule, and has a property of giving the polymer a dyeing ability of an anion dye. You It is something.
• Pd-based monomers are preferred, and in consideration of the dyeing properties of anion dyes in particular, 3 — (N, N-dimethylamino) propylene linoleamide, 3 — (N, N-dimethylamino) Propylmethacrylamide is most preferred, and these anionic dye-dyeable monomers are used alone or in combination of two or more.
• hydrophilic monomer examples include Hydroxy Shechi Le Ryo click Re les over preparative arsenide mud key Shechi zone les meta arsenate mud rk of data re les over preparative like (C, ⁇ C 4) A Luki Le (meth) ⁇ grayed Re les over preparative, One or two (C) such as acrylonitrile mid, methacrylamid, dimethylamino acrylosol, methacrylaminoacrylamide , To (: 4 ) may be (meth) acrylinoleamide, vinylpyrrolidone, etc. to which an alkyl group may be bonded, etc. These hydrophilic monomers may be used alone. Or two or more kinds are used in combination.
• the proportion of the anionic dye-dyeable monomer to the hydrophilic monomer is from 25 to 85% by weight, preferably from 30 to 8% by weight. 0% by weight, 15 to 75% by weight of hydrophilic monomer, preferably 20 to 70% by weight o
• Photosensitive compounds include, for example, diazidocalcone, 44'-diazidostilbene-1,2,2 * -disulfonic acid, 4,4'-diazidostilbene-1,2,2'-1 Sodium disulfonate, 4,4'-diazidostilbene 1,2,2 '-Disulfonic acid (bis (methoxethyl)) amide 4,4'-diazidostilbene 1-2 , 2'-, 4,4'-diazidostilbene-1,2,2,-, such as disulfonate (bis (ethoxystyl)) amide, -disulfonate (mono or bis ((C, ⁇ C 4 ) Alkoxy (C) to C 4 ) alkyl))
• Amid compounds such as amides, and conventionally known acrylic compounds having two or more functional groups.
• photosensitive compounds may be used alone or in combination of two or more. It is.
• an azide compound is used as the photosensitive compound, it is preferably used in an amount of about 2 to 15% by weight, particularly 3 to 8% by weight, based on the anionic dye-dyeable polymer. It is preferable to use it.
• a compound having a (meth) acryloyl group other than the anion dye-dyeable monomer and the hydrophilic monomer is used as a dye-dyeable polymer. It is preferable to add 0.1 to 10 parts by weight, especially about 0.5 to 6 parts by weight with respect to 0 parts by weight, because the curing speed increases.
• Examples of the compound having a (meth) acryloyl group include, for example, spiroglycolate [3,9-bis (2—acryloyloxy 1,1 2,4,8,10 — Tetraoxaspiro [5,5] ⁇ decane] cyclohexane dimethyl methyl crelate, ethylene Recall Refill Recall Recall Recall, Recall Recall Recall, Polyethylene Recall Relet, Boll Propylene glycol resin acrylate, butylene glycol resin acrylate, neopentyl glycol resin acrylate, 1,4, butanediol acrylate, 1, 6—Hexane diol diacrylate , Penta erythritol, solresia tallate, pentaerythritol, triacrylate, trimethylolpropane triacrylate, Novola Epoxy acrylate, bisphenol A epoxy acrylate, alkylene epoxy acrylate, glycidyl ester Acrylate, Polyester-
• the photosensitive compound When an acrylic compound having two or more functional groups, which is conventionally known, is used as the photosensitive compound, about 10 to 40% by weight based on the anion dye-dyeable polymer is used. It is preferable to use it, and it is particularly preferable to use about 15 to 35% by weight. In this case, a photosensitizer may be used in combination.
• the polymer may be used.
• a hydrophobic monomer is used in combination as a monomer constituting the compound, the strength of the monomer can be increased.
• hydrophobic monomers examples include methyl acrylate, methyl methacrylate, ethyl butyl butyl acrylate, butyzo acrylate, and 2 — Alkyl esters of (meth) acrylic acid, such as ethylhexyl acrylate and 2-ethylethyl methacrylate Styrene, p-methyl styrene and the like.
• the proportion of the anion dye-dyeable monomer, hydrophilic monomer and hydrophobic monomer is preferably 20 to 70% by weight, preferably anion dye-dyeable monomer.
• the molecular weight of the anion dye-dyeable polymer prepared in this manner is preferably 5,000 to 200,000, more preferably 1,000. 0, 0000 to 1 000 000.
• the photosensitive resin composition having the above composition is usually used after being diluted with an organic solvent or the like.
• the organic solvent include methyl sorb, ethyl sorb, oxoxy, oxicellosolve, ethylene glycol monoethyl acetate, diethyl alcohol, ethylene glycol, diethyl alcohol, alcohol, and ethyl alcohol.
• the proportion of the organic solvent in the photosensitive resin solution cannot be specified unconditionally because it varies depending on the composition in the resin solution, but the viscosity should be such that the resin solution can be applied to the substrate surface. It is preferred that When an azide compound is used as a photosensitive compound, its decomposition and side reactions are avoided.
• the water content in the photosensitive resin liquid is preferably 1 wZw% or less.
• Examples of the photosensitive resin liquid include CFR633DHP and CFR633L1 (both manufactured by Nippon Kayaku Co., Ltd.). ) And so on.
• the anion dye is preferred as the dye used in the dye solution for ink jet.
• the anionic dye include an acidic dye, a direct dye, and a reactive dye.
• the yellow pigment for example, CI Acid Yellow 3, 17: 38, 40: 1, 42, 44: 1, 49, 61, 61 6 5, 6 7, 7 2, 7 9 9, 11 10, 11 4, 11 6, 11 7, 11 9, 12 1, 12 7 , 129, 139, 143, 143, 155, 158, 161, 194, 204, 207 , 224, 232, 235, 241, CI Direct Yellow 12, 86, 87, 130, 134, CI Reactive Yellow 8 4, 102, etc., and dye PC for color filter manufactured by Nippon Kayaku Co., Ltd.
• orange color pigments include, for example, I. Orange 10, 19, 33, 50, 56, 67, and 67. 80, same 108, same 122, same 142, same 66, same 130, I. Direct Orange 26, same 39 I. Reactive Orange 1, same 4, etc. .
• red pigments examples include CI Acid Red 1, 6, 9, 9, 14, 18, 35, 37, 42, 50, 52, 57, Same 73, Same 87, Same 88, Same 89, Same 9 2, 97, 10 6, 11 1, 11 4, 11 18, 12 28, 13 4, 13 8, 14 3, 14 3: 1, 145, 158, 183, 186, 221, 216, 215, 217, 219, same 2 25, 2 2 6, 2 4 9, 2 5 4, 2 5 6, 2 7 7, 2 5 9, 2 6 0, 2 6 1, 2 6 3, 2 266, 274, 276, 278, 289, 299, 310, 303, 307, 307, 315, same 3 16, 3 17, 3 3 6, 3 3 7, 3 4 1, 3 5 5, 3 5 7, 3 5 9, 3 6 2, 3 6 6, 3 383, 3939, 4105, 4107, 41.4, 41.6, 42.6, I.
• Magenta 10P, etc., and examples of purple dyes include, for example, I. Acid Violet 21; 42, 43; 47; 48; 49; 49; 54;
• Examples of blue pigments include, for example, C. Acid Blue 7, 9, 9, 15, 22, 23, 23, 25, 40, and 40. 45, 47, 59, 61: 1: 1, 62, 78, 80, 83, 90, 104, ⁇ 109, 111 2 and 1 2 7, 1 2 7: 1, 1 2 9, 1 3 8, 1 4 0, 2 3, 2 4 4, 2 7 7, 2 2 7, 2 8, Same 23, Same 24, Same 26, Same 26, Same 27, Same 28, Same 28, Same 28, Same 29, Same 33 , 343, CI Direct Blue 106, 108, etc., and Nippon Kayaku Co., Ltd.
• color filter dyes PC Blue 43P, PC Cyan 2P, etc.
• green pigments include I. Acid Green 3, 5, 22, 25, 27, 28, 41, and Nippon Kayaku Co., Ltd. Luster dyes PC GreenF OP, PC Green 100 P and the like.
• black pigments include: I. Acid Black 1. 26, 31, 48, 50, 52, 52: 1, 58, 60, 63: 2, 64, 107, 109, 110, 110, 112, 113, 118, 140, 150, 55, 170 1 7 2 1 7 7, 1 8 7, 1 8 8, 1 9 4, 2 7 7 2 2, CI Direct Black 17, 19, 2 2 5, 6 2, 9 1 1 1 1 2, 1 1 1 7, 1 1 8 1 2 2, 1 3 2, 1 4 6, 1 5 4, 1 5 9, 1 6 9, Same as 17.3.
• dyes acid dyes and dyes for color filters are preferred. These dyes may be used alone or as a mixture to make an ink. If the mixture tends to cause color unevenness, a single component dye may be used alone. Is preferred.
• solvent for the ink water or an organic solvent aqueous solution that can be mixed with water is used.
• Organic solvents include methyl alcohol, ethyl alcohol, butyl alcohol, methylcellosolve, ethylcellosolve, ethyl alcohol, and ethyl glycol.
• One-hole, diethylene glycol monomethyl ether, diethylene glycol monoether ether, dimethyl methyl amide, dimethyl methyl amide, N-methyl Chill-pigs, etc. are available.
• the dye concentration in the ink is preferably 0.5 to 20%, and particularly preferably 3 to 10%. If necessary, the color ligating solution may be used after being filtered using a membrane filter or the like.
• Solvents are obtained by copolymerizing anionic dye-dyeable monomers, hydrophilic monomers and water-hydrophobic monomers, and dye-polymerizable dyes and azide compounds as solvents.
• 100 parts of CFR 633 DHP (manufactured by Nippon Kayaku Co., Ltd.) and a silane coupling agent KB 603 (Shin-Etsu Chemical) (Industrial Co., Ltd.) Mix 0.05 parts. This was coated on a glass plate by the spin coating method, dried at 110 ° C for 3 minutes, passed through a belt conveyor UV irradiator, and exposed to a light of about 15 Expose the entire surface at 0 mJ / cm 2 and cure.
• the cured film has a thickness of 0.6 m.
• the maximum absorption wavelength (The transmittance at 660 nm) is 0.2% or less.
• the glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical processing method, and set in an ink jet screen.
• 4% aqueous solution of PC Blue 43P (color pigment for Nippon Kayaku Co., Ltd.) Is sprayed with an ink jet as a dye solution through a 0.2 membrane lamp and attached to a portion of the thin film to be dyed to be colored blue.
• a 0.2% aqueous membrane solution of PC GreenF0P (a color filter for Nippon Kayaku Co., Ltd.) is passed through the membrane filter.
• the dye solution is sprayed with an ink jet to adhere to a portion of the dyed thin film to be colored green.
• a 0.2% membranum solution of PC Red 21 P (a color filter for Nippon Kayaku Co., Ltd., color filter) of 4% methyl sorbent solution was added to the dyed thin film.
• the dyed liquid is jetted through a filter as an ink jet with an ink jet, and adheres to the portion of the dyed thin film to be colored red. This is heated and dried on a hot plate heated to 150 ° C for 10 minutes.
• the stained glass substrate is immersed in a solution containing 3 g of tannin, 1 g of tartar, and 3 g of acetic acid in 1 liter of water, and the mixture is kept at 70 ° C for 7 minutes.
• the R, G, and B three-color color filters each have a roughly square pattern of about 150 m each, and a color filter formed by a conventional so-called dyeing method. It has equivalent performance.
• Anion dye-dyeable monomers, hydrophilic monomers and water-hydrophobic monomers are copolymerized to obtain anion dye-dyeable polymers, azide compounds, and dyeable dyes.
• mono CFR 63 3 L which is a resin solution of a dyeable photosensitive resin composition type in which a compound having a (meth) acryloyl group other than a monomer and a hydrophilic monomer is dissolved in a solvent. 1 100 parts (Nippon Kayaku Co., Ltd.) and 0.05 parts of silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.) are mixed.
• This is coated on a glass substrate having a black stripe made of a pigment dispersion resist by the spin coating method, dried at 110 for 3 minutes, and then dried from the glass surface. The entire surface is exposed and cured. Then, immerse in 2% tetramethyl thiol hydroxide aqueous solution, develop, wash with water, dry at 150 ° C for 20 minutes, and perform high staining with black stripe on substrate. Obtain a conductive resin film. The thickness of this cured film is 0.6 m, and when dyed by the method (b) above using PC GreenF0P which is a dye having a molecular weight of 100 or more, its maximum absorption wavelength (66 0 nm) is 0.4% or less.
• PC GreenF0P which is a dye having a molecular weight of 100 or more, its maximum absorption wavelength (66 0 nm) is 0.4% or less.
• This glass substrate is set on an ink jet printer.
• a 2% aqueous solution of PC Magenta 41P color pigment for Nippon Kayaku Co., Ltd.
• PC Magenta 41P color pigment for Nippon Kayaku Co., Ltd.
• the thin film to be dyed is sprayed with a jet to adhere to a portion of the thin film to be dyed which is to be colored magenta.
• a 2% aqueous solution of PC Yellow 42P (a color filter dye manufactured by Nippon Kayaku Co., Ltd.) was passed through the 0.2 m membrane filter through the dyed thin film. It is sprayed with an ink jet as a dye solution, and adheres to the portion of the dyed thin film to be colored yellow.
• a 4% aqueous solution of PC black 181P (a color filter for Nippon Kayaku Co., Ltd.) for coloring is passed through a 0.2 / m membrane filter to form a dye solution.
• Spray with an ink jet to stain the stripe pattern black This is dried at 150 ° C for 10 minutes, then immersed in a solution containing 3 g of tannin, 1 g of tartar and 3 g of acetic acid in 1 liter of water, fixed and dried. .
• CFR6333L1 is applied on the substrate having the black stripe, and the same operation as in Example 2 is performed to obtain a color filter.
• the present invention it is not necessary to perform patterning and dyeing fixation treatments three times each as in conventional dyeing, and the process is significantly simplified.
• the yield decrease due to the adhesion of rubbing in the conventional developing and dyeing processes is very small.
• the control of the jetting position of the dye solution by the ink jet method is easy, and the accuracy can sufficiently meet the needs of the user.
• the highly dyeable photosensitive resin thin film used in the present invention has an extremely high affinity for dyes and very little color bleeding. Therefore, a power filter having a coloring pattern with high density and high accuracy can be obtained.
• a color filter having good heat resistance, chemical resistance, light resistance and color characteristics can be obtained.

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• Optics & Photonics (AREA)
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• 1994
  • 1994-07-15 KR KR1019950700997A patent/KR950703746A/ko not_active Application Discontinuation
  • 1994-07-15 GB GB9503696A patent/GB2286063B/en not_active Expired - Fee Related
  • 1994-07-15 SG SG1996000360A patent/SG43738A1/en unknown
  • 1994-07-15 WO PCT/JP1994/001163 patent/WO1995002839A1/ja unknown
  • 1994-07-15 CN CN94190500A patent/CN1112376A/zh active Pending

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