JP2009074094A - Black ink for correcting microscopic defect in coloring pattern, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide black ink for correcting microscopic defects in a coloring pattern that has sufficient blackness and light shielding properties, keeps corrected portions from becoming conspicuous, produces no protrusion that could cause new problems even if it is applied to void portions, i.e., white defects, prevents spots from spreading after application and increasing areas overlapping with normal color pixel portions, maintains good stability of physical properties such as ink viscosity during use and storage, keeps low the rate of decrease in volume after application, and makes it possible to make a film thickness sufficiently thick where it is applied to void portions; a method for correcting microscopic defects in a coloring pattern using the black ink; and a color filter manufactured using them. <P>SOLUTION: The black ink for correcting microscopic defects in a coloring pattern contains at least red, yellow and blue coloring agents, a polymer, a monomer having a reactive functional group, and a solvent, with the solvent being blended by 25 to 70 wt.% of the entire ink, and the viscosity of the ink being 40 to 300 mPa sec. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a micro-colored pattern defect correcting black ink for correcting a pattern defect in a predetermined pattern formed on a substrate, and a color filter corrected using the ink.

  For example, when a finely colored pattern of Bk (black), R (red), G (green), and B (blue) is formed on a substrate, such as a color filter for a liquid crystal display element, A pattern defect is generated with a certain probability due to a minute foreign substance or the like existing in the material. Pattern defects are mainly classified into black defects caused by adhesion of minute foreign matters, etc., and white defects (color loss defects or pattern defect defects) that have a whitish color loss. White defects are attached to the black defect portion. It also occurs when is removed. The black defect is not only visually recognized as a dark point, but also because the defect has a protrusion, when the color filter is bonded to the TFT substrate and the display panel is assembled, the protrusion reaches the TFT substrate. This can cause a short circuit and cause a serious product failure. The white defect is a defect that should be avoided when a liquid crystal display element is assembled and displayed, even if it is a small defect of several tens of microns, it shines like a pinhole and stands out. Recently, with the increase in pattern area accompanying the increase in the screen size of liquid crystal display elements, black defects and white defects are becoming more likely to occur, and the importance of solving such problems is increasing.

  In order to improve the yield and not deteriorate the productivity even if a defective portion is generated, a technique for partially correcting the defective portion as disclosed in JP-A-6-109919 has been established. This defect repair apparatus burns a black defect with a laser and volatilizes it, or applies a color ultraviolet curable resin to a color defect portion of a white defect and cures it with ultraviolet light.

  As a means for applying the color ultraviolet curable resin, the tip forms a flat surface as shown in the above publication, such as a method of dripping a required amount of paste with a dispenser, an ink jet method, or JP-A-8-182949. For example, there is a means for attaching a color ultraviolet curable resin to the tip of the needle-like material and pressing it against the defective part. Among these, a method of directly applying a color ultraviolet curable resin with a needle-like material is considered preferable because it can cope with finer white defects.

  However, even if the ink used for forming the fine coloring pattern is used as it is, it cannot be corrected well. For example, the ink for forming the colored layer of the color filter by the printing method is prepared in consideration of the adhesion to the blanket. In addition, there is a problem that when the ink overlaps to a normal color pixel portion, the overlap portion tends to become a new protrusion. In addition, for example, for a colored resist composition formed by pattern exposure, the viscosity is too low to be applied to the correction portion in order to apply it uniformly by spin coating or the like, and it is applied after application. The spot spreads, the area of the overlapping portion with the normal color pixel portion increases, and a new color mixing defect may occur. Further, when the viscosity is low, there is a problem that the “paste” of the ink onto the needle is poor, particularly in the case of application with a needle-like medium.

  On the other hand, Japanese Patent Application Laid-Open No. 11-142635 discloses a color paste for application to a color loss portion by a needle-like medium. However, since this color paste has a high solvent content, the stability of physical properties such as the viscosity of the color paste deteriorates due to the volatilization of the solvent during storage and use, and the volume decreases due to the volatilization of the solvent even after the color paste is applied. There is a problem that the rate increases. When the volume reduction rate is large, it is difficult to sufficiently increase the film thickness of the portion supplemented to the color loss part, and it is necessary to repeatedly apply in order to obtain a sufficient film thickness. If the volume reduction rate is increased in consideration of the volume reduction rate in order to make the thickness sufficiently thick, the fluidity is high, so that there is a problem that it protrudes to the periphery and becomes a new protrusion or a color mixing defect. Moreover, since this color paste has a high solvent content, there is a tendency that the content of the binder resin in the solid content tends to be small, and there is a problem that the adhesion of the coated film after drying to the substrate is not good. This color paste mainly uses a polyimide precursor as a binder resin. However, when the content of the binder resin in the solid content is increased, there is a problem that the viscosity becomes too high and the coating suitability is deteriorated.

  On the other hand, carbon black has been widely used as a black pigment such as black ink for forming a black matrix of a color filter or a colored resist composition for black matrix formed by pattern exposure. However, since carbon black is conductive, if it is used as a modified black ink pigment, if a new protrusion is generated at the corrected portion, the protrusion reaches the counter substrate, causing conduction, resulting in a display defect. There is.

  A proposal has been made to realize black by combining two complementary pigments instead of using carbon black as a black pigment, but there are two color pigments that can represent complementary colors themselves. Because it does not exist, even if two types of pigments that are close to complementary colors are mixed, the synthetic spectrum is high in transmittance in a part of the visible light region, and becomes bluish or reddish, and can achieve black with high optical density. could not.

JP-A-6-109919 JP-A-8-182949 JP 11-142635 A

  The present invention was devised in view of such problems, and the object of the present invention is to have sufficient black and light-shielding properties, so that the corrected portion does not cause a display defect and eliminates a defective portion of a white defect. Even if it is applied, it does not cause any new protrusions that become a problem, and the spot spreads after application so that the area that overlaps the normal color pixel area does not increase. Black ink for correcting micro-colored pattern defects, which has good physical property stability such as viscosity of the ink, has a low volume reduction rate after application, and can sufficiently increase the thickness of the application part of the color loss part, and A color filter manufactured using the same is provided.

  In the present invention, the black ink for correcting minute color pattern defects for achieving the above object contains at least red, yellow and blue colorants, a monomer having a reactive functional group, a polymer, and a solvent, The amount of the solvent is 25% to 70% by weight of the whole ink, the amount of the monomer is 15% to 65% by weight of the whole ink, and the amount of the polymer is 1% by weight to 25% by weight, and the total amount of the monomer and the polymer is 30% by weight to 85% by weight of the total solid content in the ink, and the three colorants The total blending amount is 5% by weight to 40% by weight of the whole ink, and the viscosity of the ink is 40 to 300 mPa · sec.

  The black ink for correcting microcolored pattern defects according to the present invention does not use carbon black as a colorant, but realizes black by mixing three colorants of red, yellow, and blue. Therefore, even when the corrected portion generates a new protrusion, it is possible to avoid the occurrence of conduction due to the contact between the counter substrate and the protrusion. In addition, when the three colorants of red, yellow, and blue are mixed, the transmittance of the synthetic spectrum is in the visible light region (400 nm to 400 nm˜), unlike the case of mixing the two complementary colorants of the conventional complementary colors. 760 nm), it becomes uniformly low, and it is possible to realize black having a high optical density without producing a color such as blue or red.

  Moreover, since the black ink for correcting micro-colored pattern defects according to the present invention contains both a polymer and a monomer having a reactive functional group, viscosity adjustment required for the binder component and film-formability and curability after coating, Various functions such as adhesion to the surface to be coated can be divided into both monomers and polymers having reactive functional groups. As a result, for example, the polymer does not necessarily require curability, and the degree of freedom in polymer selection. As a result, the degree of freedom in designing as a black ink for correcting the formation of minute colored patterns is increased. Therefore, by adjusting the types and amounts of the monomer and polymer having a reactive functional group, the physical properties related to the coating suitability such as viscosity are adjusted to an appropriate range, and the amount ratio between the colorant and the binder component is also appropriate. By adjusting the range, sufficient color density and sufficient adhesion to the substrate can be obtained.

  Moreover, since it contains the monomer which has a reactive functional group, compared with the case where only a polymer is contained, there exists an effect which improves the solvent resistance of a correction part, heat resistance, and the adhesiveness with respect to a to-be-coated surface.

  Furthermore, since the monomer having a reactive functional group can partially substitute for the solvent, the solvent content in the ink can be reduced. For this reason, the volatilization amount of the solvent is reduced, the stability of physical properties such as the viscosity of the ink is improved during storage and use, and the volume reduction rate due to the volatilization of the solvent is reduced after application of the ink. Since the volume reduction rate is small, it is possible to make the film thickness of the part replenished in the missing area sufficiently thick with a small amount of ink adhesion, eliminating the trouble of repeated application, and the adhered ink droplets are not dried. However, since the volume is small, it is difficult to protrude to the periphery, and the formation of new protrusions and the occurrence of color mixing defects can be avoided.

  Further, since the viscosity of the ink is in the above range, the coating spot has a gentle shape, no bleeding occurs, and the protrusion height is within the allowable range.

In the following formula (1), the black ink for correcting the minute colored pattern defect is:
τ = Kγ ^L (1)
(However, 0.081 ≦ K ≦ 0.111, 0.881 ≦ L ≦ 0.954)
When the γ value is 10, the τ value is 0.3 to 1.3, when the γ value is 100, the τ value is 4.0 to 10.0, and / or when the γ value is 10 to 100. When the τ value is 0.3 to 10, the slope is 0.075 to 0.15, and the order is 0.8 to 1.1, the ink is applied to the color loss portion by the acicular medium. From the viewpoint that the ink easily adheres to the needle tip.

  When the static surface tension of the black ink for correcting fine color pattern defects is 20 mN / m to 45 mN at 25 ° C., it does not stick out from the position where the ink is applied and spreads and blurs color mixing defects. It is preferable because it does not occur and does not create a new protrusion.

  When the black ink for correcting the minute colored pattern defect has an optical density of 1.0 or more when the film thickness upon curing is 1.9 μm or less, the corrected portion does not stand out and a sufficient shielding effect is obtained. Since it is obtained, it is preferable.

  When the monomer having a reactive functional group has two or more reactive functional groups in one molecule, it is preferable because a high crosslinking density is obtained and sufficient curability is exhibited.

  It is preferable that the black ink for correcting fine color pattern defects further contains a polymerization inhibitor from the viewpoint of preventing gelation of the ink and improving stability during storage and ink production.

The polymer is preferably a diallyl phthalate prepolymer from the viewpoint of thermosetting and electrical properties.
It is preferable that the conductivity of the colorant of each color is 10 ¹⁰ Ωcm or more because conduction can be avoided even when a relatively large protrusion is formed on the correction portion and contacts the opposing substrate.

  The color filter corrected with the black ink for correcting micro-colored pattern defects is a color filter having the same performance as a defect-free product.

  As described above, the black ink for correcting micro-colored pattern defects according to the present invention does not use carbon black as a colorant, and realizes black by mixing three colorants of red, yellow, and blue. . Therefore, even when the corrected portion generates a new protrusion, it is possible to avoid the occurrence of conduction due to the contact between the counter substrate and the protrusion. In addition, when the three colorants of red, yellow, and blue are mixed, the transmittance of the synthetic spectrum is in the visible light region (400 nm to 400 nm˜), unlike the case of mixing the two complementary colorants of the conventional complementary colors. 760 nm), it is uniformly low, and it is possible to realize black having a high optical density without producing a color such as bluish or reddish. Even when correcting the black matrix, the correcting part stands out instead. You can avoid that. Further, although it is difficult to disperse carbon black at a high concentration in an ink having physical properties such as viscosity necessary for the correction black ink and to perform optimal rheological control, the red, yellow, and blue 3 When the colorant is mixed to achieve black, the colorant is selected into the black ink for correction by selecting and using a colorant with good dispersibility for each of the red, yellow and blue colorants. In addition to being able to be dispersed at a high density, it is possible to realize an optimum rheology, and it is possible to realize a black color having good coating properties and a predetermined density or more.

  Moreover, since the black ink for correcting micro-colored pattern defects according to the present invention contains both a polymer and a monomer having a reactive functional group, viscosity adjustment required for the binder component and film-formability and curability after coating, Various functions such as adhesion to the surface to be coated can be divided into both monomers and polymers having reactive functional groups. As a result, for example, the polymer does not necessarily require curability, and the degree of freedom in polymer selection. As a result, the degree of freedom in designing as a black ink for correcting the formation of minute colored patterns is increased. Therefore, by adjusting the types and amounts of the monomer and polymer having a reactive functional group, the physical properties related to the coating suitability such as viscosity are adjusted to an appropriate range, and the amount ratio between the colorant and the binder component is also appropriate. By adjusting the range, sufficient color density and sufficient adhesion to the substrate can be obtained.

  Moreover, since it contains the monomer which has a reactive functional group, compared with the case where only a polymer is contained, there exists an effect which improves the solvent resistance of a correction part, heat resistance, and the adhesiveness with respect to a to-be-coated surface.

  Furthermore, since the monomer having a reactive functional group can partially substitute for the solvent, the solvent content in the ink can be reduced. As a result, the volatilization amount of the solvent is reduced, the physical stability such as the viscosity of the ink is improved during storage and use, and the volume reduction rate due to the volatilization of the solvent is reduced after the ink is applied. Since the volume reduction rate is small, it is possible to make the film thickness of the part replenished in the missing area sufficiently thick with a small amount of ink adhesion, eliminating the trouble of repeated application, and the adhered ink droplets are not dried. However, since the volume is small, it is difficult to protrude to the periphery, and the formation of new protrusions and the occurrence of color mixing defects can be avoided.

  Since the viscosity of the ink is in the above range, the application spot has a gentle shape, no bleeding occurs, and the protrusion height is within the allowable range.

  In the above-mentioned formula (1), when the black ink for correcting minute color pattern defect according to the present invention is 10, the τ value is 0.3 to 1.3, and when the γ value is 100, the τ value is 4.0 to 10. 0.0 and / or when the ink has the following formula (1) and the γ value is 10 to 100, the τ value is 0.3 to 10.0, the slope is 0075 to 0.15, and When the order is 0.8 to 1.1, when the ink is applied to the color loss portion by the needle-shaped medium, the viscosity is lowered for a moment, the ink is loosened, and the ink easily adheres to the needle tip.

  When the static surface tension is in the above range, there is an advantage that the ink does not protrude from the position where the ink is applied and spreads and causes a color mixing defect or a problem that a new protrusion is not generated. .

  Therefore, it has sufficient black and light-shielding properties, the corrected part is not conspicuous, and there is no new protrusion that becomes a problem even if it is applied to the color defect portion of the white defect. By spreading, the area that overlaps the normal color pixel part does not increase, and the stability of physical properties such as ink viscosity during use and storage is good, the volume reduction rate after application is low, and the color loss part Thus, it is possible to obtain a black ink for correcting a minute colored pattern defect capable of sufficiently increasing the thickness of the coated portion.

  Since the color filter in which the defect portion is corrected with the black ink for correction according to the present invention is a color filter having the same performance as a defect-free product, even if a defect occurs, the yield is improved and the productivity is improved. It has the effect of going up.

  The present invention is described in detail below. In the present specification, (meth) acryl represents acryl and methacryl, and (meth) acrylate represents acrylate and methacrylate.

  In addition, in this specification, light includes all wavelengths in the visible and non-visible regions that can cause a photoreactive functional group to undergo a photoreaction, for example, microwaves, visible light, ultraviolet rays, electromagnetic waves, electrons Although all the lines are included, ultraviolet rays, electron beams, etc. are mainly used.

  First, the black ink for correcting a minute colored pattern defect according to the present invention will be described. The black ink for correcting micro-colored pattern defects according to the present invention contains at least red, yellow and blue colorants, a monomer having a reactive functional group, a polymer, and a solvent. The ink has a viscosity of 40 to 300 mPa · sec.

  The black ink for correcting microcolored pattern defects according to the present invention does not use carbon black as a colorant, but realizes black by mixing three colorants of red, yellow, and blue. Therefore, even when a step is formed between the corrected portion and the surrounding area, and a new protrusion is generated, the opposite substrate and the protrusion are brought into contact with each other by using a colorant having low conductivity for each of red, yellow, and blue. Can be avoided. In addition, when the three colorants of red, yellow, and blue are mixed, the transmittance of the synthetic spectrum is in the visible light region (400 nm to 400 nm˜), unlike the case of mixing the two complementary colorants of the conventional complementary colors. 760 nm), it becomes uniformly low, and it is possible to realize black having a high optical density without producing a color such as blue or red.

  Moreover, since the black ink for correcting micro-colored pattern defects according to the present invention contains both a polymer and a monomer having a reactive functional group as a binder component, viscosity adjustment required for the binder component and film-formability after coating and Various functions such as curability and adhesion to the surface to be coated can be separated by both the monomer and polymer having a reactive functional group. As a result, for example, the polymer is not necessarily required to be curable. This increases the degree of freedom in designing as a black ink for correcting the formation of minute colored patterns. Therefore, by adjusting the types and amounts of the monomer and polymer having a reactive functional group, the physical properties related to the coating suitability such as viscosity are adjusted to an appropriate range, and the amount ratio between the colorant and the binder component is also appropriate. By adjusting the range, sufficient color density and sufficient adhesion to the substrate can be obtained.

  Moreover, since it contains the monomer which has a reactive functional group, compared with the case where only a polymer is contained, there exists an effect which improves the solvent resistance of a correction part, heat resistance, and the adhesiveness with respect to a to-be-coated surface.

  Furthermore, since the monomer having a reactive functional group can partially substitute for the solvent, the solvent content in the ink can be reduced. For this reason, the volatilization amount of the solvent is reduced, the stability of physical properties such as the viscosity of the ink is improved during storage and use, and the volume reduction rate due to the volatilization of the solvent is reduced after application of the ink. Since the volume reduction rate is small, it is possible to make the film thickness of the part replenished in the missing area sufficiently thick with a small amount of ink adhesion, eliminating the trouble of repeated application, and the adhered ink droplets are not dried. However, since the volume is small, it is difficult to protrude to the periphery, and the formation of new protrusions and the occurrence of color mixing defects can be avoided.

  As the colorant for the black ink for correcting the formation of a microcolored pattern according to the present invention, it is preferable to use a mixture of three colorants of red, yellow, and blue colorants having low conductivity. Although it is difficult to perform optimal rheological control so as to obtain an ink having the necessary properties such as viscosity while carbon black is dispersed at a high concentration in the correction black ink, the three colors of red, yellow and blue are difficult to control. When the colorant is mixed to achieve black, the colorant is highly concentrated in the correction black ink by selecting and using a colorant with good dispersibility for each of the red, yellow, and blue colorants. In addition, it is possible to achieve an optimal rheology, and it is possible to achieve a black color having a good coating property and a predetermined darkness.

  For each colorant, various organic or inorganic pigments can be used. From the viewpoint of spectral characteristics and conductivity, specific examples of organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), that is, the following colors: Listed with an index (CI) number.

Even when a relatively large protrusion is formed on the correction portion and comes into contact with the counter substrate, it is preferable that each of the red, yellow, and blue colorants has low conductivity from the viewpoint of avoiding conduction. Specifically, the conductivity of each colorant is preferably 10 ¹⁰ Ωcm or more, and more preferably 10 ¹³ Ωcm or more.

  Specific examples of suitable red colorants include, for example, CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, and CI Pigment Red 123. CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, CI Pigment Red 254 And red pigments such as

  Specific examples of suitable yellow colorants include, for example, CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 83 CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139 CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 180, include C.I. Pigment Yellow 185, etc. Yellow pigments of.

  Specific examples of suitable blue colorants include CI pigment blue 15, CI pigment blue 15: 3, CI pigment blue 15: 4, CI pigment blue 15: 6, CI pigment blue 21, and CI pigment blue. 22 and CI pigment blue 60, CI pigment blue 64, and the like.

  Specific examples of the inorganic pigment include red iron oxide (III) and cadmium red as red colorants, yellow lead and zinc yellow as yellow colorants, and ultramarine blue and bitumen as blue colorants. be able to.

  In the present invention, for each of the three colorants of red, yellow and blue colorants, the transmittance of the synthetic spectrum of the three colors of red, yellow and blue colorants is in the visible light region (400 nm to 760 nm). It is preferable to select a combination of three colorants and adjust the blending amount so as to be uniformly low. As a standard for selecting the three colorants, a spectrophotometer or a Macbeth transmission densitometer is used to measure an omega conversion value of visible light transmittance or light absorption rate, and these measured values are used as indexes. be able to.

  Among these, CI pigment red 177 and CI pigment red 254 are preferably used as the red colorant, CI pigment yellow 83 and CI pigment yellow 139 are preferably used as the yellow colorant, and the blue colorant is preferably used. CI Pigment Blue 15: 3 and CI Pigment Blue 15: 6 are preferable. Among them, CI Pigment Red 254 as a red colorant, CI Pigment Yellow 139 as a yellow colorant, and CI Pigment Blue 15 as a blue colorant: Preferably, CI pigment red 177 is used as a red colorant, CI pigment yellow 83 is used as a yellow colorant, and CI pigment blue 15: 3 is used as a blue colorant, and CI pigment red 254 is particularly preferable. As a colorant C.I. Pigment Yellow 139 and C.I. Pigment Blue 15: 6 as a blue colorant are preferably used in a mixing ratio of 4: 2: 4.

  In the present invention, for each of the three colorants, red, yellow and blue colorants, a single colorant or a mixture of two or more colorants can be used. Can be used. In addition, you may use the colorant to which surface treatments, such as a rosin process, an acidic process, and a basic process, are given as needed.

  The total blending amount of the three colorants is preferably 5 to 40% by weight, more preferably 5 to 25% by weight, and more preferably 7 to 18% by weight in the black ink for correcting minute color pattern defects. Is particularly preferred.

  In the black ink for correcting microcolored pattern defects of the present invention, the monomer having a reactive functional group constitutes a binder component for imparting film formability and adhesion to the coated surface together with a polymer described later, particularly a curing reaction. It acts to impart sex. In addition, this monomer is a component that can be replaced with a part of the solvent, and has an effect of reducing the amount of the solvent used, and is also a component for adjusting physical properties such as the viscosity of the ink.

  A monomer having a reactive functional group is a compound that can be a constituent unit of a polymerization reaction. For example, an oligomer in which two or more monomers are polymerized has a reactive functional group and is fluid at room temperature. If present, it can be used as a monomer in the present invention.

  Monomers having such reactive functional groups can be used alone or in admixture of two or more.

  When a polyfunctional reactive monomer having two or more reactive functional groups in one molecule is used as the monomer having a reactive functional group, it is preferable because a high crosslinking density is obtained and sufficient curability is exhibited.

  The reaction type of the reactive functional group is not particularly limited as long as it is a curing reaction. For example, it may belong to either photoreaction or thermal reaction in terms of reaction energy, radical polymerization in terms of active species, It may belong to any of cationic polymerization, anionic polymerization, photodimerization reaction and the like. Specifically, for example, when the monomer has an ethylenically unsaturated bond as a reactive functional group, photo radical polymerization and thermal radical polymerization are possible, and when the monomer has an epoxy group as a reactive functional group Thermosetting and photocationic polymerization are possible.

  As the photoreactive monomer, a monomer having an ethylenically unsaturated bond is preferably used. A monomer having an ethylenically unsaturated bond as a radical photopolymerizable group is one that undergoes a polymerization reaction either directly by light irradiation or indirectly by the action of an initiator, and is used to correct a black color for correction in a minute colored pattern defect portion. After applying the ink, it is preferably used for fixing the ink in a short time by light irradiation.

  Specific examples of the monomer having an ethylenically unsaturated bond include the following polyfunctional acrylate monomers: dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, diallyl phthalate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate propylene oxide addition Products, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropiate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meta) ) Acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, etc., among others, dipentaerythritol hexaacrylate, dipentaerythritol penta (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta Acrylate, high crosslinking density can be obtained, preferably exhibits sufficient curability.

  Examples of the cationic photopolymerizable monomer include monomers having a cyclic ether group such as an epoxy group or an oxetanyl group, a thioether group, a vinyl ether group, or the like.

  Examples of the photoanion polymerizable monomer include monomers having a vinyl group having an electron withdrawing group, a cyclic urethane group, cyclic ureas, a cyclic siloxane group, and the like.

  As the heat-reactive system, for example, a ring-opening addition reaction system such as an epoxy group and active hydrogen or a cyclic urea group and a hydroxyl group can be used. Particularly preferably, a combination of a monomer (including an oligomer) having a glycidyl group, an alicyclic epoxy group, or an oxetanyl group and a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid can be exemplified from the viewpoint of stability over time. From the viewpoint of curability, monomers having a glycidyl group, an alicyclic epoxy group, and an oxetanyl group and those disclosed in Japanese Patent Nos. 26682256, 2850897, 2894317, and JP-A-2001-350010 are disclosed. It is particularly preferred to use a combination of block carboxylic acids.

  Examples of the monomer having a glycidyl group, an alicyclic epoxy group, or an oxetanyl group include novolak epoxy, alicyclic epoxy, cardo epoxy, etc. that are liquid at room temperature. For example, the product name BPEFG (Nagase) Manufactured by Chemtex), Celoxide 2021P, 3000, 2000, Styrene oxide, Epolide GT300, GT400 (above, manufactured by Daicel Chemical Industries), Epicoat 901, 801P, 802, 802XA, 806, 806L, 807, 815, 819, 825, 827 , 828, 815XA, 828EL, 828XA, 152, 604, 630 (above, made of oil-based shell epoxy). Of these, Epolide GT400, which is an alicyclic epoxy, is preferable from the viewpoints of viscosity and reactivity.

  Specific examples of the polyvalent carboxylic acid anhydride used in combination with the monomer having an epoxy group include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, Aliphatic or alicyclic dicarboxylic anhydrides such as hexahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hymic anhydride, nadic anhydride; 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentane Aliphatic polycarboxylic acid dianhydrides such as tetracarboxylic dianhydride; aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ethylene glycol bis trimellitate, Ester group-containing acid anhydrides such as glycerin tristrimericate It can be mentioned, particularly preferably, and aromatic polycarboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

  Specific examples of the polyvalent carboxylic acid used in combination with the monomer having an epoxy group include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; Aliphatic polycarboxylic acids such as hydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, Mention may be made of aromatic polycarboxylic acids such as trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid.

  These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more. The compounding amount of the curing agent is usually in the range of 50 to 200 parts by weight per 100 parts by weight of the monomer having an epoxy group.

  Examples of the photoreactive and heat-reactive monomer include monomers having an ethylenically unsaturated bond and an epoxy group. Specifically, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n -Glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -4,5-epoxypentyl methacrylate, acrylate-6, (Meth) acrylates such as 7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl; o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p -Vinyl phenyl glycidyl ether, o-vinyl benzyl group Vinyl glycidyl ethers such as sidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene di Glycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, and 1,3,5-trihydroxymethylstyrene triglycidyl ether, cycloaliphatic epoxy (meth) acrylate Etc.

  The amount of the monomer having a reactive functional group is preferably 15% by weight to 65% by weight, more preferably 20% by weight to 55% by weight, and more preferably 25% by weight to 45% by weight in the black ink for correcting minute coloring pattern defects. Is particularly preferred.

  In the black ink for correcting minute coloring pattern defects of the present invention, the polymer has a higher viscosity than the monomer as a binder component for imparting film formability and adhesion to the coated surface, and in the ink state. Therefore, it is blended as a component for adjusting physical properties such as the viscosity of the ink.

  In the present invention, in particular, the function as the binder component is shared with the monomer having the reactive functional group, so that the choices of polymers that can be used are expanded, and the degree of freedom in design is increased.

  The polymer that can be used is not particularly limited as long as it is soluble in the solvent to be used or compatible with the monomer having the reactive functional group to be used. In the present invention, a monomer having a reactive functional group is more preferably compatible with the monomer having a reactive functional group to be used, in order to partially provide the solvent with an alternative function of the solvent.

  The polymer used has a higher viscosity than the monomer in the ink state, and is used to adjust the viscosity to a high level. Therefore, the weight average molecular weight is 30,000 or more (measured by gel permeation chromatography (GPC)). Polystyrene-converted weight average molecular weight) is preferable, and 50,000 or more is more preferable. In such a case, a sufficient viscosity increase effect can often be obtained with a small amount.

  Such polymers can be used alone or in admixture of two or more.

  In particular, the same type of polymer as the polymer used in the coloring pattern to be corrected is preferable in terms of familiarity with the correction site of the correction color paste and adhesion. For example, a polymer generally used for a color pattern in a color filter is an acrylic resin or the like, and these can be preferably used when correcting the color pattern of the color filter.

  The polymer may be either reactive or non-reactive. However, when a reactive polymer is used, it is preferable because the film strength can be increased by reacting and curing the coating film. The reaction form of the reactive functional group is the same as that of the monomer having the reactive functional group, and is not particularly limited.

  Here, as the non-reactive polymer, for example, a polymer comprising the following monomers or a copolymer using two or more monomers: (meth) acrylic acid, methyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, benzyl (meth) acrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer, cyclohexyl (meth) acrylate, α-hydroxymethyl (meth) acrylate, α-hydroxyethyl (meth) acrylate, tricyclode Nical (meth) acrylate; etc. can be used.

  The reactive polymer may be a polymer having a reactive functional group, for example, a polymer having an ethylenically unsaturated bond, a polymer having an epoxy group, a polymer having an oxazoline group, a polymer having a cyclic urea group, A polymer having a cyclic ester group, a polyimide precursor (polyamic acid), a melamine resin, or the like can be used. From the viewpoint of stability and reactivity, a polymer having an ethylenically unsaturated bond and a polymer having an epoxy group are preferable. Used.

  As the polymer having an ethylenically unsaturated bond, polymers and copolymers using one or more of the above-mentioned polyfunctional acrylate monomers containing an ethylenically unsaturated bond can be used. Among these, diallyl phthalate prepolymers and polymers described in JP-A No. 2000-239497 are preferably used from the viewpoint of thermosetting.

  The blending amount of the polymer is preferably 1 to 25% by weight, more preferably 2 to 20% by weight, and particularly preferably 2 to 12% by weight in the black ink for correcting minute coloring pattern defects.

  The solvent that can be used in the black ink for correcting the formation of a microcolored pattern according to the present invention is not particularly limited, but a solvent having good dispersibility of the colorant or a monomer having a reactive functional group or a polymer having good solubility or dispersibility is used. A mixed solvent using two or more kinds of solvents is preferable.

Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbitols such as methoxyethoxyethanol and ethoxyethoxyethanol. Solvents; Ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; Ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate Cellosolve acetate solvents such as carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; Ether solvents such as ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolactone Non-aqueous organic solvents such as solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are particularly preferably used. Particularly preferably, PGMEA (propylene glycol monomethyl ether acetate, CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ) (trade name: methoxypropyl acetate (manufactured by Daicel Chemical Industries)), MBA (3-methoxybutyl acetate, CH ₃ CH (OCH ₃ ) CH ₂ CH ₂ OCOCH ₃ ), DMDG (diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ), or a mixture thereof can be used.

  The blending amount of the solvent is 25% to 70% by weight in the black ink for correcting minute coloring pattern defects, more preferably 25 to 55% by weight, and particularly preferably 30 to 45% by weight.

  The black ink for correcting microcolored pattern defects according to the present invention contains a monomer having a reactive functional group as an essential component, so that polymerization is performed in order to prevent gelation of the ink and improve stability during storage. It is preferable to add an inhibitor.

  The polymerization inhibitor is not particularly limited, and diphenylpicrylhydrazide, tri-p-nitrophenylmethyl, p-benzoquinone, p-tert-butylcatechol, picric acid, copper chloride, methylhydroquinone, methoquinone, tert-butylhydroquinone. Polymerization inhibitors for reactions such as these can be used, but among these, hydroquinone polymerization inhibitors are preferred from the viewpoint of storage stability, and methylhydroquinone is particularly preferred.

  The blending amount of the polymerization inhibitor is preferably 0.01% by weight to 1% by weight, more preferably 0.01% by weight to 0.5% by weight in the black ink for correcting minute coloring pattern defects, and 0.01% by weight. ˜0.05% by weight is particularly preferred.

  The pigment dispersant is preferably blended for the purpose of improving the dispersibility of the colorant in the ink.

  Specific examples of the pigment dispersant include amide compounds such as nonanoamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, Amine compounds such as diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N , N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′- Tetra (hydroxyethylpolyoxyethylene) -1,2-di Amines having hydroxy groups such as aminoethane, 1,4-bis (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) piperazine, etc., nipecotamide, isonipecotamide, nicotinamide, etc., polyurethane, polyacrylate, etc. Polycarboxylic acid ester, unsaturated polyamide, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, Examples of these modified products include polyester-based high molecular weight pigment dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, but the colorant concentration is low. Dispersibility even when high From good point, it is preferable to use a polyester-based high-molecular weight pigment dispersant, it is particularly preferable to use Solsperse 24000GR (manufactured by Avecia).

  The blending amount of the pigment dispersant is preferably 1 to 25% by weight, more preferably 1 to 15% by weight, and particularly preferably 1 to 10% by weight in the black ink for correcting minute coloring pattern defects.

  The polymerization initiator is preferably blended for the purpose of improving the reactivity of the monomer having a reactive functional group or the reactive polymer.

  For example, when a monomer and / or polymer having a radical polymerizable group such as an ethylenically unsaturated bond is used, a radical polymerization initiator is usually added. Examples of radical polymerization initiators include acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamines. A compound or the like is used. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethylketone, 1- (4-dodecyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane Examples thereof include -1-one and benzophenone. Among these, initiators of acetophenones and thioxanthones are preferably used, and specifically, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1, 2-methyl -1- (4-Methylthiophenyl) 2-morpholino-propan-1-one and diethylthioxanthone are preferably used in the present invention in terms of sensitivity and low oxygen inhibitory properties. These can be used either alone or in combination.

Photocationic polymerization initiators include sulfonic acid esters, imide sulfonates, dialkyl-4-hydroxysulfonium salts, arylsulfonic acid-p-nitrobenzyl esters, silanol-aluminum complexes, (η ⁶ -benzene) (η ⁵ -cyclopenta Dienyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto. .

Examples of photo radical polymerization initiators and photo cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, etc. More specifically, diphenyliodonium, ditolyliodonium, iodonium chloride such as bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, Iodonium salts such as hexafluoroantimonate salt, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromide, borofluoride, hex Sulfonium salts such as fluorophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. It is not limited to these.

  Examples of photoanionic polymerization initiators include compounds that generate amines upon irradiation with ultraviolet light, and more specifically 1,10-diaminodecane, 4,4′-trimethylenedipiperidine, carbamates and derivatives thereof, and cobalt-amines. Complexes, aminooxyiminos, ammonium borates and the like can be exemplified, and a commercial product is Midori Chemical Co., Ltd. NBC-101.

  The blending amount of the polymerization initiator is preferably 2% by weight to 20% by weight, more preferably 2% by weight to 15% by weight, and particularly preferably 5% by weight to 9% by weight in the black ink for correcting minute coloring pattern defects.

  In addition, the black ink for correcting minute color pattern defects according to the present invention may contain a surfactant, a crosslinking agent, and the like.

  When various surfactants are used in combination, it is possible to prevent the top surface of the coating from being sharpened during coating or to improve the dispersion stability of the colorant. However, in the present invention, it may be preferable not to blend in order to bring the static surface tension described later into the range described later. There are no particular limitations on the surfactant, but specific examples include anionic surfactants typified by alkylnaphthalene sulfonates and phosphate ester salts, cationic surfactants typified by amine salts, and aminocarboxylic acids. And amphoteric surfactants typified by the betaine type.

  The blending amount of the surfactant is preferably 0.01% by weight to 2% by weight, more preferably 0.01% by weight to 0.5% by weight in the black ink for correcting minute coloring pattern defects, and 0.01% by weight. -0.1 wt% is particularly preferred.

  When a crosslinking agent is used, the solvent resistance and heat resistance of the corrected portion can be improved, and particularly in the case of a silane-based crosslinking agent, the adhesion of the corrected portion can be improved.

The crosslinking agent is not particularly limited as long as it is effective for curing the monomer or polymer to be used. For example, an aminoalkyl polyvalent alkoxysilane or a hydrolyzate of aminoaryl polyvalent alkoxysilane or a condensate thereof is preferable. Can be used. In addition to aminoalkyl polyvalent alkoxysilanes or aminoaryl polyvalent alkoxysilanes, or their hydrolyzates or condensates and polyvalent carboxylic acids or polycarboxylic dianhydrides, as well as metal chelates, etc. It can be preferably used.
The blending amount of the crosslinking agent is preferably 0.1% by weight to 5% by weight, more preferably 0.1% by weight to 3% by weight, and more preferably 0.1% by weight to 1.% by weight in the black ink for correcting minute coloring pattern defects. 5% by weight is particularly preferred.

  In the production of the black ink for correcting microcolored pattern defects according to the present invention, a method of mixing and dispersing the three colorants, a monomer having a reactive functional group, a polymer, a solvent, and other components as a whole, or A method of mixing each component separately in advance and then mixing them together, for example, a monomer solution having a polymer and a reactive functional group is added to a dispersion of a colorant in which a solvent and a colorant are mixed and dispersed in advance. A mixing method or the like can be used. At this time, the colorant dispersion may be obtained by mixing and dispersing the solvent and the whole of the three colorants, or by preparing and mixing each of the three colorant dispersions. May be. Regarding the selection of these production methods, it is preferable to select an appropriate one mainly depending on the type of colorant. However, in the present invention, since the amount of the solvent is relatively small, one of the functions of the solvent at the time of production is shown. It is preferable to produce a part in place of a monomer having a reactive functional group. In this case, for example, a polymer and a monomer having a reactive functional group are mixed in advance and mixed to prepare a varnish, and a dispersion of a colorant dispersed in advance by mixing a solvent and a colorant is separately prepared. After mixing the dispersion of the colorant, the ink can be produced by further adjusting the viscosity with a solvent or the like. The other optional components are appropriately blended so as to exhibit their functions.

  In the production of the black ink for correcting minute color pattern defects according to the present invention, the dispersion method of the colorant in the ink or in the dispersion of the colorant is not particularly limited, and the kneader, roll mill, attritor, super mill, dissolver, Various methods such as a known disperser such as a homomixer and a sand mill can be used.

  The black ink for correcting microcolored pattern defects thus obtained preferably has a solid content concentration of 30% to 75% by weight, more preferably 45% to 75% by weight, and 50 More preferably, it is from 70% by weight.

  The colorant concentration in the solid content is preferably 5% by weight to 40% by weight, more preferably 10% by weight to 35% by weight, and still more preferably 15% by weight to 35% by weight.

  The concentration of the binder component in the solid content is preferably 30% by weight to 85% by weight, more preferably 35% by weight to 80% by weight, and still more preferably 40% by weight to 75% by weight. .

  In addition, solid content concentration here is weight% with respect to the ink total weight of the net weight of ink content other than a solvent, ie, a coloring agent, the monomer which has a reactive functional group, a polymer, and other arbitrary components. . Further, the concentration of the colorant in the solid content is expressed as the weight percent of the colorant with respect to the weight of the solid content contained in the ink. Furthermore, the density | concentration of the binder component in solid content is represented by weight% of the binder component (namely, in this invention, the total amount of the monomer and polymer which has a reactive functional group) with respect to the weight of the solid content contained in ink.

  The ink produced in the present invention tends to have a high solid content because the amount of the solvent can be reduced by blending a monomer having a reactive functional group and partially replacing the solvent function. Accordingly, since the solvent volatilization amount is small, the stability of physical properties such as the viscosity of the ink is improved during storage and use, and the volume reduction rate due to the volatilization of the solvent is reduced after the ink is applied. Since the volume reduction rate is small, it is possible to make the film thickness of the part replenished in the missing area sufficiently thick with a small amount of ink adhesion, eliminating the trouble of repeated application, and the adhered ink droplets are not dried. However, since the volume is small, it is difficult to protrude to the periphery, and the formation of new protrusions and the occurrence of color mixing defects can be avoided.

  Further, the binder component concentration in the solid content of the ink in the present invention tends to be high because a monomer having a reactive functional group that can partially replace the solvent function becomes a binder component after curing. Therefore, the adhesion of the coating film after drying to the substrate is good, and the solvent resistance and heat resistance of the corrected portion are also high.

  The viscosity of the black ink for correcting minute color pattern defects according to the present invention is 40 to 300 mPa · sec, more preferably 50 to 150 mPa · sec, and particularly preferably 55 mPa · s to 90 mPa · sec.

  If the ink viscosity is too low, the spots will bleed and spread after application, causing color mixing defects. Conversely, if the ink viscosity is too high, the thickness of the application spot will increase and the color will become darker, but the upper surface of the application spot will be gentle. Disappears and the height of the protrusion increases.

  If the viscosity of the ink is in the above range, the coating spot has a gentle shape, no bleeding occurs, and the protrusion height is within the allowable range.

  The ink viscosity is preferably adjusted by adjusting the amount of solvent added.

  The viscosity of the ink as used in the present invention is measured for 1 minute at 25 ° C. using a B-type viscometer (for example, product name: VISCOMETER TV-20, manufactured by TOKIMEC) using a BL adapter, M1 rotor, or M2 rotor. Then, find the value.

The relationship between the shear rate γ value and the shear stress τ value can be expressed by the following formula (1).
τ = Kγ ^L (1)
(However, 0.081 ≦ K ≦ 0.111, 0.881 ≦ L ≦ 0.954)
The shear rate γ value and the shear stress τ value of the correction black ink of the present invention are determined by measuring the viscoelasticity with a rheometer (viscoelasticity measuring device) (for example, ARES100, manufactured by Rheometric Scientific F.E.). The relationship between the shear rate γ value and the shear stress τ value can be calculated. This relationship can be plotted on a log-logarithm, an approximate expression of this plot can be calculated, and the slope of expression (1) can be obtained.

  The black ink for correcting minute color pattern defects according to the present invention has a τ value of 0.3 to 1.3 when the γ value is 10, and a τ value of 4.0 to 10.0 when the γ value is 100. Is preferable from the viewpoint of ink applicability.

  Further, when the γ value is 10 to 100, the τ value is 0.3 to 10.0, the inclination is 0.075 to 0.15, and the order is 0.8 to 1.1. From the viewpoint of sex.

  When it is within the above range, there is an advantage that the ink easily adheres to the needle tip when the ink is applied to the color loss portion by the needle-shaped medium.

  The static surface tension of the black ink for correcting minute coloring pattern defects according to the present invention is preferably 20 mN / m to 45 mN / m, more preferably 25 mN / m to 35 mN / m at 25 ° C., It is particularly preferably 25 mN / m to 32 mN / m.

  Here, static surface tension is measured by using a surface tension meter (for example, Kyowa Chemical Co., Ltd., trade name: DIGI-O-MATIC ESB-IV), taking 30 mL of ink in a small petri dish (diameter 5 cm), and the platinum plate is in contact with it. And determine the static surface tension after 1 minute.

  When the static surface tension is in the above range, there is an advantage that the ink does not protrude from the position where the ink is applied after application, spreads and causes a color mixing defect, or does not create a new protrusion.

  Further, the black ink for correcting minute color pattern defects according to the present invention has an optical density of 1.0 or more, further 1.2 or more, particularly 1.4 or more when the film thickness upon curing is 1.9 μm or less. This is preferable because a sufficient shielding effect can be obtained without making the corrected portion conspicuous.

  Next, a correction method using the black ink for correcting a minute colored pattern defect according to the present invention will be described.

  In the following, the correction of the black matrix portion of the color filter for liquid crystal display, which is a typical application of the correction black ink of the present invention, will be described as an example. Modifications can be made in the same manner after changing accordingly.

  As an outline of the color filter manufacturing process, generally, a black matrix is first formed on a transparent substrate, and then pixel patterns such as R, G, and B are formed one by one. Examples of the pixel pattern include a stripe type, a mosaic type, a triangle type, a four pixel arrangement type, and an island type arranged in a “<” shape. Further, if necessary, a protective film is formed on the pixel pattern, and a transparent conductive film is further laminated thereon to form a color filter.

  The pattern correction with the black ink for correcting minute coloring pattern defects according to the present invention may be performed at any point in the color filter manufacturing process. That is, after the black matrix is formed, the black matrix may be corrected and subsequently RGB may be formed, or the black matrix may be corrected after all the black matrix and RGB stripes are formed. However, if the correction is made after the formation of the protective film or the transparent conductive film, the protective film and the transparent conductive film layer on the corrected portion are lost, so it is common to make the correction before forming the protective film or the transparent conductive film layer. .

  There is no particular limitation on the type of pattern defect to be corrected with the black ink for correction according to the present invention. For example, black defects such as foreign matter defects or dark color defects due to pigment agglomeration are volatilized in the vicinity of the defective portion with a laser, etc., and it becomes a white defect that loses color alone, so the correction black ink of the present invention is further applied for correction. To do. Further, white defects such as color loss defects are corrected by applying the correction black ink of the present invention as it is.

  When corrected using the correction black ink according to the present invention, the level difference from the normal pixel portion is sufficiently small, so that a product defect due to a new protrusion does not occur even when a liquid crystal display panel is assembled, Since the ink does not protrude from the position where the ink is applied, it spreads and causes a color mixing defect, and the area of the correction portion increases and the correction portion does not stand out.

  In addition, since the black ink for correction according to the present invention does not contain carbon black, even when the corrected portion generates a new protrusion, avoid contact between the counter substrate and the protrusion and causing conduction. Can do.

  The method for applying the correction black ink according to the present invention is not particularly limited. However, as disclosed in JP-A-8-182949, the ink is attached to a needle-like application medium, and then finely coated. A method of coating the colored pattern defect portion is preferable because it can cope with a minute correction spot. It is more preferable that the tip of the needle-like member on the ink application side is processed into a flat shape because damage to the minute colored pattern defect portion due to contact with the needle-like member can be prevented. It is more preferable to change the diameter of the tip of the acicular application medium in accordance with the size of the defect to be corrected because it can cope with defects of various sizes.

  There is no particular need to dry after applying the correction black ink according to the present invention, but there is no particular limitation on the method for drying, for example, air drying, heat drying, vacuum drying or the like. In the case of heat-drying, it is preferable to use an oven, a hot plate, etc., and carry out at 50-300 degreeC for 1 minute-3 hours. In the case of correction, since drying in a local and short time is often required, a method of heating and drying only the corrected portion using, for example, an infrared spot heater can be preferably used.

  The step of irradiating the finely colored pattern defect correcting black ink after applying the finely colored pattern defect correcting black ink to the finely colored pattern defect part is a monomer or polymer having a photoreactive functional group in the correcting black ink according to the present invention. Is preferable because the surface of the correction portion can be temporarily hardened instantaneously or the entire correction portion can be hardened in a short time. In the case where the surface of the correction portion is temporarily hardened instantaneously, there is an advantage that the fluidity of the ink can be stopped instantaneously and the ink shape of the correction portion can be stabilized. Further, when curing is performed in a short time by the heating process, sublimation of the colorant and thermal destruction of the defective portion may occur, but such disadvantages are unlikely to occur when light irradiation is performed.

  When the black ink for correcting micro-colored pattern defects according to the present invention has a monomer or polymer having a heat-reactive functional group, a heating step is provided after the correction black ink is applied to the defective portion. . Particularly preferably, a heating step is provided after the light irradiation.

  By the above method, correction is performed by compensating for the micro-colored pattern defect portion with the cured product of the micro-colored pattern defect correcting black ink according to the present invention, and if necessary, an overcoat layer for smoothing, a protective film, A transparent conductive film is formed, and a color filter having the same performance as a defect-free product can be manufactured.

  The color filter according to the present invention corrected with the black ink for correcting micro-pattern defects is used for display panel components such as personal computers, word processors, engineering workstations, navigation systems, liquid crystal televisions, and videos. It is also preferably used for components such as liquid crystal projections with clear image quality.

  In the color filter according to the present invention, it is preferable that the thickness of the portion corrected with the black ink for correcting the minute coloring pattern defect is not different from the surrounding thickness in terms of smoothness, but the balance with the coloring density The difference between the corrected portion and the surrounding area is preferably the same in terms of smoothness, but there is no difference in thickness from the surrounding area. The step between the portion corrected with the ink and its surroundings is preferably −3 μm to +5 μm, more preferably −2 μm to +3 μm, and particularly preferably −1 μm to +2 μm.

  If it is in the above range, the film thickness of the replenished portion is sufficiently thick, the replenished portion is sufficiently colored, and does not cause defective products as new protrusions. preferable.

  The color filter according to the present invention has an optical density of 1.0 or more, and further 1.2 when the thickness of the portion corrected with the cured product of the black ink for correcting microscopic pattern defects is 1.9 μm or less. As mentioned above, it can be set as especially 1.4 or more, and sufficient shielding effect is acquired.

(Production Examples 1-3: Preparation of pigment dispersion)
Colorants, pigment dispersants, and solvents were weighed and mixed according to the blending amounts shown in Table 1. This mixed solution is dispersed for 3 hours with a paint shaker (manufactured by Asada Tekko, trade name: PAINT SHAKER) using zirconia beads (0.3 mmφ) (manufactured by Showa Shell Sekiyu, trade name: Microhaika Z Z300). A pigment dispersion was obtained.

(Production Example 4: Preparation of varnish)
A polymer, a monomer having a reactive functional group, and a polymerization inhibitor were mixed according to the blending amounts shown in Table 2. This mixed liquid was heated to 110 ° C., and the polymer was dissolved in the monomer having a reactive functional group to obtain a varnish adjusting liquid.

Example 1
With the blending amounts shown in Table 3, the pigment dispersions obtained in Production Examples 1 to 3, the polymerization initiator, and the solvent were mixed, the polymerization initiator was dissolved, and a pigment dispersion was newly obtained. Next, the varnish obtained in Production Example 4 and a monomer having a reactive functional group were mixed and dissolved to newly obtain a varnish preparation solution. The pigment dispersion and the varnish preparation were mixed, and the viscosity was measured by the viscosity measurement method described below. If necessary, the viscosity was further adjusted using a solvent. Table 4 shows the composition of the obtained black ink for correcting each minute colored pattern defect.

(Comparative Example 1)
20 g of carbon black (Special Black 250 manufactured by Degussa) and 8 g of a 50% methoxypropyl acetate (manufactured by Daicel Chemical Industries) solution of the pigment dispersant Solsperse 24000GR (manufactured by Avicia) were mixed, and the pigment was dispersed by a roll mill. This was diluted with 72 g of methoxypropyl acetate (manufactured by Daicel Chemical Industries) to prepare a pigment dispersion. Further, 6.00 g of a 40% solution of a methacrylic acid copolymer (Dainippon Ink & Chemicals, Inc., EXED binder LE-0939), 20.10 g of Kayrad DPHA (manufactured by Nippon Kayaku) as a monomer, and Irgacure 369 as a polymerization initiator A varnish preparation solution was prepared by dissolving 6.00 g (manufactured by Ciba Specialty Chemicals) and 1.5 g of EAB-F (manufactured by Hodogaya Chemical) in a solvent. 41.3 g of pigment dispersion and 41.96 g of varnish preparation were mixed, and further diluted with 16.74 g of PGMEA to prepare a colored resist for forming a black matrix.

(Comparative Example 2)
Carbon black (Degussa Special Black 250) 30.0g, Pigment Dispersant Solsperse 24000GR 50% solution (Avisia) 7.5g, PGMEA 62.5g, weighed in the same manner as in Production Examples 1-3. And a pigment dispersion was obtained. To this 65.55 g of the pigment dispersion, 4.81 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and 2.06 g of Kayacure DETX-S (manufactured by Nippon Kayaku) are mixed and dissolved as a polymerization initiator. A dispersion was obtained.

  13.76 g of the varnish obtained in Production Example 4 and 13.76 g of Kayarad DPHA were mixed to newly obtain a varnish preparation solution.

  72.42 g of the dispersion, 27.52 g of the varnish, and 0.06 g of PGMEA were mixed to obtain a correction carbon black ink.

(Evaluation methods)
1. Viscosity, shear rate γ value, shear stress τ value, slope of formula (1) The viscosity of the ink was measured at 25 ° C. using a B-type viscometer (trade name: VISCOMETER TV-20, BL adapter) Using an M1 rotor and an M2 rotor, measurement was performed for 1 minute to obtain the value.

  In addition, the shear rate γ value, the shear stress τ value, and the slope of the equation (1) were determined by measuring the viscoelasticity with a rheometer (viscoelasticity measuring instrument) (ARES100, manufactured by Rheometric Scientific F.E.). The relationship between the shear rate γ value and the shear stress τ value was calculated. This relationship was plotted on a log-logarithm, an approximate expression of this plot was calculated, and the slope of expression (1) was obtained. FIG. 1 shows an example of a graph obtained by logarithmically plotting the shear rate and shear stress of the black ink for correcting minute colored pattern defects (Example 1), and a graph showing the viscosity measurement results when the shear rate is changed.

2. Static surface tension Static surface tension was measured using a surface tension meter (trade name: DIGI-O (OH?)-MATIC ESB-IV, manufactured by Kyowa Chemical Co., Ltd.). The static surface tension 1 minute after the plate contacted was determined.

3. Step measurement and evaluation of the correction part The step of the correction part is measured by a difference in the depth of focus of the microscope using an ultra-deep shape measurement microscope (manufactured by Keyence Co., Ltd., trade name: VK8510), or a stylus type shape measuring device (manufactured by Dencor). (Trade name: P-1 LongScanProfiler). If the level difference is 6 μm or more, it is not preferable for correcting the color filter, so it was determined as defective.

4). Visual evaluation of the corrected portion The corrected color filter was placed on the backlight, and pass / fail was judged by observing the corrected portion. If the correction area is clearly visible by visual inspection because the correction area becomes too large or the color is too thin due to ink bleeding, it was judged as defective.

5). Chemical resistance test of the correction part The correction part was immersed in each solution of isopropyl alcohol, N-methylpyrrolidone and γ-butyrolactone at room temperature for 30 minutes, washed with water, dried with water, observed with a microscope, peeled off at the correction part, and cracked. If no abnormalities occur, it was accepted.

  For Example 1 and Comparative Examples 1 and 2, the viscosity, shear rate γ value, shear stress τ value, slope of formula (1), static surface tension, and the ink composition obtained above were determined. Table 5 shows the solid content concentration, the colorant concentration in the solid content, the binder component concentration in the solid content, the protrusion height measurement, the visual evaluation result of the corrected portion, and the chemical resistance test result.

  From the above results, in Example 1, the applicability to the correction part is good, and the correction can be satisfactorily corrected in all points of correction, visual appearance after curing, protrusion height, and chemical resistance. However, for Comparative Examples 1 and 2, good correction could not be performed.

It is a graph which shows an example of the viscosity measurement result when changing the shear rate and the logarithm plotting of the shear rate and the shear stress of the black ink for fine coloring pattern defect correction according to the present invention.

Explanation of symbols

1 ... Graph plotting logarithm of shear rate and shear stress 2 ... Graph showing viscosity measurement result when shear rate is changed

Claims (11)

  A black ink for correcting minute color pattern defects, which contains at least red, yellow and blue colorants, a monomer having a reactive functional group, a polymer, and a solvent, and the blending amount of the solvent is that of the entire ink. 25 wt% to 70 wt%, the blending amount of the monomer is 15 wt% to 65 wt% of the whole ink, and the blending amount of the polymer is 1 wt% to 25 wt% of the whole ink. And the total blending amount of the monomer and the polymer is 30% to 85% by weight of the total solid content in the ink, and the total blending amount of the three colorants is the entire ink. 5 to 40% by weight, and the viscosity of the ink is 40 to 300 mPa · sec.   2. The micro colored pattern defect according to claim 1, wherein the ink has an optical density of 1.0 or more in a measurement wavelength range of 400 nm to 760 nm when the film thickness upon curing is 1.9 μm or less. Black ink for correction. In the following formula (1), the ink is
τ = Kγ ^L (1)
(However, 0.081 ≦ K ≦ 0.111, 0.881 ≦ L ≦ 0.954)
The τ value is 0.3 to 1.3 when the γ value is 10, and the τ value is 4.0 to 10.0 when the γ value is 100. The black ink for correcting the minute coloring pattern defect described. In the following formula (1), the ink is
τ = Kγ ^L (1)
(However, 0.081 ≦ K ≦ 0.111, 0.881 ≦ L ≦ 0.954)
The τ value is 0.3 to 10 when the γ value is 10 to 100, the slope is 0.075 to 0.15, and the order is 0.8 to 1.1. Or the black ink for correcting the minute colored pattern defect according to any one of 2;   5. The black ink for correcting fine color pattern defects according to claim 1, wherein the static surface tension of the ink is 20 mN / m to 45 mN / m at 25 ° C. 5.   6. The black ink for correcting microcolored pattern defects according to claim 1, wherein the monomer having a reactive functional group has two or more reactive functional groups in one molecule.   The black ink for correcting minute coloring pattern defects according to any one of claims 1 to 6, further comprising a polymerization inhibitor.   The black ink for correcting a minute coloring pattern defect according to any one of claims 1 to 7, wherein the polymer is a diallyl phthalate prepolymer. The ink for correcting a minute colored pattern defect according to any one of claims 1 to 8, wherein the conductivity of the colorant of each color is 10 ¹⁰ Ωcm or more.   10. A color filter, wherein a defect of a black matrix pattern is compensated and corrected by a cured product of the black ink for correcting a minute coloring pattern defect according to any one of claims 1 to 9.   The step between the portion corrected with the black ink for correcting a minute colored pattern defect according to any one of claims 1 to 9 and the periphery thereof is -3 µm to +5 µm. Color filter.

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