JP2011002550A - Method for manufacturing color filter substrate with spacer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for placing and forming a spacer having a predetermined height at a predetermined position on a color filter formed on a transparent substrate with high accuracy by using an inkjet method.SOLUTION: The method for manufacturing a color filter substrate includes steps of forming a light-shielding film pattern having voids in a predetermined period on a transparent substrate, ejecting spacer ink 7 containing at least spacer particles and a black pigment included in the light-shielding film to the voids by an inkjet method, and forming a color filter.

Description

  The present invention relates to a technique for selectively arranging and fixing spacer particles on a light shielding portion of a color filter substrate by an inkjet method.

  Currently, liquid crystal displays are widely used in personal computers, portable electronic devices, and the like. In this liquid crystal display, the spacer plays a role of maintaining a constant gap between the opposing substrates and maintaining an appropriate thickness of the liquid crystal layer.

  In a conventional method for manufacturing a liquid crystal display, spacers are dispersed on a substrate on which pixel electrodes are formed. Therefore, since the position control of the spacer is impossible and the arrangement is random, there is a problem that the spacer is also arranged on the pixel electrode of the display unit. The spacer is generally made of synthetic resin, glass, or the like, and when the spacer is disposed on the pixel electrode, the spacer portion leaks light due to the biasing action. Further, there is a problem that light leakage occurs due to disorder of the alignment of the liquid crystal in the vicinity of the spacer, and the display quality is deteriorated due to a decrease in contrast and color tone.

  In order to solve the problems associated with such a random distribution of the spacers, it is necessary to arrange the spacers in the light shielding layer part. As a method of arranging the spacers only at specific positions in this way, a photolithographic method, Many forming methods using an ink jet method have been proposed.

  The photolithographic method is a main manufacturing method for a color filter substrate, in which a photosensitive resist is coated on the entire surface, and exposed and developed through a photomask having an exposure pattern to sequentially form color filters. It is a way to go.

  Since this method is excellent in pattern accuracy and manufacturing stability, numerous patent applications have been filed. For example, in Patent Documents 1 to 4, a photosensitive resin composition corresponding to improvement in developability and reduction in deformation amount, etc. Things are disclosed. However, in the first place, the photolithography method is a method of forming a pattern by exposing through a photomask and then developing and removing unnecessary portions. For spacer formation in which the pattern forming portion is less than 1%, There is a demerit that material loss is very large.

  On the other hand, the inkjet method is a method with excellent material use efficiency that can apply a necessary amount of ink to a desired portion from a micro nozzle having a diameter of several tens of μm.

  This method can form a desired micropattern directly on a substrate in combination with a precision stage, and has recently been actively developed in liquid crystal related technologies. For example, Patent Documents 5 to 7 disclose a method of directly forming a spacer at a desired position. However, in order to eject droplets containing spacer particles of several microns, one having a large inkjet nozzle diameter must be selected, and the droplet diameter formed on the substrate is about 50 μm. Even if droplets are landed on the light-shielding film with high accuracy by ink jet printing, the position of the spacer particles contained in the droplets after the liquid drying is uncontrollable, so the light-shielding film has a narrow line width of about 10 μm. However, it is difficult to selectively dispose spacers only on the light-shielding film.

As a means for solving this problem, for example, Patent Documents 7 to 8 propose a method of changing the surface state of a region where ink jet printing is performed and a non-printing region. However, a separate process must be performed for this purpose, which is not preferable because the process becomes complicated.

JP 2007-206328 A JP 2007-204588 A JP 2007-65640 A JP 2006-276696 A JP 2001-83524 A JP 2001-188235 A JP 2004-021199 A JP 2008-96515 A

  The present invention provides a method for accurately arranging and forming a spacer having a predetermined height at a predetermined position on a color filter formed on a transparent substrate by using an inkjet method.

In order to achieve the above object in the present invention, first, in the invention of claim 1, a step of forming a light-shielding film pattern having voids at a predetermined cycle on a transparent substrate;
Discharging a spacer ink having at least spacer particles and a black pigment contained in the light shielding film into the gap by an inkjet method;
Forming a colored pixel, and a manufacturing method of a color filter substrate with a spacer.

  According to a second aspect of the present invention, in the method for manufacturing a color filter substrate with a spacer according to the first aspect, the gap is formed simultaneously with the formation of the light shielding film pattern.

  According to a third aspect of the present invention, in the method for producing a color filter substrate with a spacer according to the first or second aspect, the gap is circular and has a diameter of 5 μm or more. is there.

  Next, according to a fourth aspect of the present invention, the spacer according to any one of the first to third aspects, wherein the light-shielding film exhibits a liquid repellency with a contact angle of 90 ° or more with respect to the spacer ink. This is a method for manufacturing an attached color filter substrate.

  Next, in the invention of claim 5, the spacer ink is mainly composed of an organic solvent having a boiling point of 150 ° C. or higher, a black spacer particle having a particle diameter of 1 to 10 μm, 0.1 to 10% by weight, and a particle diameter of 10 The black pigment of ˜500 nm is contained in an amount of 1 to 30% by weight, the viscosity of the spacer ink at 23 ° C. is 30 cps or less, and the surface tension is 20 to 50 mN / m. 4. The method for producing a color filter substrate with a spacer according to any one of 4 above.

  Next, according to a sixth aspect of the present invention, the spacer ink includes an adhesive component, and the adhesive component is thermally cured / energy ray cured / ultraviolet cured. The manufacturing method of the color filter substrate with a spacer described in item 1 is used.

In the next seventh aspect, according to any one of claims 1 to 6 in which the spacer particle number density arranged in said gap, characterized in that in the range of 1,000 to 50,000 pieces / cm ² This is a method for manufacturing a color filter substrate with a spacer.

  Next, in the invention of claim 8, the red, green, and blue pixels of the color filter are all formed by an ink jet printing method and formed in a lump including the spacer. 7. The method for producing a color filter substrate with a spacer according to any one of 7 above.

  Since the present invention has the above features, the following effects are obtained.

  That is, according to the first aspect of the present invention, the spacer material can be arranged in a necessary amount in a necessary position by ink jet printing. Arrangement can be realized.

  That is, according to the second aspect of the present invention, it is possible to simultaneously provide the spacer-arrangement gap in the light shielding film forming process, so that it is not necessary to make a gap again and the process is rationalized.

  That is, according to the third aspect of the present invention, since the gap of the light shielding film is circular and the diameter thereof is 5 μm or more, it is possible to fix the spacer ink droplets by the ink jet method smoothly.

  That is, according to the fourth aspect of the invention, the light-shielding film has a liquid repellency with a contact angle of 90 ° or more with respect to the spacer ink. Thus, it can be physically moved into the gap corresponding to the recess.

  That is, according to the invention according to claim 5, when a general piezo ink jet head is used by preparing an ink having a viscosity of 30 cps or less and a surface tension of 20 to 50 mN / m at 23 ° C. In this case, accurate and stable discharge can be performed.

  That is, according to the invention of claim 6, since the spacer particles are fixed in the gap, the spacer particles are not detached from the gap even after the post-process or the panel formation.

That is, according to the seventh aspect of the present invention, the number of spacer particles arranged selectively in the gaps of the light-shielding film pattern of the color filter substrate by the above method is 1000 to 50000 / cm ² . Therefore, it can be used in a product without any non-uniformity in cell thickness due to the above, and without any obstacle in the application of an alignment film or liquid crystal in the paneling process.

  That is, according to the invention according to claim 8, the red, green, and blue pixels as the color filter are all formed by the ink jet printing method, and are formed in a lump including the spacer, thereby greatly reducing the process. Is possible.

Process drawing explaining the concept of the spacer formation process which becomes this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  As a light-shielding film forming material according to the present invention, a coating composition containing a black light-shielding material, a photosensitive polymer, a photopolymerizable monomer, a photopolymerization initiator and a solvent as a main component, and further containing a dispersant and the like is used. Can do. As material properties, performance such as excellent light shielding properties, alkali developability, and excellent sensitivity at the time of exposure is required.

  Examples of the black light shielding material include black pigments, black dyes, and inorganic materials. For example, one or two selected from the group consisting of black organic pigments, carbon black, aniline black, graphite, titanium oxide, and iron black. A mixture of seeds or more can be used.

  As the photosensitive polymer, an acrylic polymer having an ethylenically unsaturated double bond imparting photosensitivity and a carboxyalkyl group imparting developability is suitably used.

  As the photopolymerizable monomer, a bifunctional or higher monomer having an ethylenically unsaturated double bond, an oligomer, a prepolymer, or the like can be used. Specific examples of the photopolymerizable monomer include, for example, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth). ) Acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These compounds can be used alone or in admixture of two or more.

  As photopolymerization initiators, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, 2-methyl-1- {4- (methylthio) phenyl}- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)} and the like. These compounds can be used alone or in admixture of two or more.

  Examples of the dispersant include nonionic surfactants such as polyoxyethylene alkyl ethers, and ionic surfactants such as sodium alkylbenzene sulfonate, poly fatty acid salts, fatty acid salt alkyl phosphates, and tetraalkyl ammonium salts. Other examples include organic pigment derivatives and polyester. One type of dispersant may be used alone, or two or more types of dispersants may be mixed and used.

  The solvent is appropriately selected and used from the viewpoint of the coating property and dispersion stability of the black resin composition, and examples thereof include toluene, xylene, ethyl cellosolve, ethyl cellosolve acetate, diclime, and cyclohexanone.

  A light-shielding film pattern can be formed by applying a photosensitive black resin composition in which a predetermined amount of the above-described materials are mixed by a conventional method and patterning by a photolithographic technique.

  The thickness of the light shielding film is preferably 0.5 μm to 3.0 μm. When the thickness is less than 0.5 μm, it is difficult to obtain a sufficient light-shielding property.

In the present invention, at the same time when the light shielding film pattern is formed, the spacer arrangement gaps are periodically formed at predetermined positions in the light shielding film pattern. Since the light-shielding film pattern is formed by exposure through a photomask, if the space for spacer arrangement is incorporated in the mask pattern, it can be easily formed.

  The gap shape for arranging the spacers is preferably circular, because the ink discharged from the ink jet apparatus spreads to the corners of the gap in the same way. In the case of a quadrangular shape, if the ink does not penetrate into the corners of the four corners, there may be a white defect. However, it is not necessarily limited to a circle depending on the position, size, etc., used for the arrangement of the gaps.

  Moreover, it is preferable that the space | gap for spacer arrangement | positioning is the size below a light shielding film pattern width, and the diameter is 5 micrometers or more. When the thickness is 5 μm or less, it is difficult to fit all the spacer particles contained in the plate in the plate, which may cause uneven cell gap.

  The light shielding film in the present invention needs to have liquid repellency with respect to the spacer ink. Either a method for imparting liquid repellency to the material itself at the time of forming the light shielding film or a method for imparting liquid repellency separately after the formation of the light shielding film may be used, but the former is preferable in view of the efficiency of the formation process.

  As a material used for imparting liquid repellency, a release agent represented by silicone oil or silicone varnish may be used, or a thin silicone rubber may be provided. For the same purpose, fluorine-based resins and fluorine-based rubbers may be used, or the fluororesin fine powder may be mixed with silicone rubber or ordinary rubber to obtain peelability.

  Specific silicones include dimethylpolysiloxanes with various molecular weights, other methylhydropolysiloxanes, methylphenylsilicone oils, methylchlorinated phenylsilicone oils, or copolymers of these polysiloxanes with organic compounds. Can be used. Silicone rubber is a combination of two-component diorganopolysiloxane and a tri- or higher functional silane as a crosslinking agent, or a combination of siloxane and a curing catalyst, or one-component diorganopolysiloxane, acetone oxime, and various methoxys. Combinations of silane, methyltriacetoxysilane, and the like are used, and other polysiloxanes for adjusting rubber hardness are appropriately used.

  The light-shielding film in the present invention preferably has a liquid repellency with a contact angle of 90 ° or more with respect to the spacer ink, and if it is 90 ° or less, it becomes difficult to express the gathering property of the spacer ink in the gap, This is not preferable because it may cause unevenness in height.

  As the organic solvent used in the spacer ink of the present invention, an organic solvent having a boiling point of 150 ° C. or higher, preferably 180 ° C. or higher is used, and one or a mixture of two or more can be used.

  Examples of the organic solvent used in the present invention include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,2,4-butanetriol, 2 , 2'-thiodiethanol and other high-boiling and low-volatile polyhydric alcohols are used, and N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, monoethanolamine, N, N-dimethyl Organic solvents such as ethanolamine, N, N-diethylethanolamine, diethanolamine, Nn-butyldiethanolamine, triisopropanolamine, and triethanolamine can be added.

Moreover, it is preferable that the addition amount of the organic solvent whose boiling point is 150 degreeC or more in this invention is 50 to 90%. If the added amount is 50% or less, the volatility of the spacer ink is increased and the ink stability is lowered, and if it is 90% or more, the viscosity of the spacer ink is increased, causing a discharge failure during inkjet printing. This is not preferable.

  As the spacer particles used in the spacer ink of the present invention, black spherical particles having a particle diameter of 1 to 10 μm, which are colored by dispersing a black pigment in the particles themselves, can be used alone or in combination.

  The material of the spacer particles is not particularly limited, and examples thereof include resins, organic substances, inorganic substances, compounds and mixtures thereof, and the like. The resin is not particularly limited. For example, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polysulfone, polyphenylene oxide. Linear or cross-linked polymer such as polyacetal; epoxy resin, phenol resin, melamine resin, benzoguanamine resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester Examples thereof include resins having a crosslinked structure such as a polymer, diallyl phthalate polymer, and triallyl isocyanurate polymer. Moreover, silica etc. are mentioned as an inorganic substance.

  The solid content concentration of the spacer in the spacer ink according to the present invention is not particularly limited, but is preferably 0.1 to 10% of the total ink, for example.

  When the solid content concentration of the spacer particles in the spacer ink is less than 0.1%, the discharged droplets tend not to contain the spacer particles, the spacer particle density on the color filter substrate is lowered, and 10% Exceeding this is not preferable because the spacer particles are aggregated and the nozzles of the ink jet head are clogged. In addition, an increase in the average number of spacer particles contained in the droplets is undesirable because particles overflowing from the voids are generated, resulting in uneven gaps.

  As the black pigment used in the spacer ink, one or more selected types such as black organic pigment having a particle diameter of 10 to 500 nm, carbon black, aniline black, graphite, titanium oxide, and iron black can be mixed and used. . However, the black pigment is the same as the pigment used for the light shielding film.

  The solid content concentration of the black pigment in the spacer ink is not particularly limited, but is preferably 1 to 30% of the total dispersion, for example.

  If the solid content concentration of the black pigment in the spacer ink is less than 1%, the concentration is low, so that even if it is placed in the gap, the light shielding property is insufficient, which may cause white spots, and if it exceeds 30%. In addition, the black pigments or the spacer particles are aggregated, which may cause nozzle clogging of the inkjet head, which is not preferable.

  Examples of the adhesive resin component in the spacer ink include polyacrylate ester, polymethacrylate ester, polyethylacrylate ester, styrene-butadiene copolymer, butadiene copolymer, acrylonitrile-butadiene copolymer, and chloroprene copolymer. Polymer, crosslinked acrylic resin, crosslinked styrene resin, fluororesin, vinylidene fluoride, benzoguanamine resin, phenol resin, polyolefin resin, cellulose, styrene-acrylate copolymer, styrene-methacrylate copolymer, polystyrene, Styrene-acrylamide copolymer, n-isobutyl acrylate, acrylonitrile, vinyl acetate, acrylamide, silicone resin, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate , Vinylidene chloride resin, polyvinyl alcohol, cellulose resin, epoxy resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, vinyl chloride resin, polyurethane, etc. It is not something.

  A resin obtained by adding a reactive site such as an acrylic group, a carboxyl group, or an isocyanate group to the resin component, and further adding a crosslinking agent, a photoinitiator, or the like as necessary, can be used as the curable resin. These can be heat-cured, energy-ray cured, or ultraviolet-cured, and can be appropriately selected depending on the process.

  Moreover, the addition amount of the adhesive resin component in this invention is 0.2-20% according to the addition amount of spacer particle | grains, and it is preferable that it is the same amount or more as spacer particle | grains. If the addition amount is 0.2% or less, the adhesion on the color filter substrate is poor, and if it is 20% or more, the viscosity of the spacer ink is remarkably increased, and the ink head causes nozzle clogging. .

  If necessary, alcohols and surfactants are used for the purpose of controlling the wettability between the color filter substrate and the inkjet head and the spacer ink, and one or a mixture of two or more can be used.

  As alcohols, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, etc. can be used, and as the surfactant, one or more anionic, cationic, amphoteric and nonionic surfactants are used. Can be added.

  In the spacer ink according to the present invention, it is preferable that the spacer particles are dispersed in the form of single particles, and various additives such as an adhesive imparting agent, a viscosity adjusting agent, and a pH adjuster as long as the effects thereof are not hindered. An agent, a surfactant, an antifoaming agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a colorant may be added.

  The spacer ink preferably has a viscosity of 30 cps or less at 23 ° C. and a surface tension of 20 to 50 mN / m, and physical properties outside this range are not preferable because the discharge suitability for the ink jet head is remarkably lowered.

  In the present invention, the spacer particles are arranged at the positions of the gaps formed in the light shielding film by the ink jet method. Inkjet systems are classified into two systems, a continuous jet system and a drop-on-demand system, depending on the principle of ink droplet generation. In the present invention, any method can be preferably employed.

  The continuous jet method is a method in which ink droplets are continuously generated and ink droplets are selected according to a recording signal to perform recording, and there are a Sweet type, a microdot type, a Herz type, an IRIS type, and the like. The drop-on-demand method is a method for ejecting ink droplets according to a recording signal, and includes a pressure pulse method, a thermal jet method, and an ERF method.

  The arrangement of the spacer particles on the substrate is not particularly limited, and may be a random arrangement or a pattern arrangement in which a pattern is arranged at a specific position. From the viewpoint of suppressing display quality deterioration such as light leakage caused by the spacer particles, it is preferable to dispose the spacer particles in the non-display portion of the panel. Further, the particle density of the spacers on the substrate is not particularly limited, but it is usually preferably 1000 to 50000 in a 1 cm square region.

  As an application development of the present invention, all processes including the formation of red, green, and blue pixels after the formation of the light shielding film pattern can be collectively formed by an ink jet method.

  The substrate that is the subject of the present invention can be applied to a substrate in which spacer particles are arranged to prevent a short circuit between the upper and lower electrodes, particularly a substrate for a touch panel, but the material of the substrate is particularly limited. Not a thing but a glass plate, a resin plate, etc. can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

<Example 1>
-Preparation of spacer ink-
85 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), 1.5 parts of black spacer particles having a particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., Micropearl KB), photoinitiator (manufactured by Ciba Specialty Chemicals) , Darocur TPO) 1.5 parts was mixed, ultrasonically dispersed, and diluted with 12 parts of propylene glycol monomethyl ether acetate to obtain a spacer ink. The viscosity of the obtained dispersion was 9.4 mPa · s (23 ° C.).

-Formation of patterned light-shielding film-
On a glass substrate, 96 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), 2 parts of photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO), fluorine-based water repellent treatment agent (manufactured by 3M) , EGC-1720) A coating solution in which 2 parts were mixed was applied by spin coating so that the film thickness was about 1 μm after drying, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 10 μm-diameter circular gap at the intersection of light-shielding film patterns arranged in a matrix with a line width of 20 μm, after exposure and development, the film is heat-cured at 180 ° C. for 30 minutes to form a pattern-shaped light shielding A film was formed.

-Spacer formation in the light shielding film gap-
The spacer ink is vacuum defoamed and filled in an inkjet printing apparatus equipped with a piezo-type inkjet head having a discharge amount of 40 pl and a precision stage having an alignment mechanism, and after the alignment of the light shielding film pattern, it corresponds to a gap. Spacer ink droplets were discharged at the positions. After pre-drying at 80 ° C. for 5 minutes, exposure treatment was performed, and heat curing treatment was performed at 180 ° C. for 30 minutes to form a spacer.

~ Preparation of colored ink ~
20 parts of methacrylic acid, 10 parts of methyl methacrylate, 55 parts of butyl methacrylate and 15 parts of hydroxyethyl methacrylate are dissolved in 300 g of butyl lactate, and 0.75 part of azobisisobutylnitrile is added in a nitrogen atmosphere, and the reaction is carried out at 70 ° C. for 5 hours. As a result, an acrylic copolymer resin was obtained. The obtained acrylic copolymer resin was diluted with propylene glycol monomethyl ether acetate so that the resin concentration would be 10% to obtain a diluted solution of the acrylic copolymer resin. 19.0 g of pigment and 0.9 g of dispersant were added to 80.1 g of this diluted solution, and kneaded with three rolls to obtain red, green and blue colored varnishes. Each colored varnish is adjusted with propylene glycol monomethyl ether acetate so that the pigment concentration is 12 to 15% and the viscosity is 10 mPa · s (23 ° C.), and the colors are red (R), green (G), and blue (B). Ink was obtained.

~ Formation of color filter ~
The ink-jet printing apparatus equipped with a piezo-type ink-jet head having a discharge amount of 12 pl and a precision stage having an alignment mechanism is filled with the above-described colored ink by vacuum defoaming treatment, and the alignment of the light-shielding film pattern is performed. The color ink was discharged to form a color filter.

<Example 2>
Example 1 was performed in the same manner as in Example 1 except that the formation of the patterned light-shielding film was performed as follows.

-Formation of patterned light-shielding film-
On a glass substrate, 96 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), 2 parts of photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO), fluorine-based water repellent treatment agent (manufactured by 3M) , EGC-1720) A coating solution in which 2 parts were mixed was applied by spin coating so that the film thickness was about 1.5 μm after drying, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 20 μm-diameter circular gap at the intersection of light-shielding film patterns arranged in a matrix with a line width of 30 μm, after exposure and development, heat-cured at 180 ° C. for 30 minutes to form a pattern-shaped light shielding A film was formed.

<Example 3>
The spacer ink of Example 1 was prepared in the same manner as in Example 1 except that it was prepared as follows.

-Preparation of spacer ink-
86 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), black spacer particles having a particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., Micropearl KB), photoinitiator (manufactured by Ciba Specialty Chemicals) , Darocur TPO) 1.5 parts was mixed, ultrasonically dispersed, and diluted with 12 parts of propylene glycol monomethyl ether acetate to obtain a spacer ink. The viscosity of the obtained dispersion was 8.9 mPa · s (23 ° C.).

<Example 4>
Example 3 was performed in the same manner as in Example 3 except that the formation of the patterned light-shielding film was performed as follows.

-Formation of patterned light-shielding film-
On a glass substrate, 96 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), 2 parts of photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO), fluorine-based water repellent treatment agent (manufactured by 3M) , EGC-1720) A coating solution in which 2 parts were mixed was applied by spin coating so that the film thickness was about 1.5 μm after drying, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 20 μm-diameter circular gap at the intersection of light-shielding film patterns arranged in a matrix with a line width of 30 μm, after exposure and development, heat-cured at 180 ° C. for 30 minutes to form a pattern-shaped light shielding A film was formed.

<Comparative Example 1>
Example 1 was performed in the same manner as in Example 1 except that the formation of the patterned light-shielding film was performed as follows.

-Formation of patterned light-shielding film-
On a glass substrate, 96 parts of black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK), 2 parts of photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO), fluorine-based water repellent treatment agent (manufactured by 3M) , EGC-1720) A coating solution in which 2 parts were mixed was applied by spin coating so that the film thickness was about 1 μm after drying, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 4 μm-diameter circular gap at the intersection of light-shielding film patterns arranged in a matrix with a line width of 20 μm, after exposure and development, the film is heat-cured at 180 ° C. for 30 minutes to form a pattern-shaped light shielding A film was formed.

<Comparative Example 2>
Example 1 was performed in the same manner as in Example 1 except that the formation of the patterned light-shielding film was performed as follows.

-Formation of patterned light-shielding film-
A coating solution in which 98 parts of a black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK) and 2 parts of a photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO) is mixed on a glass substrate and dried by spin coating. The film was applied so that the post film thickness was about 1 μm, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 10 μm-diameter circular gap at the intersection of light-shielding film patterns arranged in a matrix with a line width of 20 μm, after exposure and development, the film is heat-cured at 180 ° C. for 30 minutes to form a pattern-shaped light shielding A film was formed.

<Comparative Example 3>
Example 1 was performed in the same manner as in Example 1 except that the formation of the patterned light-shielding film was performed as follows.

-Formation of patterned light-shielding film-
A coating solution in which 98 parts of a black resist containing carbon black (manufactured by Nippon Steel Chemical Co., Ltd., V-259BK) and 2 parts of a photoinitiator (manufactured by Ciba Specialty Chemicals, Darocur TPO) is mixed on a glass substrate and dried by spin coating. The film was applied so that the post film thickness was about 1 μm, and pre-dried at 80 ° C. for 5 minutes. Next, through a photomask having a 10 μm square gap at the intersection of light shielding film patterns arranged in a matrix with a line width of 20 μm, after exposure and development treatment, heat curing treatment is performed at 180 ° C. for 30 minutes to obtain a patterned light shielding film Formed.

The spacer placement accuracy in the light-shielding part gap in the color filter substrate with spacers obtained as described above was evaluated based on the following criteria by microscopic observation.
○: Presence rate in voids is 90% or more ×; Presence rate in voids is less than 90%

Further, the height of the spacer upper surface with respect to the surface of the light-shielding film in the obtained color filter substrate with a spacer was measured and evaluated based on the following criteria.
○: Height average is 5.0 μm or more and less than 5.2 μm ×; Height average is 5.2 μm or more

Moreover, the presence or absence of white spots in the light shielding part gaps in the obtained color filter substrate with a spacer was evaluated based on the following criteria by microscopic observation.
○: No whiteout ×;

  A list of evaluation results of Examples 1-4 and Comparative Examples 1-3 based on the above evaluation criteria is shown in the following table.

  INDUSTRIAL APPLICABILITY The present invention can be applied to a product including a process of selectively forming a minute protruding structure at a predetermined position on a fine pattern, for example, a product such as various display elements or a touch panel. And can be used for forming a spacer of a liquid crystal display using a film substrate.

DESCRIPTION OF SYMBOLS 1 Light shielding film pattern 2 Light shielding film space | gap 3 Red pixel area 4 Green pixel area 5 Blue pixel area 6 Inkjet head 7 Spacer ink 8 Black spacer

Claims (8)

Forming a light-shielding film pattern having voids at a predetermined period on a transparent substrate;
Discharging a spacer ink having at least black spacer particles and a black pigment contained in the light-shielding film into the gap by an inkjet method;
Forming a colored pixel, and a method of manufacturing a color filter substrate with a spacer.   2. The method for manufacturing a color filter substrate with a spacer according to claim 1, wherein the gap is formed simultaneously with the formation of the light shielding film pattern.   3. The method for manufacturing a color filter substrate with a spacer according to claim 1, wherein the gap is circular and has a diameter of 5 [mu] m or more.   The method for producing a color filter substrate with a spacer according to any one of claims 1 to 3, wherein the light-shielding film exhibits a liquid repellency with a contact angle of 90 ° or more with respect to the spacer ink.   The spacer ink is mainly composed of an organic solvent having a boiling point of 150 ° C. or higher as a dispersion solvent, 0.1 to 10% by weight of black spacer particles having a particle size of 1 to 10 μm, and 1 to 30 black pigments having a particle size of 10 to 500 nm. 5. The composition according to claim 1, wherein the spacer ink has a viscosity of 30 cps or less and a surface tension of 20 to 50 mN / m. Manufacturing method of color filter substrate with spacer.   6. The color filter with a spacer according to claim 1, wherein the spacer ink includes an adhesive component, and the adhesive component is thermally cured / energy ray cured / or UV cured. A method for manufacturing a substrate. Method for producing a spacer with a color filter substrate as claimed in any one of claims 6 to the spacer particle number density arranged in said gap, characterized in that in the range of 1,000 to 50,000 pieces / cm ² .   The red, green, and blue pixels of the color filter are all formed by an ink jet printing method, and are formed in a lump including the spacers. Manufacturing method of color filter substrate with spacer.