JP2009229663A - Method of manufacturing color filter substrate with spacer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an inexpensive color filter substrate with spacers that precisely disposes and form spacer particles of different kinds at the same time at prescribed pattern positions on a color filter formed on a transparent substrate using ink jet printing. <P>SOLUTION: The color filter substrate with the spacers is obtained which has spacer particles with different particle sizes selectively disposed on a light shield layer in the color filter by arranging and drying spacer ink wherein the spacer particles 104 having the different particle sizes are dispersed selectively at fixed points by ink jet printing on a recessed plate 100 where a pattern corresponding to prescribed positions on a light shield film of the color filter formed on the transparent substrate is formed, and then positioning both the color filter substrate side and the recessed plate side and transferring the spacer particles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a spacer-equipped color which can selectively arrange and fix a spacer on a light-shielding layer of a color filter substrate by ink jet printing to produce a liquid crystal display with high display quality without light leakage or display unevenness due to the spacer. The present invention relates to a method for manufacturing a filter substrate.

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 the liquid crystal layer at a constant interval and maintaining an appropriate thickness of the liquid crystal layer.

  In a conventional liquid crystal display manufacturing method, spacers are dispersed and arranged on a substrate on which pixel electrodes are formed, so position control is impossible, and as a result, random arrangement results in the display part of the liquid crystal display. However, there was a problem that spacers were arranged. 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 causes light leakage due to the depolarizing action. In addition, there is a problem in that the alignment of the liquid crystal on the surface of the spacer is disturbed, light is lost, the contrast and color tone are lowered, and the display quality is deteriorated.

  In order to solve the problems associated with the random dispersion of spacers, it is necessary to place the spacers at fixed points on the light shielding layer. Thus, as a method of arranging the spacers only at specific positions, photolithography can be used. Many forming methods using the ink jet printing method and the ink jet printing method have been proposed.

  The photolithographic method is a main manufacturing method in forming a color filter substrate. A photosensitive resin is applied onto the entire surface of the substrate, and a color filter pattern is sequentially formed by exposure and development through a mask on which a pattern is drawn. It is a way to do.

  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, with respect to the photosensitive resin composition, development property is improved and deformation amount is reduced. A composition corresponding to the above has been proposed. However, since the photolithography method forms an arbitrary pattern by developing after exposure through a mask, especially in spacer formation, the pattern formation portion is less than 1%, so material loss is extremely high. There is a disadvantage that it is big.

On the other hand, the ink jet printing method is a printing method excellent in material efficiency that can give a necessary amount to a necessary portion from a minute nozzle of several tens of μm.
This method can apply a micropattern of any design in combination with a precision stage, and in recent years, it has been actively applied to liquid crystal related technologies. For example, Patent Documents 5 to 7 propose a method of directly arranging a spacer at an arbitrary position.

  However, in order to eject spacer particles of several microns, one having a large inkjet nozzle diameter must be selected, and the droplet diameter formed on the substrate is approximately 50 μm. Even if it is placed on the light shielding layer with high accuracy by inkjet printing, it is difficult to control the position of the spacer particles in the droplet after drying, so it is selected for mobile applications with a narrow light shielding layer width of about 10 μm. Therefore, it is difficult to dispose spacer particles on the light shielding layer.

On the other hand, liquid crystal displays have been widely used and have been used in large-sized panels and various environments, and high performance is also expected for spacer materials.
In a liquid crystal display, for example, in order to prevent plastic deformation and destruction of the spacer when an excessive load is applied to the panel, the density of the spacer distribution may have to be increased. However, if the density of the spacers is sufficiently high, plastic deformation and destruction can be prevented, but there is a problem that vacuum bubbles (low temperature bubbles) are generated in the panel.

  Generation | occurrence | production of a vacuum bubble (low temperature bubble) generate | occur | produces, for example in the case of panel assembly. The members constituting the panel, such as liquid crystal and spacers, are once thermally expanded by heating when the substrates are bonded together. And after bonding, all those structural members are going to shrink. Among the constituent members, since the contraction rate of the liquid crystal is the largest, it tends to shrink in the direction of reducing the gap between the substrates. At this time, if the deformation of the spacer becomes unable to follow the amount of change in which the gap between the substrates tends to shrink, vacuum bubbles (cold bubbles) are generated in the panel.

  Alternatively, the problem of this vacuum bubble (low temperature bubble) also occurs when the liquid crystal display is used. When the environment when the liquid crystal display is used is a low temperature environment such as −20 ° C., all members constituting the liquid crystal cell tend to contract. Among the constituent members, the contraction rate of the liquid crystal is the largest, so it tends to shrink in the direction of reducing the gap between the substrates. Therefore, as in the above example, vacuum bubbles (low temperature bubbles) are generated in the panel. For this reason, the density of the spacer is set to an appropriate density so that the spacer elastically deforms following the thermal expansion and contraction of the liquid crystal due to temperature (Patent Document 8).

  However, problems remain such as plastic deformation and fracture of the spacer when an excessive load is applied to the panel. As a technique for overcoming the problem of vacuum bubbles (low temperature bubbles) and dealing with problems such as plastic deformation and destruction due to excessive load, the first spacer for setting the gap between the substrates and the height higher than the first spacer are used. There has been proposed a color filter substrate for a liquid crystal display having different types of spacers at the same time, such as a second spacer that prevents plastic deformation and destruction of the spacers when a low and excessive load is applied (Patent Documents 9 and 10).

Regarding the method of manufacturing a color filter substrate for a liquid crystal display having such different types of spacers, the photolithography method is mostly used, but the method of repeating exposure, development and heat curing for each type of spacer to be produced, A method of forming a columnar pattern having a difference in cross-sectional area using a negative photosensitive resin and causing a difference in the height of the columnar pattern (Patent Document 11). There has been proposed a method of performing exposure in a lump using a halftone mask as a photomask to be used (Patent Document 12).
However, even when exposure is repeated or when an expensive mask is used, the loss of material is still large.
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-A-9-105946 JP 2001-13506 A JP 2003-84289 A JP-A-2005-122150 JP 2003-121857 A JP 2003-121857 A

  The present invention provides an inexpensive method for producing a color filter substrate with a spacer, in which different kinds of spacer particles are simultaneously arranged and formed at a predetermined pattern position on a color filter formed on a transparent substrate using inkjet printing. It is an issue to provide.

The present invention is a method for producing a color filter substrate with a spacer,
1) a step of producing an intaglio plate provided with a concave pattern corresponding to a predetermined pattern position on a color filter formed on a transparent substrate;
2) A step of selectively placing fixed positions of the spacer ink in which the spacer particles are dispersed in a solvent in the concave pattern of the intaglio by inkjet printing,
3) Using the self-arrangement phenomenon in which spacer particles gather in the recess pattern during the drying process of the ink, accurately placing the spacer particles in the recess pattern;
4) at least a step of aligning both of the alignment marks on the color filter substrate side and the intaglio side and transferring spacer particles to a predetermined pattern position on the color filter;
In the method for producing a color filter substrate with a spacer, a plurality of types of spacer particles having different particle diameters and elastic moduli are used as the spacer particles dispersed in the spacer ink.

  In the method for producing a color filter substrate with a spacer according to the present invention, the plate depth of the intaglio is not more than ½ of the small particle diameter of the spacer particles dispersed in the spacer ink. This is a method for producing a color filter substrate with a spacer.

  According to the present invention, in the method for manufacturing a color filter substrate with a spacer according to the above invention, the concave pattern diameter of the intaglio is 30 to 100% of the width of the light shielding layer on the color filter. A method for manufacturing a substrate.

  Further, the present invention provides a method for producing a color filter substrate with a spacer according to the above invention, wherein a surface treatment is performed such that the contact angle of the solvent of the spacer ink on the surface of the intaglio is 100 ° or more. It is a manufacturing method of a color filter substrate.

Further, the present invention provides the method for producing a color filter substrate with a spacer according to the above invention, wherein the density of the spacer particles on the intaglio is 1000 to 20000 / cm ^2. Is the method.

  The present invention also provides the method for manufacturing a color filter substrate with a spacer according to the above-described invention, wherein the intaglio comprises a glass substrate.

  Further, the present invention provides a method for producing a color filter substrate with a spacer according to the above invention, wherein, when transferring from the intaglio to the color filter substrate, heat is applied to at least one of the intaglio side or the color filter substrate side. It is a manufacturing method of the color filter substrate with a spacer characterized.

  Further, the present invention is the method for producing a color filter substrate with a spacer according to the above invention, wherein the solvent of the spacer ink is mainly composed of a water-soluble organic solvent having a boiling point of 150 ° C. or more, and the particle diameter of the spacer particles is 3 to 6 μm. A spacer-attached color characterized in that the spacer particles having different contents are 1.0% by weight or less, the viscosity of the spacer ink at 23 ° C. is 20 cps or less, and the surface tension is 40 mN / m or less. It is a manufacturing method of a filter substrate.

  Further, the present invention is the method for producing a color filter substrate with a spacer according to the above invention, wherein the spacer ink includes a resin adhesive component mainly composed of a resin, and these include at least one of heat, light, and electron beam. It is a manufacturing method of a color filter substrate with a spacer, characterized by curing with the above energy.

  In the present invention, spacer particles having different particle diameters and elastic moduli are dispersed in the ink, so that it is possible to reduce the material used by ink jet printing and simultaneously dispose different spacer particles at predetermined pattern positions. In addition, it is possible to improve the transferability of the spacer particles to the color filter substrate side while expressing the self-arrangement phenomenon that acts in the drying process of the spacer ink that has landed in a wide area including the concave pattern formed on the intaglio. In addition, since the pattern diameter of the intaglio is 30 to 100% of the width of the light shielding layer on the color filter substrate, the spacer particles can be accurately placed on the light shielding layer on the color filter substrate.

  In the present invention, since the surface treatment was performed so that the contact angle of the solvent of the spacer ink is 100 ° or more, the liquid film end face promotes the movement of the spacer particles in the drying process of the landed ink droplets. It becomes possible to promote the self-arrangement phenomenon in the concave pattern provided on the intaglio. Further, since the intaglio plate is made of a glass substrate, it is possible to reduce positional displacement due to shrinkage / expansion of the substrate even when heating or pressurization is used in the transfer process of the spacer particles arranged on the intaglio plate.

Further, according to the present invention, it is possible to improve transferability by applying heat to at least one of the intaglio side or the color filter substrate side in the transfer step of the spacer particles. In addition, even when a general ink jet head is used, accurate and stable ejection can be performed. In addition, since the spacer particle number density is 1000 to 20000 particles / cm ² , the cell thickness is not uneven due to panelization, and the product does not become an obstacle when applying an alignment film or liquid crystal in the paneling process. It can be used.

Hereinafter, the best mode for carrying out the present invention will be described in detail.
As the intaglio substrate in the present invention, a glass substrate such as soda glass or non-alkali glass, or a substrate such as plastic can be used. Furthermore, by using a light-transmitting substrate, alignment can be facilitated during pattern superposition.

As the plastic substrate, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, cycloolefin polymer, polyimide, nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, triacetyl cellulose, or other films or sheets are used. However, a glass substrate is preferable from the viewpoint of dimensional stability.
When the intaglio plate is made of a glass substrate, even when heating or pressurization is used in the transfer process of the spacer particles arranged on the intaglio plate, it is possible to reduce positional deviation due to shrinkage or expansion of the substrate.

  As a processing method of the concave pattern in the present invention, a photosensitive resin is applied to the surface of the substrate, a pattern is formed through a mask, and then processed using an existing dry etching process, wet etching process, or sand blasting process. A method is mentioned. As the plate depth of the concave pattern, a plate depth of 0.3 μm to 5 μm can be used according to the particle diameter and arrangement density of the spacer particles to be used. Similarly, it is possible to use a substrate in which a photosensitive resin is applied to the substrate surface, a pattern is formed through a mask, and a pattern having a thickness of 0.3 μm to 5 μm is provided.

  The plate depth of the concave pattern of the intaglio is preferably ½ or less of the small particle diameter of the spacer particles dispersed in the spacer ink. This makes it possible to improve the transferability of the spacer particles to the color filter substrate side while expressing the self-arrangement phenomenon that acts in the drying process of the spacer ink that has landed in a wide area including the concave pattern formed on the intaglio. .

  The concave pattern diameter of the intaglio is preferably 30 to 100% of the light shielding layer width on the color filter. As a result, it is possible to accurately place the spacer particles on the light shielding layer on the color filter substrate.

  Further, the thickness of the transfer layer is preferably 2 μm to 5 μm depending on the particle diameter and arrangement density of the spacer particles to be used.

  For the surface treatment layer provided on the intaglio, a release agent represented by silicone oil and 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.

As a method for forming the surface treatment layer provided on the intaglio shown above, a known coating method can be used depending on the viscosity of the ink and the drying property of the solvent. Examples thereof include spin coating, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like. Among them, the die coat, cap coat, roll coat, and applicator can form a uniform ink liquid film for ink having a wide range of viscosity.

  The surface of the intaglio is preferably subjected to a surface treatment so that the contact angle of the solvent of the spacer ink is 100 ° or more. Thereby, in the drying process of the landed ink droplets, the liquid film end face promotes the movement of the spacer particles, thereby promoting the self-arrangement phenomenon in the concave pattern provided on the intaglio.

As the water-soluble organic solvent used in the spacer ink in the invention, those having a boiling point of 150 ° C. or higher, preferably 180 ° C. or higher are used, and one or a mixture of two or more can be used.
Examples of the water-soluble organic solvent used in the present invention include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, High boiling point and low volatility polyhydric alcohols such as 2,4-butanetriol, 2,2′-thiodiethanol, polyethylene glycol, polypropylene glycol, etc. are used, and N-methyl-2-pyrrolidone, 1,3- Water-soluble organic materials such as dimethylimidazolidinone, monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, Nn-butyldiethanolamine, triisopropanolamine, triethanolamine A solvent can be added.

  Moreover, it is preferable that the addition amount of the water-soluble organic solvent whose boiling point is 150 degreeC or more in this invention is 50 to 90%. When the added amount is 50% or less, the volatility of the spacer forming ink is increased and the stability of the ink is lowered. When the added amount is 90% or more, the viscosity of the spacer forming ink is increased, resulting in poor ejection during ink jet printing. This is not preferable.

  As the spacer particles used in the spacer ink in the present invention, spherical particles having a particle diameter of 3 to 6 μm can be used alone or in combination of two or more. For the purpose of countermeasures against problems such as plastic deformation and fracture of the spacer when an excessive load is applied to the panel, the particle size of the spacer with a small particle size is set within the elastic deformation range of the spacer with a large particle size. In view of the range of commonly used spacer particles, the difference in particle diameter between the types of spacer particles is preferably 0.02 μm to 0.5 μm.

  The material for the spacer particles is not particularly limited, and examples thereof include resins, organic substances, inorganic substances, and compounds and mixtures thereof. 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-acrylate copolymer 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 particles in the spacer ink is not particularly limited, but is preferably 0.2 to 3% of the total dispersion, for example.
When the solid content concentration of the spacer particles in the spacer ink is less than 0.2%, the discharged droplets tend not to contain the spacer particles, the density of the spacer particles on the color filter substrate decreases, and 3% Exceeding the amount of spacer particles is not preferable because the spacer particles agglomerate and the nozzles of the inkjet head are clogged, and the content of the spacer particles in the discharged droplets tends to be excessive.

  Examples of adhesive resin components in the spacer ink include polyacrylate, polymethacrylate, polyethylacrylate, 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. Is not to be done. Those obtained by adding a reactive site such as an acrylic group, a carboxyl group or an isocyanate group to these resin components, and those obtained by adding a crosslinking agent, a photoinitiator or the like to these can be used as the curable resin.

  Further, the addition amount of the adhesive resin component is 0.2 to 10% according to the addition amount of the spacer particles, and is preferably equal to or more than the spacer particles. If the addition amount is 0.2% or less, the adhesion on the color filter substrate is poor, and if it is 10% or more, the viscosity of the spacer ink is remarkably increased, and the ink head causes nozzle clogging, which is not preferable. .

  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 kind of water-soluble anionic, cationic, amphoteric, nonionic surfactant is used. Or multiple types can be added.

  In the spacer ink, it is preferable that the spacer particles are dispersed in the form of single particles, and various additives such as a tackifier, a viscosity adjuster, a pH adjuster, an interface are used as long as the effect is not impaired. An activator, an antifoaming agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a colorant may be added.

  In the present invention, the spacer particles are arranged at predetermined positions on the intaglio by inkjet printing. 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 in which a spacer dispersion liquid is ejected according to a recording signal, and includes a pressure pulse method, a thermal jet method, an ERF method, and the like.

  The target substrate of the present invention is used for the purpose of arranging spacer particles and can be used for various display elements, touch switches, and the like, but is particularly suitable for a liquid crystal display. The substrate is not particularly limited, and may be one generally used as a liquid crystal display such as a glass plate or a resin plate.

  The liquid crystal display is formed by overlapping two substrates. For this reason, the spacer ink according to the present invention is usually disposed on one substrate in a transfer process via an intaglio. Then, a liquid crystal display element is manufactured by overlapping with the other substrate. The intaglio plate from which the spacer ink is ejected preferably has a concave pattern at a position corresponding to the light shielding layer of the color filter substrate from the viewpoint of alignment.

  If necessary, the color filter substrate on which the spacer is formed may be subjected to a surface treatment for the purpose of controlling the wettability with the spacer ink. As the surface treatment method, any method such as corona treatment, atmospheric pressure plasma treatment, or UV ozone treatment can be selected.

  The spacer ink may be ejected onto the substrate on which the concave pattern is formed. The spacer ink may be ejected to all the concave patterns, and in some cases, a concave pattern that does not eject the spacer ink may be used to adjust the density of the spacer arrangement locations. You may choose.

  Further, when the arrangement density of the concave patterns is high, the width between the patterns is narrower than the droplet diameter at the time of landing of the spacer ink, and the liquid droplets stick to each other in one continuous discharge, for example, the concave pattern 1 Alternatively, continuous ejection may be performed every other time, and after waiting for drying, continuous ejection may be performed on a concave pattern that has not yet been ejected.

  The density of the spacer particles on the intaglio is not particularly limited, but it is usually preferably 1000 to 20000 in a 1 cm square area. Thereby, it becomes possible to use it for a product without causing a non-uniformity in cell thickness due to panelization, or an obstacle when applying an alignment film or liquid crystal in the paneling process.

  Next, the manufacturing method of the color filter substrate with a spacer according to the present invention will be described in detail with reference to the drawings. First, a method for arranging spacer particles by ink jet printing on an intaglio according to the present invention will be described with reference to FIG.

  In the present invention, in order to dramatically improve the arrangement accuracy of the spacer particles 104 included in the spacer ink 103 as compared with the case of direct arrangement by ink jet printing, first, the spacer ink 103 is applied to the target color filter substrate 203. It discharges on the intaglio 100 made according to the pattern. This is because, when the landing droplets of the spacer ink 103 land so as to include the concave pattern 102, the spacer particles 104 naturally gather in the concave pattern 102 in the drying process (FIGS. 1A to 1C). Is used.

  The self-arrangement phenomenon includes a phenomenon in which the spacer particles 104 also gather to the center of the droplet when the solvent interface in the spacer ink 103 moves to the center of the droplet by drying, and the spacer ink 103 that has landed on the concave pattern 102. Since the solvent film thickness is thicker than the surroundings, the drying is slower than the surroundings, and the phenomenon that the spacer particles 104 easily gather in the concave pattern 102 in order to keep up the surrounding solvent, and the spacer particles 104 once dropped in the concave pattern 102 are It appears for several reasons, such as staying in the recess pattern 102 as it is.

Next, a transfer method for transferring the spacer particles 104 arranged in the concave pattern 102 according to the present invention to the color filter substrate 203 will be described with reference to FIG. The adhesive resin component 201 contained in the spacer ink 103 covers the surface of the spacer particles 104 arranged in the concave pattern 102.
The color filter substrate 203 and the intaglio 100 are checked in advance and alignment marks and patterns provided on the color filter substrate 203 and the intaglio 100, respectively, and after alignment, the intaglio 100 side or the intaglio 10
Heat treatment is performed from both sides of 0 and the color filter substrate 203, and both substrates are peeled off after pressurization, whereby the spacer particles 104 are transferred to the color filter substrate 203 side. In the step of transferring the spacer particles, it is possible to improve transferability by applying heat to at least one of the intaglio side or the color filter substrate side.

  Hereinafter, examples will be given to describe the present invention in more detail, but the present invention is not limited to these examples.

<Example 1>
-Preparation of spacer ink-
While stirring the polyvinyl acetal resin (Sekisui Chemical Co., Ltd., KW-1, solid content 20%), the epoxy compound (manufactured by Nagase ChemteX, Denacol EX-521) is added in an amount of 5% in the solid content ratio. A small amount was added to prepare a thermosetting polymer solution. Next, spacer particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl EX004, particle diameter 4.2 μm / 4.0 μm = 1 / 1.5 (weight ratio)), the thermosetting polymer liquid, ethylene glycol / butyl cellosolve / A mixed solvent of water = 65/5/30 (weight ratio) was mixed and ultrasonically dispersed so that spacer particles / polymer solution / mixed solvent = 0.2 / 5 / 94.8 (weight ratio). The mixture was filtered through a 10 μm stainless steel mesh to obtain the spacer ink of Example 1. The obtained spacer ink had a viscosity of 13.4 mPa · s (23 ° C.).

~ Creation of glass intaglio ~
A positive resist (Shipley Co., Ltd., S1813) was applied to alkali-free glass (Corning, 1737 glass, 300 mm square, 1.1 mm thickness) by spin coating, and a width of 10 on the light shielding layer of the color filter substrate. It is exposed through a mask designed with a pattern having an opening width of 10 to 30 μm so that various resolution patterns of ˜30 μm can be arranged, and the pattern is obtained by developing with an alkaline developer (manufactured by Shipley, MFCD-26). Formed.

  The opening portion of this pattern was etched with hydrofluoric acid to a plate depth of 0.5 μm, and the resist was stripped with a resist stripping agent (manufactured by Shipley, remover 1165) to obtain a glass intaglio. A surface treatment layer was provided on the glass intaglio by dip coating a fluorine-based water repellent treatment agent (manufactured by 3M, EGC-1720) and drying at 80 ° C. for 30 minutes.

-Spacer formation on color filter substrate-
The spacer ink is vacuum defoamed in an ink jet printing apparatus equipped with a 40 pl piezo ink jet head and a precision stage having an alignment mechanism, and then filled and aligned with the intaglio plate. Spacer ink droplets were placed at fixed positions at corresponding positions, and dried on a hot plate at 80 ° C. for 1 minute. This plate was mounted on a transfer device having an alignment mechanism for upper and lower substrates, and after aligning the color filter substrate and the glass intaglio, transfer processing was performed with a roller while applying heat at 100 ° C. to the glass intaglio side. The color filter substrate on which the spacer was formed was cured at 120 ° C. for 30 minutes to obtain a color filter substrate on which spacer particles having different particle sizes were formed.

<Example 2>
A glass intaglio plate of Example 1 was prepared in the same manner as in Example 1 except that it was performed as follows.

~ Creation of glass intaglio ~
First, 100 parts by weight of an acrylate resin (manufactured by Daicel Chemical Industries, Ltd .: trade name “Cyclomer P-ACA200M”) as an alkali-soluble resin, and dipentaerythritol hexaacrylate (Toagosei Co., Ltd.) as a photopolymerizable monomer Company: Trade name: M400) 30 parts by weight, Irgacure 369 (manufactured by Ciba Special Chemicals) as a photopolymerization initiator, 6 parts by weight, and 300 parts by weight of propylene glycol monomethyl ether acetate as a diluent solvent are diluted by stirring. Thus, a negative resist composition was prepared.

  The negative resist composition is applied to an alkali-free glass (Corning, 1737 glass, 300 mm square, 1.1 mm thickness) by spin coating so that the film thickness after drying is 0.5 μm, and the light shielding layer of the color filter substrate The glass substrate is exposed and developed through a mask designed with a pattern with an opening width of 10 to 30 μm so that various resolution patterns with a width of 10 to 30 μm can be arranged thereon, and cured under conditions of 210 ° C. and 1 hr. A pattern was formed on the material to obtain a glass intaglio. A surface treatment layer was provided on the glass intaglio by dip coating a fluorine-based water repellent treatment agent (manufactured by 3M, EGC-1720) and drying at 80 ° C. for 30 minutes.

<Comparative Example 1>
The spacer ink prepared in the same manner as in Example 1 was vacuum degassed and filled into an inkjet printing apparatus equipped with a piezo inkjet head having a discharge amount of 40 pl and a precision stage having an alignment mechanism. After alignment of the color filter substrate, spacer ink droplets were directly placed at fixed positions on the light shielding layer, and dried on a hot plate at 80 ° C. for 1 minute. The color filter substrate on which the spacers were formed was subjected to a main curing process at 120 ° C. for 30 minutes to obtain color filter substrates on which spacer particles having different particle sizes were formed.

The positional accuracy of the spacer arrangement on the light shielding layer (width 10, 20, 30 μm) in the color filter substrate obtained as described above was evaluated based on the following criteria by microscopic observation.
○: Presence rate on the pixel portion is 10% or less Δ; Presence rate on the pixel portion is 10% or more and less than 50% ×; Presence rate on the pixel portion is 50% or more Also, on the color filter substrate of the formed spacer The sticking property to water was evaluated based on the following criteria under conditions of 0.25 MPa and 30 sec using water as a fluid with an air brush.
○: 10% or less of the peeled part Δ; 10% or more of the peeled part and less than 30% ×; 30% or more of the peeled part Shown in

AC is the schematic of the process of arrange | positioning the spacer particle | grains to a recessed part pattern. It is the schematic which shows the transfer process of the spacer particle | grain to a color filter board | substrate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Intaglio 101 which formed the recessed pattern ... Inkjet head 102 ... Recessed pattern 103 ... Spacer ink 104 ... Spacer particle 201 ... Adhesive resin component 202 ... Water-repellent layer 203 ... Color filter substrate 204 ... Light transmission layer 205 ... Light shielding layer

Claims (9)

In the method of manufacturing a color filter substrate with a spacer,
1) a step of producing an intaglio plate provided with a concave pattern corresponding to a predetermined pattern position on a color filter formed on a transparent substrate;
2) A step of selectively placing fixed positions of the spacer ink in which the spacer particles are dispersed in a solvent in the concave pattern of the intaglio by inkjet printing,
3) Using the self-arrangement phenomenon in which spacer particles gather in the recess pattern during the drying process of the ink, accurately placing the spacer particles in the recess pattern;
4) at least a step of aligning both of the alignment marks on the color filter substrate side and the intaglio side and transferring spacer particles to a predetermined pattern position on the color filter;
A method for producing a color filter substrate with a spacer, wherein a plurality of types of spacer particles having different particle diameters and elastic moduli are used as spacer particles dispersed in the spacer ink.   2. The method for producing a color filter substrate with a spacer according to claim 1, wherein the intaglio has a plate depth that is 1/2 or less of a small particle size of spacer particles dispersed in spacer ink.   The method for producing a color filter substrate with a spacer according to claim 1 or 2, wherein a concave pattern diameter of the intaglio is 30 to 100% of a width of a light shielding layer on the color filter.   The method for producing a color filter substrate with a spacer according to claim 1, 2 or 3, wherein a surface treatment is performed so that the contact angle of the solvent of the spacer ink on the surface of the intaglio is 100 ° or more. 5. The method for producing a color filter substrate with a spacer according to claim 1, wherein the density of spacer particles on the intaglio is 1000 to 20000 particles / cm ² .   The method for producing a color filter substrate with a spacer according to any one of claims 1 to 5, wherein the intaglio is made of a glass substrate.   The spacer-attached color according to any one of claims 1 to 6, wherein when transferring from the intaglio to the color filter substrate, heat is applied to at least one of the intaglio side and the color filter substrate side. Manufacturing method of filter substrate.   The solvent of the spacer ink is mainly composed of a water-soluble organic solvent having a boiling point of 150 ° C. or higher, the spacer particles have a particle diameter of 3 to 6 μm, and the spacer particles having different contents are 1.0% by weight or less, 8. The method for producing a color filter substrate with a spacer according to claim 1, wherein the spacer ink has a viscosity at 23 ° C. of 20 cps or less and a surface tension of 40 mN / m or less.   The spacer ink contains a resin adhesive component mainly composed of a resin, and these are cured by at least one energy of heat, light, and electron beam. 2. A method for producing a color filter substrate with a spacer according to item 1.

Images