JP2013073212A - Precise pattern printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing method which continuously forms a high precision pattern on a glass substrate or a flexible substrate like a plastic film and is capable of securing the position precision of different ink patterns relative to each other.SOLUTION: An ink liquid film 205 is applied on an ink release layer 203 of an ink releasable film substrate 201 and is pre-dried. A removal plate 211 on which a projecting pattern being a negative pattern of an image pattern is formed is pressed against the ink liquid film 205 to remove a part of the ink liquid film 205 corresponding to the projecting pattern, whereby the image pattern is formed on the ink releasable film substrate 201. The ink releasable film substrate 201 and a substrate 202 to be printed to are aligned to transfer the image pattern on the ink releasable film substrate 201 to the substrate 202 to be printed to. The substrate 202 to be printed to is preliminarily provided with base patterns 204 which are to be a base of the image pattern. The ink liquid film 205 is transferred to selected base patterns 204 of the substrate 202 to be printed to.

Description

  The present invention relates to a printing method for continuously forming an aligned high-definition pattern on a flexible substrate such as a glass substrate or a plastic film, in particular, a long plastic film with high production efficiency. is there.

  In recent years, flat panel displays have been used as image display devices for various uses such as stationary, wall-mounted, and portable types in terms of energy saving, space saving, and portability.

  In particular, in the portable type, there is a demand for plasticization from the viewpoints of impact resistance that does not break even when dropped while carrying, light weight, and thinning. In addition, the wall-hanging type also has a demand for a flexible display from the viewpoint of installing the display on a columnar column. As for display methods, reading terminals using electronic paper methods such as EPD (Electrophoretic Display) as well as liquid crystal display methods that have been used in the past have begun to become widespread, and competition for thinner terminals has been made. Yes.

  However, devices that use electronic paper that are currently distributed generally still perform monochrome display, and in the future, colorization that can withstand use in education and business fields, advertisement display, etc. is desired. Yes.

  When using a widely used EPD device as a device using electronic paper, a color filter (CF) is used in the same way as a liquid crystal display, or a method for colorizing the powder used. The method to do is examined.

  When powders used in the EPD method are colored, it is very difficult to separate the powders or the microcapsules containing the powders pixel by pixel. It has only been done.

  On the other hand, in the case of a method using CF, since colorization can be performed by simply attaching CF to a conventional monochrome display device, practical use is expected as a practical method.

  The CF used in the liquid crystal display is colored by transmitting light from the backlight because of its structure. Therefore, the color used for the CF is the same as the color that is supposed to be transmitted in a certain pattern. It was. Further, in a CF for a liquid crystal display, in order to prevent light leakage and improve the contrast at the time of black display, a partition pattern by a light shielding ink called a black matrix (BM) is provided between the color patterns. Usually, since the pixel pattern is provided by overlapping the BM pattern, the shape of the pixel itself and the positional accuracy between the pixels are often determined by the BM pattern.

  On the other hand, in the CF used in the reflective EPD system, since the entire panel becomes dark, the BM pattern cannot be used, so that the shape of the pixel pattern itself and the positional accuracy of the pixel patterns can be ensured. It becomes very difficult.

  Further, all CFs used in conventional flat panel displays are manufactured on a glass substrate, and it is difficult to manufacture on a plastic substrate. The reason is that until now, the fabrication of CF has included a photolithography process using a heating process at a high temperature.

  For example, in the production of CF for a liquid crystal display, there are processes such as development, washing, baking, etc. in patterning a photosensitive resin. When a general-purpose film substrate is used, Expansion and contraction occurs. Furthermore, since the photolithography process performs film formation, exposure, development, and peeling for each ink type, the manufacturing equipment becomes large and the manufacturing cost is high.

  From the above, in colorization of devices using electronic paper, a method of performing precise patterning on an inexpensive film substrate has been required.

  As a patterning method on a plastic substrate or a film substrate, an ink jet method has been studied. The ink-jet method is expected to be the most simple and excellent on-demand patterning method because a material can be patterned only in a predetermined part, so that the use efficiency of the material is high and a mask and a plate are not used.

  However, the diameter of ink droplets of the current ink jet is about several tens of μm, and it is usually necessary to consider the landing accuracy of about several tens of μm. Therefore, it is often difficult to reproduce a pattern having a size of 100 μm or less and resolution required for a mobile display. In addition, in order to perform precise patterning using the ink jet method, a process for receiving ink on the substrate is required in advance. One is a processing method of providing a pattern called a partition for preventing ink flow and color mixing. However, in the case of this method, it is necessary to form a partition pattern or a pattern by a special surface treatment that selectively fixes ink by a photolithography process.

  On the other hand, in order to limit the diffusion of the landed ink, a surface coating called an image receiving layer has been studied. In this case, it is not necessary to carry out the partition wall pattern or the substrate side treatment for selectively fixing the ink, but it becomes difficult to make the shape of the ink droplet, for example, square according to the pixel.

  As a method other than the ink jet method, there is a screen printing method that has been put to practical use in printing of wirings, resistors, and dielectrics in electronic components. However, because of screen printing stencil printing, the ink is limited to paste-like high-viscosity, and even if it can be adopted as a printing method for thick films of about several tens of μm from the fineness of the screen mesh, When producing CF, it cannot employ | adopt as a method of forming a pattern of 100 micrometers or less.

  As a method other than the ink jet method and the screen printing method, a so-called dry film in which a dry ink film is previously provided on a film substrate is removed by patterning by hot pressure, and then a transfer method for transferring the remaining pattern to the target substrate is devised. It was done. (See Patent Document 1)

  However, this method uses thermal pressure when transferring the ink layer from the film base material, and therefore involves expansion / contraction of the film base material, expansion of the plate, and melting / softening of the ink layer. It is difficult to obtain the reproducibility of a minute pattern. In addition, the apparatus for uniformly applying the heat pressure becomes complicated, and it becomes difficult to cope with a large screen.

  Therefore, in recent years, ink is applied on a blanket wound around a plate cylinder and pre-dried to form an ink film, and then an image pattern on the blanket is pressed by pressing the relief plate on which the non-image area pattern is formed. Next, a printing method in which an image pattern on a blanket is transferred onto a substrate to be printed and an image pattern is formed on the substrate to be printed has been attempted. (See Patent Document 2)

  This printing method called reverse printing is easy to adjust the ink film thickness, and forms an image pattern on an ink-peeling blanket. Good ink transfer to printing substrate. In addition, by pre-drying the ink film on the blanket, it is possible to suppress the fluidity of the ink, and it is possible to form a fine pattern with a thin film compared to existing printing methods such as screen printing, letterpress printing, and intaglio printing. It is.

  However, the method of Patent Document 2 has a problem that ink wettability and transferability of the blanket surface become unstable when ink is pre-dried on a blanket made of silicone rubber or silicone resin.

  This is because drying is performed while the blanket is fixed to the plate cylinder, so that uniform pre-drying is difficult, and the solvent in the coated ink is absorbed into the blanket and swells. This is due to variations in accuracy. Moreover, since it is necessary to adjust the amount of solvent swelling by cleaning the blanket or drying each time it is printed, it is not suitable for continuous processing. Furthermore, in this printing method, since the blanket is fixed to the plate cylinder, it is difficult to align the pattern on the blanket and the mark on the substrate when transferring the pattern onto the substrate on which a pattern is formed. It was.

  Therefore, we have developed a printing method in which a transparent ink peelable film substrate is rolled up as a blanket, and ink coating, drying, and transfer are performed while intermittently feeding out the required length. (See Patent Document 3)

  With this new printing method, printing alignment with the existing pattern on the substrate to be printed can be performed while simultaneously checking the pattern patterned on the ink peelable film substrate and the pattern on the substrate to be printed. Therefore, accurate printing can be performed. In addition, by sending out a certain amount of the ink peelable film base material for each printing, it is not necessary to clean the blanket every time the printing process is completed, and the solvent in the ink gradually becomes the ink peelable film base material. Since the printing conditions do not change due to absorption, continuous printing under uniform conditions is always possible.

  However, even if this method is used, when an inexpensive general-purpose film is used as a substrate to be printed, the pattern is a fine pattern of 100 μm or less mainly due to shrinkage of the substrate due to absorption of environmental temperature and moisture. It was difficult to maintain the positional accuracy between adjacent different ink patterns.

JP-A-9-90117 JP 2001-56405 A JP 2008-105400 A

  The object of the present invention is to continuously form a high-definition pattern on a flexible substrate such as a glass substrate or a plastic film, particularly a long plastic film with a high production efficiency, and position different ink patterns. It is to provide a printing method capable of ensuring accuracy.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the invention shown in the following configuration.

In order to achieve the above object, the invention according to claim 1
(A) A first liquid film is coated on the ink release layer of the ink peelable film substrate which is made of a transparent material and has an ink release layer on one side which is one side in the thickness direction. Process,
(B) a second step of pre-drying the ink liquid film;
(C) A removal plate on which a negative pattern convex pattern of a predetermined image pattern is formed is pressed against the preliminarily dried ink liquid film, and the ink liquid film portion corresponding to the convex pattern is removed. The third step of forming the image pattern with the ink liquid film remaining on the ink peelable film substrate,
(D) The image pattern formed by the ink liquid film remaining on the ink peelable film substrate and the pattern provided in advance on the surface of the substrate to be printed are superposed and observed, and the ink peelable film base A fourth step of aligning the material and the substrate to be printed;
(E) transferring the image pattern formed by the ink liquid film remaining on the ink peelable film substrate onto the surface of the substrate to be printed, and printing the image pattern on the substrate to be printed; A method of printing a precision pattern including the steps of:
A basic pattern serving as a base of the image pattern is provided in advance on the substrate to be printed,
Transfer of the ink liquid film according to the fifth step is performed by transferring the image pattern onto the selected basic pattern among the basic patterns.
It is characterized by that.

The invention according to claim 2 is the method for printing a precise pattern according to claim 1,
The basic pattern is
(A ′) An ink liquid film for forming a basic pattern is applied on the ink peeling layer of an ink peeling film base material for forming a basic pattern having an ink peeling layer on one surface which is one surface in the thickness direction. And a process of
(B ′) a step of pre-drying the ink liquid film;
(C ′) The basic pattern forming removal plate on which the convex pattern of the negative pattern formed in the shape opposite to the basic pattern is pressed against the preliminarily dried ink liquid film, Forming a pattern of the ink liquid film on the ink peelable film substrate for forming the basic pattern by removing the corresponding part of the ink liquid film;
(D ′) The ink liquid film pattern is transferred onto the surface of the substrate to be printed, and the basic pattern is transferred to the substrate to be printed.

The invention described in claim 3 is the printing method of the precision pattern according to claim 1,
The basic pattern is
(A ″) A light-shielding ink liquid film for forming a basic pattern is formed on the ink peeling layer of an ink-peeling film substrate for forming a basic pattern having an ink peeling layer on one surface which is one surface in the thickness direction. Coating process,
(B ″) a step of pre-drying the light-shielding ink liquid film;
(C ″) The base pattern-forming removal plate on which a convex pattern having the same concave and convex shape as the basic pattern is pressed against the preliminarily dried light-shielding ink liquid film, and the light-shielding ink corresponding to the convex pattern Forming a pattern of the light-shielding ink liquid film on the ink-peeling film substrate for forming the basic pattern by removing a portion of the liquid film;
(D '') transferring the pattern of the light-shielding ink liquid film onto the substrate to be printed coated with an ultraviolet curable resin;
(E ″) The surface of the substrate to be printed on which the pattern of the light-shielding ink liquid film has been transferred is irradiated with ultraviolet rays, and the portion other than the part to which the pattern of the light-shielding ink liquid film is transferred is transferred from the ultraviolet curable resin. Curing, and
(F ″) provided by the step of forming the basic pattern with the light-shielding ink liquid film and the ultraviolet curable resin remaining by removing the ultraviolet curable resin that has not been ultraviolet cured with a soluble solvent. It is characterized by that.

  According to a fourth aspect of the present invention, in the precision pattern printing method according to any one of the first to third aspects, a silicone resin layer is laminated on a transparent film base material as the ink peelable film base material. It is provided.

  According to a fifth aspect of the present invention, in the precision pattern printing method according to any one of the first to fourth aspects, the basic pattern is made of a transparent material, and the basic pattern is provided for alignment. Ink that can be visually or machine-recognized is transferred onto the alignment pattern including the alignment pattern, and the alignment pattern to which the ink has been transferred is applied to the surface of the substrate to be printed in the fourth step. It is used as a pattern provided in advance.

  A sixth aspect of the present invention is a method for producing a color filter, wherein a colored layer is formed by the precision pattern printing method according to any one of the first to fifth aspects.

According to the present invention, (a) an ink liquid film is formed on the ink release layer of the ink peelable film substrate which is composed of a transparent material and has an ink release layer on one side which is one side in the thickness direction. A first step of coating, (b) a second step of pre-drying the ink film, and (c) a removal plate on which a convex pattern of a negative pattern of a predetermined image pattern is formed, The image pattern is formed by the ink liquid film remaining on the ink peelable film substrate by pressing against the preliminarily dried ink liquid film and removing a portion of the ink liquid film corresponding to the convex pattern A third step, (d) observing the image pattern formed by the ink liquid film remaining on the ink peelable film substrate, and a pattern provided in advance on the surface of the substrate to be printed, Said A fourth step of aligning the peelable film substrate and the substrate to be printed, and (e) the image pattern formed by the ink liquid film remaining on the ink peelable film substrate, A fifth step of transferring the image pattern onto the surface of the substrate to be printed and printing the image pattern on the substrate to be printed, and a base pattern serving as a base for the image pattern is provided in advance on the substrate to be printed The transfer of the ink liquid film in the fifth step is performed by transferring the image pattern onto the selected basic pattern among the basic patterns. Reproduction of the pattern shape when performed, and higher alignment accuracy than existing printing methods can be ensured.
In particular, the ink film that has undergone process drying (a) to (b) can be used for patterning to minimize ink bleeding and crushing, and after the preliminary drying of the ink (c ) Is not advantageous in the alignment process of printing position accuracy and pitch accuracy, and (d) because there is almost no dimensional deformation of the substrate to be printed, since there is no step of applying heat before patterning by the removed plate. Become. The positioning step (d) is different from other printing methods in that the pattern already patterned on the ink-peeling film substrate and the pattern on the substrate to be printed already overlapped and directly observed. Can be combined.
In addition, by providing a basic pattern that is the basis of the printed pattern on the substrate to be printed, when the ink film is transferred onto the basic pattern, the ink film can be transferred only where there is a difference in the basic pattern. By using the phenomenon that the ink film is not transferred to the concave part of the basic pattern and the basic pattern, a pattern with higher accuracy than the accuracy obtained by repeating the alignment process (d) multiple times for each ink type. The position accuracy can be reproduced.

  Furthermore, in the present invention, the basic pattern is (a ′) on the ink peeling layer of the ink-peeling film substrate for forming a basic pattern having an ink peeling layer on one side which is one side in the thickness direction. A step of applying an ink liquid film for pattern formation; (b ′) a step of pre-drying the ink liquid film; and (c ′) a convex pattern of a negative pattern in which the concave and convex shapes are formed opposite to the basic pattern. The base pattern forming removal plate on which the ink is formed is pressed against the pre-dried ink liquid film, and the ink liquid film corresponding to the convex pattern is removed to remove the ink for forming the basic pattern. A step of forming a pattern of the ink liquid film on the base film substrate; and (d ′) transferring the pattern of the ink liquid film onto the surface of the substrate to be printed, and applying the basic pattern to the substrate to be printed. By providing the a step of transferring a, it is possible to form a fine pattern without heating the substrate to be printed.

  Further, the basic pattern is (a ″) for forming a basic pattern on the ink peeling layer of an ink peelable film substrate for forming a basic pattern having an ink peeling layer on one side which is one side in the thickness direction. A step of coating the light-shielding ink liquid film, (b ″) a step of pre-drying the light-shielding ink liquid film, and (c ″) a basic pattern on which a convex pattern having the same concave-convex shape is formed. An ink-releasable film substrate for forming the basic pattern is formed by pressing a removal plate for formation against the preliminarily dried light-shielding ink liquid film and removing a portion of the light-shielding ink liquid film corresponding to the convex pattern (D '') transferring the light-shielding ink liquid film pattern onto the substrate to be printed coated with an ultraviolet curable resin; '') The surface of the substrate to be printed on which the pattern of the light-shielding ink liquid film is transferred is irradiated with ultraviolet rays to cure the portion of the ultraviolet curable resin excluding the part to which the pattern of the light-shielding ink liquid film is transferred. And (f ″) a step of forming the basic pattern with the light-shielding ink liquid film and the ultraviolet curable resin remaining by removing the ultraviolet curable resin that has not been ultraviolet cured with a soluble solvent. By using a light-shielding ink that contains a sufficient amount of pigment for pattern formation of the basic pattern, it is possible to reproduce the pattern edge and film thickness of the basic pattern rather than using a transparent ink directly for the basic pattern. Can be easily changed, and a printed matter with higher definition can be obtained.

  In the present invention, as the ink releasable film substrate, a pattern formed on the ink releasable film substrate at the time of alignment of the printed material by providing a silicone resin layer on a transparent film substrate. And a pattern provided on the substrate to be printed can be superimposed and directly observed.

  In the present invention, the basic pattern is made of a transparent material, the basic pattern includes an alignment pattern provided for alignment, and an ink that can be visually or machine-recognized is transferred onto the alignment pattern. The pattern for alignment on which the ink has been transferred is used as a pattern provided in advance on the surface of the substrate to be printed in the fourth step. When the pattern provided on the printing base material is superposed and observed, it becomes easy to confirm the mark and recognize the machine, and the result alignment accuracy can be improved.

  Even when a color filter using a film substrate is manufactured by forming a colored layer and manufacturing a color filter (CF) by the printing method of the present invention, the color filter (CF) having high positional accuracy between pixels. Can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing for demonstrating an example of the manufacturing method and printing apparatus of printed matter of 1st embodiment of this invention, (a) is a figure explaining an example of the printing apparatus of embodiment of this invention, (b). FIG. 8 is a diagram for explaining patterning using a removal plate using the printing apparatus according to the embodiment of the present invention, and FIG. 8C is a diagram for explaining transfer to a printing substrate using the printing apparatus according to the embodiment of the present invention. is there. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing for demonstrating an example of the manufacturing method of the printed matter of embodiment of this invention, (a) is the figure which imitated the ink composition to the layer structure and peeling layer of an ink peelable film base material, (b) ) Is a diagram simulating the previous stage of transferring the ink liquid film to the removed plate, (c) is a diagram showing the state of transferring the ink liquid film to the removed plate, and (d) is the transfer facing the substrate to be printed. The figure which imitated the stage before performing, (e) is the figure which showed transfer of the ink pattern to a to-be-printed base material, (f) is sectional drawing of the to-be-printed base material which provided the basic pattern. It is sectional drawing for demonstrating an example of the manufacturing method of the printed matter of embodiment of this invention, (a) is a figure which shows a mode that the liquid film of light shielding ink is patterned with a removal plate, (b) is an ultraviolet curable film. The figure which shows a mode that a light-shielding pattern is printed on the to-be-printed base material provided with (c) is a figure which shows a mode that the surface of the to-be-printed base material which printed the light-shielding pattern is ultraviolet-cured, (d) is an uncured ultraviolet-ray It is a figure which shows a mode that the basic film was obtained on the to-be-printed base material by removing the cured film and light-shielding ink. It is sectional drawing for demonstrating an example of the manufacturing method of the printed matter of embodiment of this invention, (a) is a figure which shows the step before printing a light shielding pattern selectively on the alignment mark of a basic pattern, (b) is The figure which showed lamination | stacking of the light shielding pattern to the alignment mark of a basic pattern, (c) is a figure which shows a mode that it aligns with the pattern on an ink peelable film base material using an alignment mark, (d) is a basic pattern The figure which shows a mode that the ink film was selectively provided in a part of FIG., (E) is a figure which shows a mode that the ink already different from the ink already provided in a part of basic pattern was provided. .

  As shown in FIG. 1A, a flexible substrate such as plastic can be used as the film substrate used for the ink peelable film substrate 201 of the present invention.

  For example, films and sheets of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, cycloolefin polymer, polyimide, nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, triacetyl cellulose, and the like can be used.

  As shown in FIG. 1 (c), by using a light transmissive substrate as the film substrate used for the ink peelable film substrate 201, the substrate to be printed 202 is passed over the ink peelable film substrate 201. Can be observed, and alignment (alignment) can be facilitated when the patterns are superimposed.

  These flexible substrates are supplied by a long take-up roll, coated with an ink peeling layer 203 (FIG. 2 (a)), and in some cases, laminated with a protective film of polyethylene terephthalate or polypropylene, and then applied to the machine. Installed.

  The ink release layer 203 provided on the ink peelable film substrate 201 used in the present invention may be coated with a release agent represented by silicone oil or silicone varnish on the film substrate, or a thin film layer of silicone rubber may be used. It may be formed. Also, for the same purpose, a fluororesin and a fluororubber can be used, or the fluororesin fine powder may be mixed with silicone rubber or ordinary rubber to give a peelability.

  These silicone-based coatings usually have low adhesion to the film substrate, but are more adhesive to the substrate with respect to thermosetting or UV-curable acrylic resins, epoxy resins, and silicone layers on the outermost surface. It is also possible to provide a high resin layer as an anchor layer on the film substrate in advance and to provide it as an upper layer.

  In any case, it is desirable that the ink release layer 203 has a suitable ink receptivity and at the same time has a complete ink releasability of the ink once received.

  As the silicone, addition curing type, UV curing type and other curing reaction type silicone coating agents for release films can be used. Various molecular weights of dimethylpolysiloxane, other methylhydrogen polysiloxane, methylphenyl silicone oil, Modified ones such as methyl chlorinated phenyl silicone oil or copolymers of these polysiloxanes and 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.

  Specific silicone materials include “SRX211”, “LTC750A”, “LTC760A”, “BY24-510” manufactured by Toray Dow Corning Co., Ltd., “KS774”, “KS847”, “KS847” manufactured by Shin-Etsu Chemical Co., Ltd. Use KS5508, “TPR6700”, “TPR6702”, “TPR6710”, “TPR6721”, “TPR6500” manufactured by Momentive Performance Materials, “UV-POLY200”, “UV-POLY201” manufactured by Arakawa Chemical Industries, Ltd. However, these are not limited.

  Further, various curing catalysts and photoinitiators are used according to the curing type, and are appropriately added. For example, when a silicone coating material is used as the release layer forming material, “PLX” manufactured by Shin-Etsu Chemical Co., Ltd., such as “SRX212”, “NC-25”, “BY24-835” manufactured by Toray Dow Corning Co., Ltd. -50T ", such as" CM670 "and" UV9380 "manufactured by Momentive Performance Materials, and" UV-CATA211 "manufactured by Arakawa Chemical Industries, Ltd. can be used as the curing catalyst and photoinitiator.

  These silicone materials are mainly diluted with a solvent such as toluene, applied to the substrate surface using a known coating method such as gravure coater, roll coater, die coater, etc., and then dried to achieve the printing method of the present invention. Can be used. In addition, as the ink release layer 203 of the ink peelable film substrate 201 used in the present invention, an inorganic film may be provided on the film substrate and then a surface treatment with a silane coupling agent may be used.

  As the silane coupling agent, trimethoxysilanes, triethoxysilanes, and the like can be used. One part of this silane coupling agent can be selected from those having a reactive group with an organic compound such as a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an alkyl group or a part thereof. Those in which fluorine atoms are substituted and those in which siloxane is bonded and bonded to a substituent capable of forming a surface having a small surface free energy can be used.

  When the former silane coupling agent having a reactive group is used, the surface of the substrate is treated with the silane coupling agent, and then another monomer component is applied so as to obtain a predetermined surface free energy. Can be made.

  Examples of the silane coupling agent having a reactive group include vinyl methoxy silane, vinyl ethoxy silane, p-styryl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 2- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane. , 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc., and styrene, ethylene glycol diglycidyl ether, trimethylpropane triglycidyl ether, lauryl acrylate, dipentaerythritol hexa Acrylate or the like can be used. As the silane coupling agent having no reactive group, methyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane and the like can be used. However, it is not limited to an alkyl group.

  As a method for fixing the silane coupling agent to the substrate, a known surface treatment method using a silane coupling agent can be used. For example, a solution obtained by diluting a silane coupling agent in water, an acetic acid aqueous solution, a water-alcohol mixed solution, or an alcohol solution is prepared.

  The silane coupling agent can be fixed by coating the solution on the surface of the substrate using a known coating method such as a gravure coater, a roll coater, a die coater, and the like, followed by drying. When a silane coupling agent having a reactive group is used, other monomer components can then be applied and bonded in the same manner.

In order to immobilize the silane coupling agent on the substrate, it is preferable that SiO ₂ , TiO ₂ , ZrO ₂ or a composite film thereof is provided on the substrate in advance. As these inorganic oxide films, those provided by using a known vapor deposition method or sputtering method can be used. As a method of providing the inorganic oxide film, a metal alkoxide represented by the general formula M (OR) _n (M is a metal such as Si, Ti, Al, Zr, R is an alkyl such as CH ₃ , C ₂ H _5, etc.) It is possible to use a so-called sol-gel method in which an inorganic oxide film is formed by coating a gel solution obtained by hydrolyzing and condensation polymerization in the presence of water and alcohol on the surface and then heating. it can.

  Furthermore, the silane coupling agent can be added in advance to the metal alkoxide solution used in the sol-gel method. In this case, an effect is particularly obtained for surface property modification. In addition, the ink peelability with respect to the ink release layer 203 is preferably such that the contact angle when ink is dropped onto the treated surface is 10 ° or more and 90 ° or less, and more preferably 20 ° or more and 70 ° or less. If this contact angle is small, ink releasability in the subsequent process is reduced and pattern defects (such as poor reproducibility) are likely to occur. If the contact angle is large, repelling occurs when the ink film 205 is formed, It becomes difficult to form a uniform ink film 205.

  As a method of forming the ink film 205 (FIG. 2 (a)) on the ink release layer 203 of the ink release film substrate 201 shown above, a known coating method is used depending on the viscosity of the ink and the drying property of the solvent. Can be used. That is, for example, 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 can be mentioned. Among them, the die coat, cap coat, roll coat, and applicator can form a uniform ink film for inks with a wide range of viscosities. In the case of forming, die coating is the most efficient and preferable forming method.

  After forming the ink film 205 on the ink peelable film substrate 201 by the above method, the ink film 205 is preliminarily dried. For this preliminary drying, natural drying, cold / hot air drying, microwave, vacuum drying, or the like can be used, and radiation such as ultraviolet rays or electron beams can also be used. The purpose of this preliminary drying is to increase the viscosity, thixotropy and brittleness of the ink film 205.

  When the drying by the preliminary drying is insufficient, the ink film 205 is torn and defective when the convex part of the removal plate 211 (FIGS. 2B and 2C) in the subsequent process is pressed and peeled off. End up. On the other hand, when the drying is excessive, the tackiness on the surface of the ink film 205 is lost, and the ink is not transferred to the removal plate 211. Therefore, although the drying state is adjusted by the drying time and the atmospheric temperature depending on the composition of the ink to be used, a state in which 0.5% to 4% of solvent remains in the dried ink film 205 is preferable.

  The so-called dry film has a residual amount of solvent on the order of ppm, and the drying is excessive, and there is a problem that the ink is not transferred or the ink film 205 is partially peeled by pressing the removal plate 211 and causes dust. This is not suitable as a condition for the pre-dried ink film 205.

  As the removal plate 211 used in the printing method of this patent, after forming a mask pattern on the surface of low expansion glass such as non-alkali glass using a photosensitive resin, an existing dry etching process, wet etching process, or sand blasting process is performed. A plate having a plate depth of 2 μm to 30 μm can be used.

  For example, when fine patterning of about 5 μm to 200 μm is performed, etching in the width direction proceeds in accordance with processing in the plate depth direction during the etching process, so that the plate depth is about 2 μm to 10 μm, and 200 μm to If the plate depth is shallow at the periphery of a process control mark or the like having a width of several millimeters, the ink film 205 on the ink peeling layer 203 comes into contact with the vicinity of the center of the concave pattern, so that the plate depth is about 10 μm to 30 μm. Good to do. In order to mix patterns with different plate depths in the same plate, a mask corresponding to each plate depth is prepared, and a deep plate depth is etched in advance, and then a shallow plate depth is etched. Is preferred.

  The removal plate 211 used in the printing method of the present invention may be made of nylon, acrylic, silicone resin, styrene-diene copolymer or the like. Also, rubber plates such as ethylene-propylene, butyl, and urethane rubbers can be used. Such a resin removal plate 211 has already been used for letterpress printing and flexographic printing, and can be produced by pouring a predetermined resin into a previously produced mold, or by engraving, A method using a photosensitive resin can be manufactured with higher accuracy.

  The removal plate 211 used in the printing method of the present invention is further provided with a photosensitive resin using photolithography with a film thickness of 0.5 μm to 2 μm on a plate having irregularities formed on a part of the glass substrate by various methods. It is possible to use a curable resin or inorganic film coated as a protective layer on a surface that has been patterned and sufficiently cured.

  In the printing method of the present invention, glass or a plastic plate can be used as the substrate 202 to be printed. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone, cycloolefin polymer, polyimide Films and sheets of nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, triacetyl cellulose, etc. can also be used.

  The substrate to be printed 202 may be selected in accordance with the drying conditions of the ink applied for printing. When heat resistance is required, polyethylene naphthalate, polyethersulfone, cycloolefin polymer, polyimide and the like are suitable. Moreover, the base material which consists of material which added the inorganic filler to resin and improved heat resistance may be sufficient. These films and sheets as the substrate to be printed 202 may be stretched films or unstretched films. In addition, a gas barrier layer, a smoothing layer, and an ink image receiving layer may be laminated on the printing surface or other surfaces as necessary on the flexible substrate.

  As the ink material constituting the ink film 205, an image pattern forming material in which a solvent is dissolved or dispersed can be used. For example, when a color pattern (colored layer) consisting of red, green, and blue or a black matrix is formed by the production method of the present invention in a color filter, the pigment component and the resin component are dissolved and dispersed in a solvent to form an ink. Become.

  Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, H.264, 272, 279, etc. can be used.

  Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc. can be used. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37 and the like can be used, and C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.

  In order to improve the color adjustment of these red, blue and green pigments and the fluidity of the ink, the following pigments can be added in necessary amounts.

  In addition to the pigment dispersion, the ink used as the light-shielding ink or the coloring ink further comprises a polyfunctional monomer, a photosensitive resin or a non-photosensitive resin, a polymerization initiator, a solvent, and the like.

  The resin includes a thermoplastic resin, a thermosetting resin, and, if necessary, a photosensitive resin. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Examples thereof include resins, acrylic resins, alkyd resins, polybutadiene, polyethylene, polypropylene, and polyimide resins. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

  As the solvent, an ester solvent, an alcohol solvent, an ether solvent, a hydrocarbon solvent, or the like is used. As ester solvents, propylene glycol monomethyl ether acetate, ethoxyethyl propionate, as alcohol solvents, 1-butanol, 3methoxy-3methyl-1butanol, 1-hexanol, 1,3 butanediol, 1-pentanol, 2-methyl 1-butanol, 4-methyl-2-pentanol, ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol Ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether, hydrocarbon As the solvent, Solvesso 100, Solvesso 150 (trade name, manufactured by Exxon Chemical Co., Ltd.).

  In addition, when forming a basic pattern that is the basis of the colored ink, which is a feature of the present invention, by printing, particularly as an ink used for forming a basic pattern for producing a color filter, the above-mentioned transparent resin is a main component. Inorganic transparent fine particles that improve pattern cutting, a photosensitive resin or a non-photosensitive resin, a polymerization initiator, a solvent, and the like. The transparent resin and the transparent fine particles are resins and fine particles having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  As the transparent fine particles, particles such as LiF, MgF, 3NaF.AlF or AlF, Na3AlF6, ZrO2, or silica can be used. The average particle size is preferably 1 nm or more and 100 nm or less. When the particle diameter exceeds 100 nm, light is remarkably reflected by Rayleigh scattering, and the transparency tends to decrease. On the other hand, when the particle size is less than 1 nm, a problem of particle aggregation occurs. The average particle diameter means a 50% particle diameter (d50 median diameter) when particles in a solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed by a cumulative distribution.

  In addition, dispersants, surfactants, antioxidants, viscosity modifiers, adhesion improvers, ultraviolet absorbers, leveling agents, and the like are added to these light-shielding inks, colored inks, and basic pattern inks as necessary. Also good. The light-shielding ink, the color ink, and the basic pattern ink used in the present invention are not limited to these.

In the case of forming the basic pattern serving as the basis of the colored ink, which is a feature of the present invention, by printing and removing the uncured pattern using an ultraviolet curable resin and a light shielding pattern, as the ultraviolet curable resin composition, an unsaturated polyester system, Mainly composed of various UV-curable oligomers and monomers such as acrylic, vinyl ether, maleimide, and epoxy, and use reactive diluents, polymerization initiators, polymerization accelerators, organic solvents, etc. as necessary. be able to.
In particular, when a monomer (such as a prepolymer of a high molecular weight acrylic resin) having a property of eliminating the adhesiveness of the surface when applied and dried on a film substrate is wound up in a state before UV curing. Is preferable.
Examples of such ultraviolet curable resins and inks include “Unidic RC29-117” and “Unidic RC29-120” manufactured by DIC, and “8KX018C” manufactured by Taisei Fine Chemical.

  As the ultraviolet (UV) lamp used for ultraviolet curing, a high-pressure mercury lamp or a metal halide lamp can be applied, and the wavelength of the ultraviolet is about 200 to 400 nm, and the wavelength may be selected according to the resin and the initiator. The irradiation amount and irradiation time can be selected according to the material and film thickness of the composition, the output of the UV lamp, and the processing speed.

  Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 2-ethoxyethyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanone, methyl lactate, A general-purpose organic solvent such as ethyl lactate, butyl lactate, toluene, xylene, ethyl acetate, methyl ethyl ketone, and isopropanol can be used.

  In the printing method according to this embodiment, the ink film 205 is applied to the ink peelable film substrate 201 supplied in the form of a winding roll, and after the ink film 205 is preliminarily dried, the removal plate 211 is pressed, An unnecessary pattern of the ink film 205 is transferred to and removed from the convex portion of the removal plate 211, and the remaining image pattern is transferred to the printing substrate 202.

  When alignment printing on the substrate to be printed 202 is necessary, the patterned alignment mark and a pattern previously provided on the substrate to be printed 202 are overlapped, and the position is adjusted while observing the mark to transfer position It is characterized by determining.

That is, the printing method according to the present embodiment includes the following first to fifth steps.
(A) The ink liquid film 205 is applied on the ink peeling layer 203 of the ink peeling film base 201 which is made of a transparent material and has the ink peeling layer 203 on one side which is one side in the thickness direction. First step.
(B) A second step of pre-drying the ink liquid film 205.
(C) The removal plate 211 on which the negative pattern convex pattern of the predetermined image pattern is formed is pressed against the preliminarily dried ink liquid film 205 to remove the portion of the ink liquid film 205 corresponding to the convex pattern. A third step of forming an image pattern with the ink liquid film 205 remaining on the ink peelable film substrate 201.
(D) The image pattern formed by the ink liquid film 205 remaining on the ink peelable film substrate 201 and the pattern provided in advance on the surface of the substrate 202 to be printed are superposed and observed, and the ink peelable film substrate is observed. 4th process which aligns 201 and the to-be-printed substrate 202. FIG.
(E) An image pattern formed by the ink liquid film 205 remaining on the ink peelable film substrate 201 is transferred onto the surface of the substrate to be printed 202, and the image pattern is printed on the substrate to be printed 202 Process.
In this case, a basic pattern 204 serving as a base of an image pattern is provided in advance on the substrate to be printed 202, and the ink liquid film 205 is transferred in the fifth step in the basic pattern 204 selected from the basic patterns 204. This is done by transferring the image pattern on top.

The basic pattern 204 can be provided by the following process.
(A ′) An ink liquid film 205 for forming a basic pattern on an ink peeling layer 203 of an ink-peeling film base material 201 for forming a basic pattern having an ink peeling layer 203 on one surface which is one surface in the thickness direction. The process of apply | coating (FIG. 2 (a)).
(B ′) A step of pre-drying the ink liquid film.
(C ′) The basic pattern forming removal plate 211 on which the negative pattern convex pattern formed opposite to the basic pattern 204 is pressed against the preliminarily dried ink liquid film 205 to form the convex pattern. A step of forming a pattern of the ink liquid film 205 on the ink peelable film substrate 201 for forming the basic pattern by removing the corresponding part of the ink liquid film 205 (FIGS. 2B and 2C).
(D ′) A step of transferring the pattern of the ink liquid film 205 onto the surface of the substrate to be printed 202 and transferring the basic pattern 204 to the substrate to be printed 202 (FIGS. 2D, 2E, and 2F). )).

The basic pattern 204 can be provided by the following process.
(A ″) A light-shielding ink solution for forming a basic pattern on the ink peeling layer 203 of the ink-peeling film substrate 201 for forming a basic pattern having the ink peeling layer 203 on one side which is one surface in the thickness direction. A step of applying the film 206.
(B ″) A step of pre-drying the light-shielding ink liquid film 206.
(C ″) A base pattern forming removal plate 211 on which a convex pattern having the same concave and convex shape as the basic pattern 204 is pressed against the preliminarily dried light-shielding ink liquid film 206, and the light-shielding ink liquid corresponding to the convex pattern A step of forming a pattern of the light-shielding ink liquid film 206 on the ink-peeling film substrate 201 for forming the basic pattern by removing the film 206 (FIG. 3A).
(D ″) A step of transferring the pattern of the light-shielding ink liquid film 206 onto the printing substrate 202 coated with the ultraviolet curable resin 205 (FIG. 3B).
(E ″) A portion excluding a portion of the ultraviolet curable resin 205 to which the pattern of the light-shielding ink liquid film 206 is transferred by irradiating the surface of the substrate 202 to which the pattern of the light-shielding ink liquid film 206 is transferred with ultraviolet light. Step of curing (FIG. 3C).
(F ″) A step of forming a basic pattern 204 from the light-shielding ink liquid film 206 and the ultraviolet curable resin 206 that has been cured by removing the ultraviolet curable resin 206 that has not been ultraviolet cured with a soluble solvent (FIG. 3 (d)).

  Next, an example of a printing apparatus embodying the printing method according to the present invention is shown in FIG. 1 as a case where the substrate to be printed 202 is a flexible substrate, and will be described according to an actual printing process.

  As shown in FIGS. 1A to 1C, the printing apparatus includes an ink peelable film substrate unwinding unit 101, an ink peelable film substrate unwinding unit 107, a substrate to be printed unwinding unit 108, Ink peelable film substrate 201 such as printing substrate take-up unit 110 or an apparatus unit related to conveyance of substrate to be printed 202, coating unit 102, drying unit 103, pattern removing unit 104, alignment unit 105, pasting The combining unit 106 and the printing substrate drying unit 109 are configured.

  Ink peelable film substrate unwinding section 101, ink peelable film substrate unwinding section 107, printed substrate unwinding section 108, printed substrate unwinding section 110, and the like are each a take-up roll. A cylinder having a mounter on which a core having a diameter of 3 inches to 30 inches can be mounted in order to install or wind the supplied raw material, and a motor for transporting the film substrate by controlling rotation and tension.

  Although the film original fabric width as the printing substrate 202 to be mounted can be selected from 100 mm to 1000 mm, the width of 300 mm is selected in consideration of the practicality of the pattern and the transfer position accuracy.

  In addition, the tension of the film substrate such as the ink-peelable film substrate 201 and the substrate to be printed 202 can be controlled by installing a nip portion in the transport system and holding the substrate in addition to these devices. Can do.

  The nip part is a metal roll or sandwiched between a metal roll and a metal roll coated with a rubber, or an adsorption nip formed by an air adsorption hole provided in the conveyance roll, and is used when conveying the coating area of the ink film 205. , The mechanism that releases the nip and prevents the transport roll and the ink film 205 from contacting each other.

  When the transport is provided with a buffer for continuously transporting the film, the time difference required in each process is eased, but the continuous film can be transported at 5 m / sec to 10 m / sec. It is preferable to use a method in which 201 and the substrate to be printed 202 are drawn out for each process.

  The coating unit 102 is provided with a movable stage and a coating apparatus that applies the ink film 205 (FIG. 2A) to the ink peelable film substrate 201 provided on the movable stage.

  The movable stage can be driven by a ball screw, a linear motor, etc., and can be made of metal, stone, etc., but can reciprocate while maintaining at least the horizontal direction, The ink peelable film substrate 201 can be adsorbed.

  In order to prevent unevenness of the surface due to adsorption, a method of providing adsorption holes only near the edge of the film or a method of using an adsorption surface using a porous material can be selected.

  The coating apparatus will be described with respect to a die type which is excellent in continuous processing and film thickness uniformity, but is not limited thereto. The die head used as the coating head 209 can be supplied with a predetermined amount of ink from a separately prepared ink supply pump.

  The gap between the coating head 209 and the ink peelable film substrate 201 may be set before the start of printing, or may be adjusted by moving the coating head 209 up and down according to the conveyance of the movable stage. . The film thickness is preferably set by combining the ink supply amount, the gap between the heads, the gap between the head and the substrate, the coating speed, and the like, and is preferably set between 0.3 μm and 4 μm in dry film thickness. When the film thickness is thin, it becomes difficult to obtain a uniform coating surface. When the film thickness is large, the reproducibility of the patterning shape by the removal plate is deteriorated, and crushing at the time of transfer onto the substrate to be printed can be seen. .

  As shown in FIG. 1A, the drying unit 103 is installed to dry the ink film 205 coated on the ink-peeling film substrate 201 by the coating unit 102. Further, a drying device such as hot air, reduced pressure drying, and ultraviolet irradiation may be provided.

  As shown in FIG. 1A, the pattern removing unit 104 has a movable plate made of a resin or glass removed plate 211 attached thereto by suction, and as shown in FIGS. 2B and 2C, After the surface of the ink film 205 on the ink peelable film substrate 201 is brought close to the removal plate 211, the ink film 205 in contact with the convex portion of the removal plate 211 is removed by applying a load by the impression cylinder as the movable stage moves. 211 is transferred to the surface of the convex portion.

  As shown in FIG. 1C, the alignment unit 105 is composed of a movable stage and a plurality of microscope cameras 210 (FIG. 4C), and is on the substrate 202 to be printed adsorbed on the movable stage. Further, after the ink film 205 on the ink peelable film substrate 201 is brought close to 100 to 250 μm, it is obtained on the ink peelable film substrate 201 by utilizing the fact that the ink peelable film substrate 201 is transparent. A part of the pattern and the mark pattern for alignment and the pattern on the substrate 202 to be printed are recognized by the transmission image, and the movable stage is operated based on the image in which each substrate pattern is recognized to correct the transfer position. It can be performed.

  Also, a method of inserting a microscope camera 210 between the ink peelable film substrate 201 and the substrate to be printed 202 and correcting the position based on an image in which a pattern on each substrate is recognized can be selected.

  The microscope camera 210 may be either an optical microscope or a CCD (Charge Coupled Device) microscope. However, the microscope camera 210 requires the functions of either autofocus, an electrically controllable manual focus control mechanism, or both. It can have an interface to an external monitor for observation and an image processing device for position correction.

  As shown in FIGS. 1A and 1B, the bonding unit 106 is provided with a metal roller or a rubber roller on a movable stage installed in the alignment unit 105.

  A roller is pressed against the substrate 202 to be printed fixed on the movable stage and the ink peelable film substrate 201 installed with a slight gap, and the roller is rotated as the movable stage moves. The image portion pattern can be transferred onto the substrate to be printed 202 by applying pressure and then peeling the ink peelable film substrate 201 from the substrate to be printed 202.

  As shown in FIG. 1C, the film substrate drying unit 109 is installed to dry the image pattern transferred onto the substrate to be printed 202, and is a hot plate, oven, hot air, reduced pressure. Although it is possible to provide a drying device such as drying and ultraviolet irradiation, it is sufficient that drying necessary to prevent blocking at the time of winding of the substrate to be printed is possible, depending on the ink used, When UV curable ink is used, it is preferable to perform heat drying for about 1 to 10 seconds.

  Printing in each process, such as printing of the basic pattern, printing of the light shielding pattern, and printing on the basic pattern, which constitutes the printing method according to the present invention, is performed in the same manner as described above.

A red ink for a color filter was prepared as follows. A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and further filtered through a 5 μm filter to obtain a red pigment dispersion.
[Composition of red pigment dispersion for color filter]
・ Red pigment:
C. I. Pigment Red 254 (“Ilgar Forred B-CF” manufactured by Ciba Specialty Chemicals)
18 parts by weight C.I. I. Pigment Red 177 (Ciba Specialty Chemicals “Chromophthal Red A2B”)
2 parts by weight / acrylic varnish (solid content 20%) 108 parts by weight Thereafter, a mixture having the following composition was stirred and mixed uniformly, and then filtered through a 5 μm filter to obtain a red colored ink.
(Composition of red coloring ink)
-100 parts by weight of the above dispersion-20 parts by weight of methylated methylol melamine: MW-30 (manufactured by Sanyo Kasei Co., Ltd.)-3 parts by weight of leveling agent: Megafac F-483SF (manufactured by DIC)-85 parts by weight of propylene glycol monomethyl ether・ 45 parts by weight of propylene glycol monomethyl ether acetate

Moreover, the blue ink for color filters was prepared in the following way. A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and further filtered with a 5 μm filter to obtain a blue pigment dispersion.
[Composition of blue pigment dispersion for color filter]
・ Blue pigment:
C. I. Pigment Blue 15: 6 ("Chromofine Blue 5201A" manufactured by Dainichi Seika Kogyo)
25 parts by weight acrylic varnish (solid content 20%)
108 parts by weight Thereafter, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a blue colored ink.
(Composition of blue coloring ink)
-100 parts by weight of the above dispersion-20 parts by weight of methylated methylol melamine: MW-30 (manufactured by Sanyo Kasei Co., Ltd.)-2 parts by weight of leveling agent: Megafac F-483SF (manufactured by DIC)-85 parts by weight of propylene glycol monomethyl ether・ 45 parts by weight of propylene glycol monomethyl ether acetate

Moreover, the transparent ink for basic pattern formation was prepared in the following way. A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and further filtered through a 5 μm filter to obtain a dispersion.
[Composition of transparent particle dispersion for basic pattern]
・ Silica fine particles 20 parts by weight ・ Acrylic varnish (solid content 20%) 108 parts by weight (composition of transparent ink for basic pattern)
-100 parts by weight of the above dispersion-20 parts by weight of methylated methylol melamine ("MW-30" manufactured by Sanyo Chemical Co., Ltd.)-2 parts by weight of a leveling agent ("Megafac F-383SF" manufactured by DIC)-Propylene glycol monomethyl ether 85 Parts by weight ・ 45 parts by weight of propylene glycol monomethyl ether acetate

A light-shielding ink was prepared as follows.
(Composition of shading ink)
-Polyimide precursor ("Semicofine SP-510" manufactured by Toray Industries, Inc.) 15 parts by weight-Carbon black 10 parts by weight-N-methylpyrrolidone 130 parts by weight-Dispersant (copper phthalocyanine derivative) 5 parts by weight-Propylene glycol monomethyl 15 parts by weight of ether acetate The above material was dispersed for 3 hours while cooling with a bead mill disperser, and further filtered with a 5 μm filter to prepare a partition wall ink.

  As an ink peelable film substrate, a transparent polyethylene terephthalate (PET) film (Diafoil T600 manufactured by Mitsubishi Plastics Co., Ltd.) having a substrate thickness of about 100 μm is 500 mm wide, and a die coater is used at the center 300 mm width on 300 m. A peelable silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd.) KS847 and a curing agent coated with a solid content weight ratio of 2% so as to have a thickness of about 10 μm was used.

  As a removal plate for providing a pattern, a mark for alignment and a mask pattern for a display panel were provided by etching on an alkali-free glass with Cr of 300 mm × 300 mm × 0.7 mm using a photomask. Provided at the four corners of the alignment mark 250 mm □, the display panel pattern was provided with a continuous tile pattern with a convex portion of 20 μm width and a concave portion of 80 μm width within a plate central portion of 180 mm □ with a plate depth of 2 μm.

  Further, a light-transmitting polyethylene naphthalate (PEN) substrate (“Teonex Q65F” manufactured by Teijin DuPont Films Ltd.) having a film thickness of 125 μm was prepared as a substrate to be printed in a roll shape of 300 mm width and 20 m.

  Using the above members, processing was performed using the apparatus of FIG.

(Printing basic patterns on the substrate)
First, the ink-releasable film base material 201 was drawn out so that the surface of the new ink peeling layer 203 came on the stage of the coating unit 102, vacuum fixed to the stage of the coating unit 102, and then a 300 mm wide head was used. The basic pattern transparent ink was coated with a die coater with a coating length of 350 mm and a film thickness of 0.8 μm (FIG. 2A).

  Then, after drying for 30 seconds in the installed 40 degreeC IR furnace and conveying until the coating part 102 was installed on the stage of the pattern removal part 104, it waited for 120 second at room temperature further. The ink-coated portion on the ink-peelable film substrate 201 was conveyed so as to be on a transfer stage on which a removal plate 211 in which various marks including an electronic paper CF pattern and alignment marks were etched (FIG. 2 ( b)). A pressure was applied to the transfer rubber roller from the back side of the ink-peeling film substrate 201 (the surface opposite to the surface coated with the ink) to transfer the non-image portion to the convex portion of the removal plate 211. Further, along with the movement of the metal roller, the ink peelable film substrate 201 was peeled from the removal plate 211 (FIG. 2 (c)). The stage supporting the removal plate 211 was slid in the horizontal direction, and the transfer unit in which the conveyance system of the printing substrate 202 and the alignment stage were integrated was raised.

  Next, the pattern remaining on the ink-peeling film substrate 201 was conveyed onto the alignment unit stage on which the substrate 202 to be printed on which the alignment mark had been printed was fixed by suction (FIG. 2D). The basic pattern 204 is applied to the substrate to be printed by laminating the ink peelable film substrate 201 and the substrate to be printed 202 with a rubber roller, and then peeling the ink peelable film substrate from the substrate to be printed while moving from the stage. Was transferred (FIG. 2 (e)). The transferred basic pattern 204 was dried at 80 ° C. for 2 minutes.

  Next, the light-shielding ink was transferred to the substrate 202 to be printed only in the vicinity of the alignment mark provided around the pixel pattern of the color filter in the same manner as described above. As a result, the shading ink was laminated on the alignment mark provided with the basic pattern 204 and having a convex shape, and the alignment mark was easily recognized.

(Printing on the selected basic pattern)
Further, in the same manner as in the above printing step, the red ink 205 was applied on the ink peelable film substrate 201 to a coating length of 350 mm and a film thickness of 0.8 μm, and was dried only at room temperature for about 7 minutes. . With respect to the panel pattern provided by the basic pattern 204, a red subpixel pattern was formed on the ink-peelable film substrate 201 by using a removal plate 211 corresponding to a quarter of the subpixels.

  As shown in FIGS. 4A and 4B, the basic pattern 204 is printed, and the substrate 202 to be printed on which the light shielding ink is laminated on the alignment mark 208 is fixed on the alignment stage. And as shown in FIG.4 (c), the alignment mark formed with the red ink 205 patterned using the removal plate 211 on the ink peelable film base material 201, and the alignment mark 208 of the to-be-printed base material 202 While observing both alignment marks, the alignment stage on which the substrate to be printed 202 was fixed was moved for alignment.

Next, the substrate to be printed 202 and the ink peelable film substrate 201 are bonded together, the ink peelable film substrate 201 is peeled off, and the basic pattern on the substrate to be printed 202 is shown in FIG. A pixel pattern created with red ink 205 was laminated on 204.
Similarly, blue ink 205 (shown by hatching different from red ink 205 in the figure) was laminated on another basic pattern 204. In both color inks, the color ink was transferred only to the convex portion provided with the basic pattern 204, and the pixel pattern accuracy as designed by the CF was obtained.

  Using a die-type coater, an ultraviolet curable resin (“Unidic RC29-117” manufactured by DIC) is coated on the substrate to be printed with a MEK solvent to a thickness of about 1 μm, and then in an 80 ° C. environment for 2 minutes. Dried.

  In the same manner as in Example 1, after printing a negative pattern of a pixel pattern using a light-shielding ink 206 on a printing substrate 202 coated with an ultraviolet curable resin 205, the surface is irradiated with ultraviolet light using a high-pressure mercury lamp. (FIGS. 3A to 3C).

  Next, the alignment mark portion is protected with an adhesive film so that only the pixel pattern portion on the substrate 202 to be printed is exposed, and then the uncured ultraviolet curable resin 205 of the pixel pattern portion is removed with a waste dipped in MEK solvent. By removing the light shielding pattern (light shielding ink 206), a basic pattern 204 was obtained on the substrate 202 to be printed (FIG. 3D).

  Subsequently, the red ink and the blue ink were stacked on the selected pixel pattern on the basic pattern 204 and printed in the same manner as in Example 1. As a result, in both color inks, the color ink was transferred only to the convex portion provided with the basic pattern 204, and the pixel pattern accuracy as designed by the CF was obtained.

  Since the printing method of the present invention can continuously and stably perform thin film printing of high-definition patterns on flexible substrates such as glass substrates and plastic films, especially long flexible substrates. Used for manufacturing color filter members such as color patterns, black matrix, white matrix, spacers, gate electrodes, source electrodes, drain electrodes, gate insulating films, transistor members such as organic semiconductor materials, and organic EL elements such as organic light emitting layers it can.

DESCRIPTION OF SYMBOLS 101 ... Ink peelable film base material unwinding part 102 ... Coating part 103 ... Drying part 104 ... Letter-press bonding / pattern removal part 105 ... Alignment part 106 ... Adsorption stage / Laminating part 107 ... Ink peelable film substrate winding part 108 ... Printed substrate unwinding part 109 ... Printed substrate drying part 110 ... Printed substrate winding part 201 ..Ink peelable film substrate 202... Substrate to be printed 203... Ink peel layer 204... Basic pattern 205 .. ink film 206 .. light shielding ink layer 207. 208... Alignment mark 209... Coating head 210... Microscope camera 211.

Claims (6)

(A) A first liquid film is coated on the ink release layer of the ink peelable film substrate which is made of a transparent material and has an ink release layer on one side which is one side in the thickness direction. Process,
(B) a second step of pre-drying the ink liquid film;
(C) A removal plate on which a negative pattern convex pattern of a predetermined image pattern is formed is pressed against the preliminarily dried ink liquid film, and the ink liquid film portion corresponding to the convex pattern is removed. The third step of forming the image pattern with the ink liquid film remaining on the ink peelable film substrate,
(D) The image pattern formed by the ink liquid film remaining on the ink peelable film substrate and the pattern provided in advance on the surface of the substrate to be printed are superposed and observed, and the ink peelable film base A fourth step of aligning the material and the substrate to be printed;
(E) transferring the image pattern formed by the ink liquid film remaining on the ink peelable film substrate onto the surface of the substrate to be printed, and printing the image pattern on the substrate to be printed; A method of printing a precision pattern including the steps of:
A basic pattern serving as a base of the image pattern is provided in advance on the substrate to be printed,
Transfer of the ink liquid film according to the fifth step is performed by transferring the image pattern onto the selected basic pattern among the basic patterns.
A method for printing a precision pattern. The basic pattern is
(A ′) An ink liquid film for forming a basic pattern is applied on the ink peeling layer of an ink peeling film base material for forming a basic pattern having an ink peeling layer on one surface which is one surface in the thickness direction. And a process of
(B ′) a step of pre-drying the ink liquid film;
(C ′) The basic pattern forming removal plate on which the convex pattern of the negative pattern formed in the shape opposite to the basic pattern is pressed against the preliminarily dried ink liquid film, Forming a pattern of the ink liquid film on the ink peelable film substrate for forming the basic pattern by removing the corresponding part of the ink liquid film;
(D ') The pattern of the ink liquid film is transferred onto the surface of the substrate to be printed, and the step of transferring the basic pattern to the substrate to be printed is provided.
The printing method of the precision pattern of Claim 1. The basic pattern is
(A ″) A light-shielding ink liquid film for forming a basic pattern is formed on the ink peeling layer of an ink-peeling film substrate for forming a basic pattern having an ink peeling layer on one surface which is one surface in the thickness direction. Coating process,
(B ″) a step of pre-drying the light-shielding ink liquid film;
(C ″) The base pattern-forming removal plate on which a convex pattern having the same concave and convex shape as the basic pattern is pressed against the preliminarily dried light-shielding ink liquid film, and the light-shielding ink corresponding to the convex pattern Forming a pattern of the light-shielding ink liquid film on the ink-peeling film substrate for forming the basic pattern by removing a portion of the liquid film;
(D '') transferring the pattern of the light-shielding ink liquid film onto the substrate to be printed coated with an ultraviolet curable resin;
(E ″) The surface of the substrate to be printed on which the pattern of the light-shielding ink liquid film has been transferred is irradiated with ultraviolet rays, and the portion other than the part to which the pattern of the light-shielding ink liquid film is transferred is transferred from the ultraviolet curable resin. Curing, and
(F ″) provided by the step of forming the basic pattern with the light-shielding ink liquid film and the ultraviolet curable resin remaining by removing the ultraviolet curable resin that has not been ultraviolet cured with a soluble solvent. It is characterized by
The printing method of the precision pattern of Claim 1.   4. The precision pattern printing method according to claim 1, wherein a silicone resin layer is laminated on a transparent film base material as the ink peelable film base material. The basic pattern is made of a transparent material,
The basic pattern includes an alignment pattern provided for alignment,
Transfer the ink that can be visually or machine recognized on the alignment pattern,
The alignment pattern to which the ink has been transferred is used as a pattern provided in advance on the surface of the substrate to be printed in the fourth step. Precision pattern printing method.   A method for producing a color filter, wherein a colored layer is formed by the precision pattern printing method according to any one of claims 1 to 5.

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