JP2006058838A - Fabrication process of color filters, inks, color filters, and image displays using the color filters - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To fabricate CFs, which show excellent performance in image characteristics such as pixel fineness and definitions, by a fabrication process which can economically fabricate the CFs at low cost through rationalized steps and can also meet the move toward larger CFs, and also to provide CFs and image displays at low cost. <P>SOLUTION: A fabrication process of color filters is disclosed. The color filters can each be fabricated by printing a pixel pattern for the color filter on a flexible plastic film by a central impression press. The pixel pattern is formed of pixels of three primary colors consisting of red, green and blue or pixels of three primary colors consisting of yellow, magenta and cyan. Also disclosed are inks, color filters, and image displays using the color filters. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a color filter (hereinafter abbreviated as “CF”), ink, CF, and an image display device using the CF, and more specifically, directly to a CF film or fixed to the printing surface of the film. CF in which three primary color pixels are printed using a center impression type printing machine through a mask having a vacant hole (an opening through which pixel forming ink passes, the same applies hereinafter), a material used for the production, and a production thereof Regarding the method, the display image quality is excellent in image characteristics such as pixel fineness and sharpness, can achieve rationalization of the manufacturing process, and is economically manufactured at low cost. The present invention relates to an image display device.

  With the recent development of information-oriented devices, liquid crystal color displays are used as information display members such as personal computers, mobile information devices, televisions, projectors, monitors, car navigation systems, mobile phones, electronic computers, and electronic dictionaries. It is used in a wide variety of information display related devices such as screens, information bulletin boards, information bulletin boards, displays such as function display boards and sign boards, and digital camera and video camera shooting screens. Along with that, CFs mounted on liquid crystal color displays are also required to have better quality in terms of image performance such as sharpness, transparency, and contrast. Both of them have progressed together, and in all of them, CF has been required to be provided at low cost.

  In many cases, the CF is manufactured by a manufacturing method called “photolithographic method”. In this method, when a pixel pattern of three primary colors of red color (R), green color (G), and blue color (B) in the additive color mixing method is formed, the photosensitivity of one of the three colors is used. A color resist (photosensitive ink) is applied to a CF substrate with a spin coater, and then irradiated with ultraviolet rays through a photomask having a translucent pattern corresponding to a pixel pattern of a corresponding color prepared in advance. Is cured, and an unexposed portion of the coating film is washed and removed to develop the pixel pattern of the specific color. The above means are repeated for the remaining two types to produce CF. The same applies to the formation of a CF having pixel patterns of three primary colors of yellow (Y), magenta (M) and cyan (C).

  However, in the photolithographic method, the amount of each resist applied by a spin coater to form a corresponding actual pixel pattern is, for example, about 10% of the actually used resist, and most of the resist is discarded. This is very uneconomical, and the resist forming the pixel pattern is relatively expensive.

  As a solution to the above problem, instead of spin-coating a resist, the colored films of R, G, and B coated on the entire surface of the plastic film are sequentially transferred onto the CF substrate, or are cast on the CF substrate with a slit coater. Attempts have been made to reduce the loss of color resist. However, in any case, pixels are formed by a photolithographic method, and the problem that many processes are required has not been solved.

  In addition, for the purpose of rationalizing the manufacturing method and economically, the production of CF by the printing method has been tried. However, since the R, G, and B3 primary colors are printed for each color, there is a deviation between the printed pixels. As a result, the resolution and position accuracy of the print pixels are low, and therefore the fineness and sharpness of the three primary color pixels are insufficient.

  An object of the present invention is to provide a manufacturing method capable of economically and inexpensively producing a CF having excellent performance in image characteristics such as pixel fineness and sharpness, economically at low cost, and corresponding to an increase in the size of the CF. To provide a CF and an image display device at low cost.

  The present inventors use a center impression type (center drum type) printing machine to form a CF pixel pattern, and particularly by printing through a mask having holes that match the pixel pattern, a highly accurate pixel pattern. CF with excellent performance in image characteristics such as pixel fineness and sharpness is obtained, and the resolution and positional accuracy, which are inevitable defects of the normal printing method as described above, are insufficient. It was found that this was solved.

That is, the configuration of the present invention is as follows.
1. Print a CF pixel pattern consisting of three primary pixels of red, green and blue, or three primary pixels of yellow, magenta and cyan on a flexible plastic film by a center impression printer A method for producing CF, wherein
2. 2. The method for producing CF according to 1 above, wherein the plastic film having flexibility is a plastic film for transfer or attachment, and the pixel pattern printed on the film is transferred or attached to the CF substrate.
3. 2. The method for producing CF according to 1 above, wherein the pixel pattern is printed through a hole mask having a positive-negative relationship with the pixel pattern, and then the mask is peeled off.

4). 2. The method for producing CF according to 1 above, wherein the center impression type printing machine comprises a center drum and 3 to 10 printing units installed in a satellite shape around the center drum.
5. 4. Production of CF as described in 3 above, wherein the hole mask is a mask in which holes are formed in a negative-positive relationship with respect to the pixel pattern by a laser ablation method after a mask film is formed on the plastic film. Method.
6). 4. The method for producing CF according to 3 above, wherein the hole mask is a mask obtained by printing a film in a region other than the pixel pattern to be formed on the plastic film.
7). 4. The method for producing CF as described in 3 above, wherein the pore mask is provided with an adhesive layer, and is fixed onto the plastic film via the adhesive layer.

8). The pore mask is (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, Ethylene-vinyl acetate- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer and a soluble salt comprising an ammonium salt or an amine salt thereof; (meth) acrylic acid ester -(Alkoxy) polyethylene glycol (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid ester- (alkoxy) polyethylene glycol (meth) acrylic acid ester copolymer, styrene- (alkoxy) polyethylene glycol (meth) Acrylate ester copolymer; methylcellulose, hydroxy From ethyl cellulose, hydroxypropyl cellulose, cellulose acetate phthalate; vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-ethylene copolymer; hydrophilic polyurethane, hydrophilic polyester; and ethylene oxide-alkylene (C3, C4) oxide copolymer 4. The method for producing CF as described in 3 above, which is formed from a material selected from the group consisting of:

9. 4. The hole mask is formed of a plastic film made of a material selected from the group consisting of polyester, nylon, vinyl alcohol copolymer, polyvinyl butyral, polyimide, polyamideimide, cellulose acetate, polyethylene, and polypropylene. A method for producing CF.
10. 4. The method for producing CF according to 3 above, wherein the hole forming mask contains a thermal energy ray-absorbing component and / or a self-combustible resin component.
11. 11. The method for producing CF as described in 10 above, wherein the thermal energy ray absorbing component is carbon black and / or an infrared absorbing compound.
12 11. The method for producing CF as described in 10 above, wherein the self-combustible resin component is nitrocellulose.

13. 2. The CF manufacturing method according to 1 above, wherein the center impression type printing machine is of a type using a printing method selected from the group consisting of a flexographic printing method, a gravure printing method and an offset printing method using a printing plate having a pixel pattern. .
14 The center impression type printing machine consists of liquid ink jet printing method, dispenser injection printing method, coating needle under-drop printing method, electrostatic liquid printing method, thermal transfer printing method, electrostatic powder printing method and solid ink jet printing method. 2. The method for producing CF as described in 1 above, which is of a type using a printing method selected from.

15. The ink used for the method for producing CF according to any one of 1 to 14 above, which comprises a dye and a binder.
16. 16. The ink according to 15 above, which is an organic solvent-based ink, water-based ink, solvent-free ink, or heat-meltable solid ink.
17. 16. The ink according to 15 above, wherein the pigment is a pigment.
18. The pigment is a pigment used to form red (R), green (G) or blue (B) pixels; I. Pigment Red 9, 97, 168, 177, 216, 224, 226, 242 and 254, a red pigment comprising C.I. I. A green pigment comprising CI Pigment Green 7 and 36; I. Pigment Blue 15: 6, 60, a blue pigment comprising C.I. I. Pigment Violet 23, a violet (V) pigment comprising subphthalocyanine, C.I. I. Pigment Yellow 20, 24, 83, 93, 109, 110, 113, 114, 117, 125, 138, 139, 150, 154, 180, 185, and the above-described red pigment and yellow 18. The ink according to 17, wherein the ink is selected from the group consisting of a coprecipitated pigment with a pigment, a coprecipitated pigment with a green pigment and a yellow pigment, and a solid solution pigment and a mixed crystal pigment of these pigments.

19. The pigment is a pigment used to form yellow (Y), magenta (M) or cyan (C) pixels; I. Pigment Yellow 62, 74, 93, 128, 155, 185, a yellow pigment, C.I. I. Pigment Red 122, 146 and C.I. I. A magenta pigment comprising a violet pigment comprising CI Pigment Violet 19; I. A cyan pigment composed of CI Pigment Blue 15: 3, a coprecipitation pigment of yellow pigment and cyan pigment, a coprecipitation pigment of red pigment and violet pigment, and a coprecipitation pigment of cyan pigment and yellow pigment, and their 18. The ink as described in 17 above, which is a solid solution pigment or mixed crystal pigment.
20. The pigment is kneaded and ground with a water-soluble salt and a water-soluble organic solvent in a kneader, and the pigment ground mass obtained by refining the average particle size of the pigment to 10 to 130 nm is washed with water and filtered. 18. The ink according to 17 above, which is an aqueous filter cake of a fine pigment obtained as described above.

21. 18. The ink according to 17 above, wherein the pigment is a fine powder pigment obtained by drying and pulverizing an aqueous filter cake of the pigment.
22. 18. The ink according to 17 above, wherein the pigment is a processed pigment obtained by mixing and coprecipitating an aqueous filter cake of the pigment with an easily dispersible polymer.
23. 18. The ink according to 17 above, wherein the pigment is a processed pigment obtained by kneading a fine powder of the pigment with an easily dispersible polymer.

24. Random, block and graft copolymers in which the binder may have reactive groups, hydrophobic groups and / or hydrophilic groups; may have reactive groups, hydrophobic groups and / or hydrophilic groups 18. The ink according to 17 above, which is a film-forming substance selected from the group consisting of an oligomer and a monomer, oligomer and / or polymer having an addition polymerizable unsaturated double bond or addition condensable epoxy group.
25. 18. The ink according to 17 above, wherein the average particle diameter of the pigment is 10 to 130 nm. 26. 15. A CF formed by the method according to any one of 1 to 14 above.
27. An image display device equipped with the CF described in 26 above.
28. 28. An information transmission device equipped with the image display device according to 27.

  Hereinafter, in the present invention, a plastic film having flexibility or a plastic film for transfer or pasting is referred to as “CF film”, and a glass CF substrate or plastic CF substrate is referred to as “CF substrate”, or for transfer or pasting. The plastic film may be referred to as “transfer or paste film”. The three primary colors of red, green and blue or yellow, magenta and cyan are designated as “R”, “G”, “B”, “Y”, “M” and “C”, respectively. The R, G, and B pixels or Y, M, and C pixels may be collectively referred to as “CF pixels”, “pixel patterns”, or simply “pixels”. Further, the black matrix may be referred to as “BM”.

  As pixel patterns of the R, G, and B3 primary colors of CF or pixel patterns of the Y, M, and C3 primary colors, known pixel patterns are used, a stripe arrangement suitable for displaying information such as characters and graphics, and a mosaic suitable for displaying video data. An array or a triangle array.

  The present invention uses a CF film as it is, or a hole mask having a positive-negative relationship with respect to a CF pixel pattern is fixed on the CF film in advance, and the hole mask is directly or directly attached to the CF film. When fixed, a pixel pattern of three colors is printed using the pixel impression ink by the center impression type printing machine through the hole mask, and when the mask is used, the mask is removed after printing. In addition, when a transfer / sticking film is used, a CF can be manufactured by transferring or pasting the pixel pattern of the film onto a CF substrate.

  The reason why the method of the present invention can form a pixel pattern with high precision regardless of the printing method is that the “CF film” is pressed by the center drum of the center impression type printer and rotates together with the three primary color pixels. Since it is continuously printed, the pixel pattern is printed with high accuracy. Further, when a hole mask is formed on the CF film, the holes of the three primary color pixels are formed with high accuracy by one simultaneous operation instead of for each color, and the mask is fixed to the film. Therefore, an extremely accurate pixel pattern is formed, and the obtained CF has excellent performance in image characteristics such as pixel fineness and sharpness.

  Also, from the viewpoint of economic effect, the conventional CF production is an organic solvent-based color resist coating-photolithographic method, and requires a lot of long production steps, so a great initial investment is required. Compared with the high running cost, the manufacturing method of the present invention is basically a printing method, and the initial investment is relatively small, the manufacturing process is short, rationalization can be achieved, and the running cost is also low. It is cheap, very economical, and can provide CF at low cost.

  In particular, when an aqueous ink is used as the ink, an aqueous filter cake of a finely divided pigment can be used as the colorant of the ink, and the optical characteristics such as sharpness, color purity, optical density, transparency, and contrast are excellent. In addition to being able to form pixels, there is no need for significant capital investment in terms of hygiene characteristics in the work environment, safety against fire hazards, etc., and the economic effect is remarkable due to the rationalization effect of the manufacturing process.

  Further, as described above, the CF is being increased in size in response to the recent increase in the size of image display devices such as color displays and color televisions. However, the manufacturing method using the center impression printing method of the present invention is a great investment. Therefore, it is possible to provide a CF capable of easily increasing the size of a color display without requiring the above.

  Hereinafter, the present invention will be described in detail. A method for producing a CF by printing three primary color pixels using a center impression type printer will be described below. The features of the center impression type printing machine that characterizes the present invention will be described. With reference to FIG. 1, a center impression type printing machine for flexographic printing will be described as an example. Around the center drum 1 (central impression cylinder), for example, three to ten printing units 2 are mounted in a satellite type.

  The maximum width of the plastic film printed by the printer depends on the design of the printer, but is, for example, 250 mm to 1550 mm, and the maximum print effective width is, for example, 230 mm to 1520 mm. The film to be printed is supplied from the supply unit, wound around a temperature-adjusted center drum, and rotates at the speed suitable for the rotation, so the tension applied to the film during printing, the so-called tension, does not change, and between each printing unit The film does not easily stretch or sag in the film. A film is printed on the outside of the center drum with ink from each printing unit loaded in a satellite type, and the printing film is introduced into a drying unit, dried, and taken up at a winding unit. Therefore, even a thin film is excellent in register accuracy, and each pixel constituting a pixel pattern formed on the film can be printed without being deviated from each other, which is very preferable.

  The number of printing units mounted on the center drum will be described. In order to avoid the uneven printing of the pixel pattern, it is preferable to install two or more printing units per color and repeatedly print the same color. For example, a center impression type printing machine in which six or more printing units are mounted in a satellite type so that a pixel pattern of R, G, B3 primary colors or Y, M, C3 primary colors can be printed is preferable. In order to further increase the color density, it is also possible to print one color three times or more using 7 to 10 printing units for 3 colors.

  As a printing method by the center impression type printing machine, any of a number of conventionally known printing methods as a printing unit can be used. For example, (1) printing method using a printing plate having a pixel pattern, such as flexographic printing, gravure printing, offset printing, and (2) a printing method for ejecting or transferring a pixel pattern, for example, liquid ink jet printing Plateless printing (printing plate is not used) such as printing method, dispenser injection printing method, coating needle under-drop printing method, electrostatic liquid printing method, thermal transfer printing method, electrostatic powder printing method, solid inkjet printing ink method Printing) method.

  Of the printing methods equipped with printing plates, the flexographic printing method is particularly preferable. As a flexographic printing unit, the anilox roller is a ceramic sleeve anilox roller, its linear density is 300 to 2500 lines / inch, preferably 400 to 1000 lines / inch, the plate depth is 1 to 20 μm, preferably 2 to 10 μm, Further, it is preferable to use a printing unit in which the printing plate is an endless sleeve type resin seamless printing plate and the line density is 100 to 800 lines / inch, preferably 100 to 300 lines / inch. The ink supply device is preferably a completely sealed type that is side-sealed and has two upper and lower doctors, and is provided with an ink supply device in which inflow and discharge of ink are performed in an ink doctor chamber with holes. Printing is performed wet-on-wet because of the structure of the printing unit installation described above. The printing pressure is preferably low printing pressure (kiss touch) in order not to create a marginal zone in the printed image. As a drying method, warm air drying, heat drying, ultraviolet curing, electron beam curing, gas drying, or the like is used.

  Subsequent to printing by the center impression type printing machine, in order to manufacture a liquid crystal color display online or offline, an overcoat layer or transparent electrode layer coating apparatus, an adhesive coating apparatus, a laminating apparatus such as a polarizing film, It can also be connected to various processing devices such as cutting devices. The transparent electrode layer is formed using an ink in which a known inorganic conductive fine particle material such as tin oxide, indium oxide, antimony oxide, or indium tin oxide is finely dispersed as a conductive material. Furthermore, in the case of the transfer and affixing method of (2), it is possible to connect to a glass CF substrate or a plastic CF substrate, a transfer processing apparatus, and perform continuous processing. .

  Production of CF by printing in the present invention includes a method of directly printing on a plastic film and a method of transferring a film on which a three-primary-color pixel pattern has been printed in advance onto a CF substrate or affixing the film. CF film used for printing is a film that has the flexibility to follow the rotation of the center impression type printing machine and does not extend during the transfer process such as feeding, turning, and winding the film in the printing machine. If available, it can be used. As the film, a known film such as a polyester film, a polypropylene film, or a composite film is used. The film thickness is 10 to 300 μm, preferably 12 to 150 μm, although it depends on the type and processing of the film.

When it is necessary to print a pixel pattern with higher accuracy, a hole mask having a positive-negative relationship with respect to the arrangement pattern of R, G, B pixels or Y, M, C pixels can be used. . The mask is created by any one of the following methods, for example.
(1) A film forming material is applied on a CF film to form a mask film (A), or after a mask forming film (B) is pasted, the mask film (A) or mask forming film A method of forming holes having a negative-positive relationship with respect to the pixel pattern by laser ablating the film (B);
(2) A method of printing a hole pattern on a CF film by a printing method or the like, forming a film in a region other than the pixel pattern, and forming a mask;
(3) A method of laser ablating the mask forming film (B) to form holes having a negative-positive relationship with respect to the pixel pattern, and affixing the holes on the CF film.
The thickness of the mask is determined according to the thickness of the pixel to be formed, but is approximately 1 to 10 μm.

  A method for printing and forming a pixel pattern through the hole mask will be described. The center impression type printing machine is preferably used when it is desired to reproduce the position registration when printing a pixel pattern with higher accuracy. In the printing method using the printing plate described above, the hole mask that is no longer necessary after printing is peeled off and removed, so that the pattern printing accuracy is insufficient when each pixel is printed on the mask in sequence. Even if it exists, the pixel pattern formed on the CF film is accurately formed at the positions of the holes. In addition, by setting the ink adhesion area of the printing plate to be slightly larger than the hole and making the plate, the rising edge of the pixel that tends to occur during printing without using a normal mask, the reverse thinning, or Printing defects such as bleeding occur on the mask outside the pores, and the mask that is no longer necessary after printing is peeled and removed in the same manner as described above, and the defects can be eliminated. Also, the printing method in which ink is directly injected into the holes can form a highly accurate pixel pattern by injecting an appropriate amount of ink into the holes. The ink protruding from the pores is peeled and removed together with the mask that is no longer necessary after printing, as described above.

  As a material for forming the mask film (A), it is not dissolved or swollen by the ink used subsequently, and the pixel is used as a remover for removing the mask that is no longer needed after printing the pixel. Must not be attacked. Further, as a mask removing solution, it is preferable to use water or a water-lower alcohol (carbon number: 1 to 3) mixed solvent in consideration of safety and economy. Examples of the forming material include hydrophilic polymer materials. Among them, a copolymer having a carboxyl group, which can be removed with an alkaline aqueous solution, is preferable.

  Examples of the copolymer include (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid. Copolymers, ethylene-vinyl acetate- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymers and their soluble salts such as ammonium or amine salts; ) Acrylic ester- (alkoxy) polyethylene glycol (meth) acrylic ester copolymer, styrene- (meth) acrylic ester- (alkoxy) polyethylene glycol (meth) acrylic ester copolymer, styrene- (alkoxy) polyethylene Glycol (meth) acrylate copolymer; methyl cell Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate-phthalate, etc .; vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-ethylene copolymer, etc .; hydrophilic polyurethane, hydrophilic polyester, etc .; ethylene oxide-alkylene (C3, C4) A known polymer such as an oxide copolymer may be mentioned, and these polymers are used in the state of an organic solvent solution or an aqueous solution.

  Further, as the mask forming film (B), a film material that does not dissolve or swell in the ink used subsequently is used, and known film materials such as polyester, nylon, vinyl alcohol copolymer, polyvinyl butyral, polyimide, etc. Plastic films such as polyamideimide, cellulose acetate, polyethylene, and polypropylene are used.

  In the case of the film for mask formation (B), it is necessary to affix it to the CF film, but the film for mask formation (B) may have an adhesive strength that is fixed at the time of printing. For this, a well-known bonding method is used. Since the mask forming film (B) needs to be peeled off after the pixel pattern is printed, it is preferable to apply an adhesive having an easy peelability to the CF film.

  In addition, when it is desired to perform laser ablation with low energy for manufacturing a mask, it is preferable to contain a thermal energy ray absorbing component and / or a self-combustible resin component in the mask forming film. Examples of the heat energy ray absorbing component include infrared absorbing compounds such as carbon black and cyanine compounds, and known carbon blacks for black pigments and rubber reinforcement are particularly preferable. Further, as the self-combustible resin component, known nitrocellulose for paints and inks is preferable.

  The size of the hole of the mask is determined by the pixel pattern designed according to the use of the CF, and is not particularly limited. For example, the major axis is about 30 to 500 μm and the minor axis is about 10 to 200 μm. Yes, the film thickness is about 0.2 to 5 μm.

  The material used for the ink used in the present invention will be described. The components constituting the ink include a dye, a binder, and a polymer dispersion aid, a dye dispersant, and a liquid medium that are added as necessary. As the dye, a pigment is particularly preferable from the viewpoint of excellent fastness such as heat resistance, light resistance and solvent resistance. When an ink is formed using a pigment, a binder, a pigment dispersant and a liquid dispersion medium are used. Depending on the type or presence or absence of the liquid dispersion medium, the ink is classified into organic solvent-based ink, water-based ink, addition polymerization or addition-crosslinking (that is, solvent-free) ink, or heat-meltable solid ink.

  The pigments contained in the inks for R, G, and B pixels, Y, M, and C pixels will be described. Organic pigments, dyes, inorganic pigments, and the like that have been used as conventional pigments for R, G, and B pixels and Y, M, and C pixels are similarly used. For example, as pigments, azo pigments such as insoluble azo, soluble azo, and high molecular weight azo, quinacridone red, quinacridone magenta, and other quinacridone pigments, anthraquinone pigments, perylene pigments, phthalocyanine blue, phthalocyanine Conventionally known pigments such as phthalocyanine pigments such as green pigments, isoindolinone pigments, dioxazine pigments such as dioxazine violet, complex pigments such as quinophthalone yellow pigment, and nickel azo yellow can be used. The black pigment used when forming BM by the printing method includes carbon black pigment, composite oxide black pigment, iron oxide black pigment, titanium oxide black pigment, azomethine azo black pigment, and perylene black pigment. Conventionally known black pigments such as are used.

  Regarding dispersible dyes, oil-soluble dyes, and water-soluble dyes, conventionally known dyes as R, G, B color, Y, M, and C color may be used alone or in combination with pigments. Dyes are inferior in various fastness properties compared to pigments, but pigments and various dyes are used by taking advantage of their respective characteristics because they are excellent in optical properties such as vividness of color tone, color tone, transmittance of color, and contrast.

  As a CF used for a liquid crystal color display, it is necessary to emit a color perceived by a person as an image display member. For example, since the emission wavelengths corresponding to R, G, and B in the energy distribution of a three-wavelength fluorescent lamp used as a backlight light source are 610 nm, 540 nm, and 430 nm to 480 nm, It is preferable that the color of the light emission wavelength and the color of the preferable wavelength in the light emission wavelength range, for example, the red pixel is adjusted to 610 nm, the green pixel is set to 540 nm, and the blue pixel is set to 460 nm. Therefore, as the dye forming the CF pixel, a dye having a high transmittance at the wavelength of the corresponding color and having excellent physical properties, particularly a pigment, is used.

  Although many pigments are mentioned as a pigment which forms R, G, and B described above, specific examples of typical pigments include C.I. I. Pigment Red (hereinafter referred to as PR) 9, 97, 177, 168, 216, 226, 242 and 254, and C.I. I. Pigment Green (hereinafter referred to as PG) 7, 36, etc. I. Pigment Blue (hereinafter referred to as PB) 15: 6, 60 and the like, C.I. I. Pigment violet (hereinafter referred to as PV) 23, subphthalocyanine, C.I. I. Pigment yellow (hereinafter referred to as PY) 20, 24, 83, 93, 109, 110, 113, 138, 139, 150, 154, 180, 185, and the above-mentioned red pigment and yellow pigment. Examples thereof include precipitated pigments, coprecipitated pigments of green pigments and yellow pigments, solid solution pigments or mixed crystal pigments of these pigments.

  Typical examples of pigments useful for forming each pixel of Y, M, and C include PY62, 74, 93, 128, 155, and 185 as yellow pigments, and PR122, 146, PV19, and cyan pigments as magenta pigments. PB15: 3, and coprecipitation pigments of yellow and cyan pigments, magenta pigments and violet pigments, coprecipitation pigments of cyan and yellow pigments, and solid solution pigments of these pigments Or a mixed crystal pigment is mentioned. As a typical example of the black pigment forming the above BM, C.I. I. Pigment black (hereinafter referred to as PBK) 6, 7, 11, 26.

  A preferred pigment used in the present invention is a finely divided pigment. In the present invention, even if it is a powder coarse pigment produced through a pigment synthesis step or a pigmentation step, or a powder pigment that can be used for a colorant for a normal paint or synthetic resin, it is a fine particle step of the pigment. All pigments applied to are referred to as “coarse particle pigments”. As the finely divided pigment, for example, these coarse particle pigments are kneaded and ground in a kneader with a water-soluble salt powder and a water-soluble organic solvent having a boiling point of preferably 150 ° C. or more, and the average particle size of the pigment is 10 to 130 nm. Preferably, an aqueous filter cake of a fine pigment obtained by washing and filtering a pigment ground mass obtained by refining to 20 to 110 nm, or further drying and pulverizing a fine pigment, or easy dispersibility Processed pigments co-precipitated or kneaded with the polymer are used.

  The above-obtained aqueous filter cake of a fine pigment or the processed pigment obtained by coprecipitation or kneading of the aqueous filter cake with an easily dispersible polymer is used in combination with a pigment dispersion aid that is an anionic or cationic derivative of the pigment. Without being dispersed, it is possible to obtain an aqueous pigment dispersion by dispersing together with an aqueous polymer dispersant having a hydrophilic pigment group and / or a hydrophilic pigment molecular chain. An aqueous pigment ink for CF can be provided by using this aqueous dispersion as it is or by adding a binder as necessary. When this CF aqueous pigment ink is used, a pixel pattern having excellent optical characteristics such as sharpness, color purity, optical density, transparency, and contrast can be obtained. As will be described later, the aqueous polymer dispersant is considered to stabilize the fine dispersion of the pigment by fixing the dispersant to the pigment surface due to the hydrophobic effect of the parent pigment and the hydrophobic segment. .

  The binder will be described. When the ink is a dry fixing type ink, a conventionally known dry fixing type binder is used as the binder, and these binders are used in the form of a solvent solution, an aqueous solution, an emulsion, a latex or a solid hot-melt resin. The film-forming polymer may be a random, block and / or graft copolymer with or without a reactive group, and may further be a binder containing a crosslinking agent as necessary. .

  In addition, as a binder used when the ink is a polymerization type ink, a monomer, oligomer and / or polymer having an unsaturated double bond or a polymerizable cyclic ether group having a conventionally known addition polymerization or addition crosslinkability Furthermore, a polymerization initiator added as necessary, and addition polymerization or addition crosslinkable binder composed of a liquid medium can be mentioned. Examples of the addition polymerization or addition crosslinkable ink include heat polymerization type, laser heat ray polymerization type, ultraviolet ray polymerization type, photo cationic polymerization type, and electron beam polymerization type heating or energy ray curable ink.

  The polymer dye dispersant is a random, block and / or graft copolymer having a chromophilic group and / or a chromophilic molecular chain, and a philic group and / or a philic molecule chain in the molecule. is there. The dispersing agent having a plurality of functions such as dye dispersibility and dye fixing property as one component can also be used. The amount of the coloring matter used in the ink is not generally determined, but it is desirable that the amount be an amount that satisfies the saturation and color density and satisfies the viscosity and storage stability of the ink. When a pigment is used as the coloring matter, the amount of the pigment used is 2 to 30% by mass, preferably 5 to 25% by mass, based on the total ink composition.

  The preferable monomer which comprises the said binder or a polymer dispersing agent is demonstrated. The hydrophobic group contained in the monomer acts as a philic group in the organic solvent ink, and acts as a chromophilic group in the aqueous ink. For example, aromatic vinyl monomers such as styrene, α-methylstyrene, vinylnaphthalene; alkyl (carbon number 1-30) esters of α, β-ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and Cycloalkyl (4 to 20 carbon atoms) ester, alkyl cycloalkyl (6 to 20 carbon atoms) ester; alkylene such as ethylene, propylene, butylene, isobutylene, butadiene, isoprene and the like, and a macromonomer having a hydrophobic molecular chain Includes a macromonomer in which an α, β-ethylenically unsaturated group is bonded to a monomer chain having a hydrophobic group as described above or a copolymer chain. Examples of the monomer having a polymerizable cyclic ether group include an epoxy compound and an oxetane compound.

  A hydrophilic group and / or a hydrophilic molecular chain is introduced into the binder used in the water-based ink. For example, the above-mentioned α, β-ethylenically unsaturated carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, etc. are used as the monomer having an anionic hydrophilic group; 2-hydroxy is used as a comonomer having a nonionic hydrophilic group. Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, polyethylene glycol- Polypropylene glycol mono (meth) acrylate, butoxy (polyethylene glycol-polypropylene glycol) methacrylate, (meth) acrylamide, etc .; a comonomer having a cationic hydrophilic group and N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, 4-vinylpyridine and the like, and the macromonomer having a hydrophilic molecular chain is shown above. A monomer having a hydrophilic group alone or a copolymer, or a copolymer of a monomer having a hydrophilic group and a monomer having the above-mentioned hydrophobic group has an α, β-ethylenically unsaturated group. Examples include bonded macromonomers.

  Examples of the monomer having a group that reacts with the crosslinking agent include 2-hydroxyalkyl (2 to 6 carbon atoms) (meth) acrylate having a hydroxyl group such as (meth) acrylic acid and maleic acid having a carboxyl group, polyethylene glycol ( Γ-methacryloxypropyltrimethoxysilane having a silanyl group such as N-methylol (meth) acrylamide having a methylol group, such as glycidyl (meth) acrylate having an epoxy group, such as meth) acrylate, or N-methoxymethyl (meth) acrylamide And isocyanatoethyl (meth) acrylate having an isocyanate group, 2-isocyanato-2 (p-isopropenylphenyl) propane, and the like. As a macromonomer having a group that reacts with a crosslinking agent, the monomer having a reactive group shown above or a copolymer or a monomer having a reactive group and a monomer having the above hydrophobic group And a macromonomer in which an α, β-ethylenically unsaturated group is bonded to a copolymer with the above-mentioned body.

  Cross-linking agents include polyhexamethylene carbodiimide diisocyanate and bis, which have a carbodiimide group such as methoxymethylol melamine and butoxymethylol melamine having a methylol group, such as trimethylolpropane polyglycidyl ether and pentaerythritol polyglycidyl ether having an epoxy group. Trimethylolpropane-tris (tolylene diisocyanate) adduct having an isocyanate group, such as multi-branched polycarbodiimide, which is a urethane reaction product with (monomethoxypolyethylene glycol and polyoxyethylene sorbite monolaurate), trimethylolpropane-tris (Hexamethylene diisocyanate) Adduct phenol masked isocyanate and the like.

  Regarding the ink dispersion medium used, examples of the organic solvent medium used in the oil-based ink include alcohols having 1 to 10 carbon atoms; alkylene glycols having 2 to 6 carbon atoms, and polyalkylenes (carbon number: 2). -6) Glycols, monoalkyl (carbon number: 1 to 10) ethers, dialkyl (carbon number: 1 to 10) ethers, monoalkyl (carbon number: 1 to 10) ether monoacylate of these glycols Organic acids (carbon number: 1-6) alkyl (carbon number: 1-6) esters; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alkane hydrocarbons (carbon number: 6-10), isopar , Aliphatic hydrocarbon solvents such as shell sol; alicyclic hydrocarbon solvents such as cycloalkane (carbon number: 6 to 10); aroma Hydrocarbons (carbon number: 7-10) Solvent; N- methyl-2-pyrrolidone, 2-pyrrolidone, and a nitrogen-containing solvent such as 1,3-dimethyl-2-imidazolidinone.

  The aqueous medium used in the aqueous ink is water, a mixed solvent of water and a water-soluble organic solvent, and it is preferable to use deionized water such as ion-exchanged water or distilled water. Examples of the water-soluble organic solvent used in the aqueous mixed solvent include conventionally known water-soluble organic solvents such as (carbon number: 1 to 3) alcohols; (carbon number: 2, 3) glycols; glycerin; Lower alkyl of polyhydric alcohols such as alkylene (carbon number: 2, 3) glycol alkyl (carbon number: 1-4) ether, polyalkylene (carbon number: 2, 3) glycol alkyl (carbon number: 1-4) ether Examples of ethers include nitrogen-containing solvents such as N-methyl-2-pyrrolidone and 2-pyrrolidone.

  Energy ray addition polymerization or addition crosslinkable ink such as thermal polymerization ink, ultraviolet curable ink, and electron beam curable ink will be described. Radiation curing type inks such as these known thermal polymerization type, ultraviolet ray curable type, photo cationic polymerization type, and electron beam curable type are dyes, dye dispersants, and α, β-unsaturated doubles capable of causing a curing reaction. Addition polymerizable monomer having bond or epoxy group, addition polymerizable oligomer and / or binder precursor comprising addition crosslinkable polymer, conventionally known polymerization initiator added depending on the form of the curing system and necessary It is a curable ink comprising an additive other than those described above and a diluting solvent.

  In a thermal polymerization type, ultraviolet curable ink, and electron beam curable ink using a pigment, for example, the pigment is 10 to 20% by mass, the addition polymerizable monomer 20 to 50% by mass, the addition polymerizable oligomer or the soluble resin 10 to 10%. In the case of using 40% by mass and a polymerization initiator, 3 to 10% by mass, and if necessary, additives other than the above and a diluting solvent are added to make an ink. Examples of addition polymerizable oligomers and polyfunctional monomers used include urethane acrylates such as (tetramethylene glycol-hexamethylene disissocyanate polyurethane) -bisacrylate, bisphenol A epoxy resin-bisacrylate, and phenol novolac. Epoxy resin-epoxy acrylate such as polyacrylate, poly (hexylene isophthalate)-bisacrylate, (trimethylolpropane-adipic acid polyester)-polyester acrylate such as polyacrylate, oligomers such as tetraethylene glycol Diacrylate, tripropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A-ethylene oxide adduct diacrylate Chromatography, tri triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like polyacrylate dipentaerythritol hexaacrylate.

  In the cationic photopolymerization type pigment ink, for example, the pigment is 10 to 20% by mass, the alicyclic diepoxy compound 40 to 60% by mass, the oxetane compound 5 to 20% by mass, the polymerization initiator and the sensitizer 2 to 5% by mass, Additives and diluent solvents other than those described above are included as necessary. Examples of the alicyclic diepoxy compound include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and limonene dioxide, and examples of the oxetane compound include oxetane alcohol, dioxetane, phenyl oxetane, xylylene oxetane, Examples include 2-ethylhexyl oxetane.

  A conventionally known initiator is used as a polymerization initiator used in the energy beam polymerization type ink. Preferable examples include, for example, azobisisobutyronitrile, azobiscyanoisovaleric acid, dimethyl 2,2′-azobisisobutyrate as the thermal polymerization initiator, benzyl ketal, α- Examples of photocationic polymerization initiators such as hydroxyacetophenone and α-aminoacetophenone include triarylsulfonium salts and aryliodonium salts, and examples of sensitizers include 1-chloro-4-propoxythioxanthone.

  As a pigment dispersing machine used for producing the pigment ink of the present invention, a known dispersing machine, for example, a vertical medium dispersing machine such as a ball mill, a sand mill, or a bead mill, “Dynomill” (trademark, manufactured by Shinmaru Enterprise Co.), horizontal type A horizontal medium disperser such as a bead mill, a roll mill, an ultrasonic mill, or a high-pressure collision disperser is used. The pigment is dispersed by a method of dispersing a plurality of times using one of the above-mentioned dispersers or a method of combining two or more dispersers. In the present invention, the desirable dispersed particle diameter of the pigment is a display image such as the sedimentation property of the pigment in the ink, the aggregation property during storage, and the optical density, saturation, sharpness, transparency, and contrast of the CF pixel. In view of the quality, the average particle size is 10 to 130 nm, preferably 20 to 110 nm. More preferably, it is more preferable that the average particle diameter is 100 nm or less and there are almost no particles of 150 nm or more. As a method for obtaining a pigment dispersion having a desired particle size distribution, the size of the pulverizing media of the disperser is reduced, the filling rate of the pulverizing media is increased, the processing time is increased, and the discharge speed is decreased. Methods such as classification and separation with a filter or ultracentrifuge after pulverization are used. Or the combination of those methods is mentioned.

Next, the present invention will be described in more detail with specific examples. In the text, “part” and “%” are based on mass unless otherwise specified.
Example 1
(A) Pigment refinement treatment PR254, PG36, PY138, PY139, PB15-6, and PV23 were prepared as pigments, and refinement treatment was sequentially performed by the following method. 100 parts of each pigment was charged into a kneader equipped with a pressure lid together with 400 parts of sodium chloride powder and 130 parts of diethylene glycol. Premixing was performed until a uniformly wet mass was formed in the kneader, and then kneading and grinding were started while the pressure lid was closed and the contents were pressed down at a pressure of 6 kg / cm ² .

  Kneading and grinding were performed for 7 hours while controlling the cooling water temperature and the cooling water amount so that the contents were 40 to 45 ° C. The obtained ground product was put into 3000 parts of 2% sulfuric acid heated to 80 ° C. and stirred for 1 hour, followed by filtration and washing with water to remove sodium chloride and diethylene glycol. These operations were repeated to obtain press cakes of PR254, PG36, PY139, PB15-6, and PV23 pigments. About each press cake of each pigment, 200% of a nonionic activator was added to the pigment, diluted with water, and ultrasonically dispersed to prepare a pigment dispersion. When the average particle diameter of the five types of pigment dispersions thus prepared was measured with a particle size measuring instrument “Model N-4” (trade name; manufactured by Coulter, Inc.), the average particle diameter was 50 to 80 nm.

(B) Preparation of pigment dispersion The pigment dispersion of each color was prepared using the materials shown in Table 1 below. The pigment described in Table 1 was the above-described pigment press cake (a). The pigment content in each pigment presscake was 35-45%. Additional ion exchanged water was added to calculate the moisture in the presscake and make up for the deficiency. Specifically, each pigment dispersion was prepared as follows. After mixing the materials shown in Table 1 with the indicated number of parts and stirring with a dissolver for 2 hours to confirm that the mass of the pigment has disappeared, the horizontal media disperser “Dynomill 1.4 liter ECM type” (trade name; Shin Zirconia beads (diameter: 0.65 mm) were used at Marenterprises Co., Ltd., and dispersion treatment was performed at a peripheral speed of 14 m / s. The aqueous resin pigment dispersant-1 used in the preparation was benzyl methacrylate-ethyl methacrylate- (2-ethylhexyl) methacrylate- (2-hydroxyethyl) methacrylate-ammonium methacrylate copolymer (mass ratio; 30:20:20: 10:20, weight average molecular weight; about 8,000) aqueous solution (solid content 50%, solution medium; water: n-butanol: isopropanol = 3: 2: 1).

得られた各色の顔料分散液を粒度測定機器「ＭｏｄｅｌＮ−４」で平均粒子径を測定したところ、平均粒子径は４０〜７０ｎｍであった。

When the average particle diameter of the obtained pigment dispersion liquid of each color was measured with a particle size measuring instrument “Model N-4”, the average particle diameter was 40 to 70 nm.

(C) Preparation of aqueous flexo pigment ink R, G, and B aqueous flexo pigment inks were prepared according to the formulation shown in Table 2 below. R, G, and B inks were blended with two types of pigment dispersions according to the required optical transmission wavelength characteristics of CF to adjust the color tone. Specifically, each aqueous flexo pigment ink was prepared as follows. After sufficiently stirring the material, it was filtered through a membrane filter having a pore size of 5 μm to obtain an aqueous flexo pigment ink of that color. By repeating these operations, water-based flexographic pigment inks of R, G, and B colors were obtained. The film-forming material-1 used in the preparation was methyl methacrylate-ethyl methacrylate- (2-ethylhexyl) methacrylate- (2-hydroxyethyl) methacrylate-methacrylic acid copolymer (mass ratio; 25: 40: 20: 10: 5, It is an emulsion polymerization liquid having a solid content of 40%.

In order to examine the color tone and various optical properties of the R, G and B aqueous flexo inks obtained above, each ink was uniformly applied to a polyethylene terephthalate film with a bar coater and dried. Each ink showed excellent performance in optical characteristics such as sharpness, color purity, optical density, transparency and contrast.
The reason for this is that in each of the above-mentioned aqueous flexo pigment inks, an aqueous presscake of a fine pigment obtained by kneading and grinding the pigment in a pressure kneader in the step (a) is used as it is, and further, the horizontal type media disperser Since the pigment dispersion was produced by the dispersion treatment, the particle diameter of the dispersed pigment could be made very fine, and the solvent-based pigment ink was prepared by preparing the pigment dispersion of (b). Then, since it is not necessary to add the necessary ionic derivative of the pigment to the aqueous flexographic pigment ink, it is considered that the color tone of the original pigment could be obtained.

(D) Manufacture of Pixel Transfer Film by Flexographic Printing A center impression (hereinafter abbreviated as “CI type”) type flexographic printing machine in which six printing units are mounted around the center drum was used. As a printing unit for forming a pixel pattern of R, G, B3 primary colors, overprinting was performed using two units per color in order to improve the printing quality. As the resin endless printing plate, two resin plates were made for each color from a pixel pattern of stripe arrangement of three primary colors prepared on a computer screen. Each printing unit was equipped with a ceramic anilox roller and a corresponding sleeve type resin endless printing plate made as described above. In order to avoid the occurrence of a marginal zone, each printing unit was adjusted to perform printing at a low printing pressure.

  Three sets of printing units each consisting of two printing units are connected to the respective ink storage tanks of R aqueous flexo ink-1, G aqueous flexo ink-1 and B aqueous flexo ink-1 prepared in (c) above. Each of the six printing units was loaded into a corresponding ink supply device. Each ink supply device is a completely sealed type with side-sealed upper and lower doctor blades. As a printing film, a polyethylene terephthalate (hereinafter abbreviated as “PET”) film in which polyvinyl alcohol was previously applied as a release layer was prepared. The film is supplied from the film supply section of the printing machine and rotates in accordance with the rotation of the center drum. As a result, each color of R, G and B is overprinted wet-on-wet and introduced into the drying section for drying. And wound up at the winding section. A PET film (hereinafter referred to as “transfer film 1”) having a pixel pattern printed on the release layer was obtained.

(E) Preparation of CF by Transfer Method Next, a thermosetting acrylic adhesive was applied to the entire printing surface of the transfer film 1 obtained above using a gravure printing machine. A pixel pattern was aligned with the glass CF substrate on which a black matrix formed by chromium deposition was formed, and the adhesive-coated surface of the transfer film 1 was brought into close contact while degassing. Heat treatment was performed to cure the thermosetting acrylic adhesive. Next, the PET film was peeled off, and the polyvinyl alcohol in the peeling layer adhering to the pixel pattern was dissolved and removed with pure water and dried to obtain a glass CF having the pixel pattern transferred to a glass substrate.

Example 2
(A) Preparation of hole mask for pixel transfer film An aqueous solution of polyvinyl alcohol-methylol melamine-based initial condensate (7: 3) is applied in advance to a PET film, and the initial condensate is baked and cured to form a release layer. A PET film was prepared. On top of that, a 40% methyl ethyl ketone solution of t-butyl methacrylate-styrene-methoxypolyethylene glycol methacrylate (50:10:40) copolymer: nitrocellulose: carbon black pigment (5: 4: 1) is almost dried. The film was uniformly applied to a thickness of 8 μm to form a self-burning mask film. Subsequently, according to the pixel pattern of the stripe arrangement of the R, G, B3 primary colors created on the computer screen, the mask film was laser ablated with a low energy laser to obtain a pixel transfer film on which a hole mask was formed.

(B) Production of transfer film by flexographic printing A CI-type flexographic printing machine was used according to the pixel printing operation of Example 1 (d). The pixel transfer film on which the hole mask obtained in the above (a) is formed is supplied from the film supply unit of the CI-type flexographic printing machine and rotates in accordance with the rotation of the center drum. Overprinted wet-on-wet using aqueous flexo ink-1, G aqueous flexo ink-1 and B aqueous flexo ink-1, introduced into the drying section, blown and dried, then dipped in water, extra The porous film layer with the dried ink was peeled off, removed, washed and dried. Next, the film is introduced into a heat dryer, and the coating film on which the pixels are printed is baked and cured at 180 ° C., and a R, G, B3 primary color pixel pattern is printed on the release layer (hereinafter referred to as “ Transfer film 2 ") was obtained.

(C) Preparation of CF by transfer method Next, according to Example 1 (e), an adhesive was applied to the entire surface of the transfer film 2 obtained in (a) above, and a glass-made BM formed by chromium vapor deposition was formed. The transfer film 2 was affixed to the CF substrate, and the PET film was peeled off, washed, and dried to obtain a glass CF having the pixels transferred to the glass substrate.

Example 3
(A) Preparation of red, green and blue pigment dispersions In accordance with the formulation in Table 3 below, a polymer-2 solution and ion-exchanged water were blended using a red pigment mixture, a green pigment mixture or a blue pigment mixture, and a dissolver. The mixture was stirred for 2 hours to confirm that the lump of the pigment had disappeared, and then the dispersion treatment was performed at a peripheral speed of 14 m / s using the horizontal medium disperser used in Example 1. Filtration through a 400 mesh stainless screen. This operation was repeated to prepare red, green and blue pigment dispersions. When the average particle diameter of the pigment dispersion liquid of each color was measured with a particle size measuring instrument N-4, the average particle diameter was 80 to 110 nm. The polymer-2 solution used as the pigment dispersant solution is 100 parts of styrene-methacrylic acid-alkyl methacrylate ester copolymer (acid value 97, weight average molecular weight: about 32,000) with 50 parts of butyl cellosolve and 50 parts of butyl carbitol. Part, a total of 150 parts of ammonia water for neutralization and water, were mixed and heated and dissolved in a 40% aqueous resin solution at 80 ° C. for 5 hours.

(B) Preparation of inkjet printing ink 5 parts of dipropylene glycol monoethyl ether, “Surfinol 465” (trade name; trade name; 53.6 parts of the red, green and blue pigment dispersions obtained in (a) above Air Products) 0.5 part, 40.4 parts of water, 0.5 parts of methanol was added, stirred well, filtered through a membrane filter with a pore size of 5 μm, and red, green and blue pigment inkjet printers Ink (hereinafter abbreviated as “IJ ink”) was prepared.

(C) Preparation of transfer film In order to form R, G, B3 primary color pixel patterns, a CI type IJ printer equipped with a piezo type IJ printer unit was prepared. As the IJ printer unit, overprinting was performed using two units per color. Three sets of printer units each consisting of two printer units were connected to the respective ink storage tanks of the red, green and blue pigment IJ inks prepared in (b) above, and loaded into the corresponding ink supply devices. As a printing film, a PET film coated with the same kind of polyvinyl alcohol as used in Example 1 as a release layer was used. The film was supplied from the film supply section of the CI printer, and rotated in accordance with the rotation of the center drum. The inks of R, G, and B were ejected from the IJ printer head based on the pixel pattern created on the computer screen. After each color was printed, it was introduced into the drying section, dried, and wound up by the winding section. A PET film (hereinafter referred to as “transfer film 3”) in which a pixel pattern of R, G, B3 primary colors was printed on the release layer was obtained.

(D) Preparation of CF by transfer method Next, according to Example 1 (e), an adhesive is applied to the entire printed surface of the transfer film 3 obtained in (c) above, and a BM is formed by chromium vapor deposition. The transfer film 3 was affixed to the obtained glass CF substrate, and the PET film was peeled off, washed, and dried to obtain a glass CF with the pixels transferred to the glass substrate.

Example 4
(A) Preparation of transfer film In printing on R, G, B3 primary color pixel patterns using the CI type IJ printer of Example 3 (c), the same kind as that used in Example 2 was used as a printing film. A PET film having pores formed by a release layer and laser ablation was used. On the computer screen, each color ink of R, G, and B was ejected from the IJ printer head based on the pixel pattern created slightly larger than the laser ablated holes. After each color was printed, the printed film was introduced into the drying section, blown and dried, and then immersed in water to peel off, remove, wash and dry the mask film with excess dry ink. Next, it is introduced into a heat dryer, and the pixel pattern is baked and cured, and a PET film (hereinafter referred to as “transfer film 4”) in which a pixel pattern of R, G, B3 primary colors is printed on the release layer. Obtained.

(B) Preparation of CF by transfer method Next, according to Example 1 (e), an adhesive was applied to the entire surface of the transfer film 4 obtained in (a) above, and a glass-made BM formed by chromium vapor deposition was formed. The transfer film 4 was affixed to the CF substrate, the PET film was peeled off, washed, and dried to obtain a glass CF in which the pixels were transferred to the glass substrate.

Example 5
(A) Preparation of film with pores formed by gravure printing Methyl methacrylate-2-ethylhexyl on a PET film on which a release layer of a cured methylolmelamine-polyvinyl alcohol initial condensation product was formed using a gravure printing machine By using a 30% isopropanol solution of a methacrylate-methacrylic acid (50:20:30) copolymer, holes of R, G, and B pixel patterns are printed to obtain a peelable PET film on which a hole mask is formed. It was.

(B) Preparation of transfer film and preparation of CF by transfer method Prepared in the same manner as in Example 4. Using a CI type IJ printer, R, G, and B pixels were sequentially inkjet printed on the peelable PET film on which the hole mask obtained in (a) was formed. Next, the pore mask layer was removed to obtain a transfer film (hereinafter referred to as “transfer film 5”) on which R, G, and B pixel patterns were printed. Next, an adhesive is applied to the transfer film 5, the transfer film 5 is attached to a glass CF substrate on which BM is formed by chromium vapor deposition, the PET film is peeled off, washed and dried, and the pixels are transferred to the glass substrate. A glass CF was obtained.

Example 6
(A) Preparation of pore mask film by pasting pore film A polyimide film having R, G, B pixel pattern pores prepared in advance by a laser ablation method is prepared, and a cured methylolmelamine-polyvinyl alcohol initial condensation product is prepared. The film was stuck on a PET film on which a release layer was formed to obtain a peelable PET film on which a hole mask was formed.

(B) Preparation of transfer film and preparation of CF by transfer system Using a CI type IJ printer in the same manner as in Example 4, on the peelable PET film on which the hole mask obtained in (a) was formed In addition, R, G, and B pixels were sequentially inkjet printed. Subsequently, the hole mask layer was peeled off to obtain a transfer film (hereinafter referred to as “transfer film 6”) on which R, G, and B pixel patterns were printed. Next, an adhesive is applied to the transfer film 6, the transfer film 6 is attached to a glass CF substrate on which BM is formed by chromium vapor deposition, the PET film is peeled off, washed and dried, and the pixels are transferred to the glass substrate. A glass CF was obtained.

  The glass CFs obtained in Examples 1 to 6 were coated with an overcoat layer on the entire surface in accordance with a conventional method, and an ITO transparent electrode film was formed by sputtering vapor deposition to produce CF. A liquid crystal display device was manufactured by mounting these CFs. These CFs are manufactured reasonably, economically, and with a manufacturing method that can cope with an increase in size, so it is possible to provide a low-cost liquid crystal display as well as a large liquid crystal display as well as an ordinary monitor liquid crystal display. it can.

Example 7
In the first to sixth embodiments, the RGB three primary color pixel patterns are transferred to a plastic CF substrate, specifically, a methyl methacrylate, polycarbonate, or polyester CF substrate instead of the glass CF substrate. In the same manner, plastic CFs were produced.
Example 8
Examples except that the R, G, B pixels are directly printed by printing or ink jet printing using a flexible PET sheet CF substrate instead of the PET transfer film in Examples 1 to 6 above. Each PET CF was produced in the same manner as in 1-6.
The CF made of plastic obtained in Examples 7 and 8 was coated with an overcoat layer on the entire surface in accordance with a conventional method, and an ITO transparent electrode film was formed by a printing method to produce a CF. A liquid crystal display device was manufactured by mounting these CFs. Since these CFs are manufactured by a manufacturing method that is also rational, economical, and capable of coping with an increase in size, not only ordinary liquid crystal displays for monitors but also large liquid crystal displays for liquid crystal displays can be provided at low cost. be able to.

Example 9
In place of the pigment used in Example 1 (a), PY128, PR122 and PB15-3 were used to carry out the finer treatment of the pigment in the same manner as in Example 1 (a), and the pigment dispersion was performed in the same manner as in (b). A liquid was prepared, and yellow, magenta and cyan aqueous flexo pigment inks were prepared in the same manner as in (c). Next, flexographically printed Y, M, and C pixel transfer films were produced in the same manner as in Example 1 (d) and Example 2 (b), and in the same manner as in Example 1 (e) and Example 2 (c). Thus, CFs of Y, M, and C pixels by a transfer method were prepared. Similarly, yellow, magenta and cyan ink jet printing inks were prepared according to Example 3 (b), and Example 3 (c), Example 4 (a), Example 5 (b) and Example 6 were prepared. A Y, M, C pixel transfer film is produced according to the preparation of the transfer film of (b), and is the same as Example 3 (d), Example 4 (b), Example 5 (b), and Example 6 (b). Thus, CFs of Y, M, and C pixels were prepared by the transfer method.

Example 10
In Example 9, the YMC3 primary color pixel pattern was transferred to the CF substrate made of plastic instead of the glass CF substrate, specifically, the CF substrate made of methyl methacrylate, polycarbonate, or polyester, in the same manner as in Example 9. A plastic CF of each Y, M, and C pixel was prepared.
Example 11
Example 9 is the same as Example 9 except that a Y-, M-, and C-pixel are directly printed by printing or ink jet printing using a flexible PET sheet CF substrate instead of the PET transfer film in Example 9 above. Similarly, CFs for Y, M, and C pixels made of PET were manufactured.
Using the CFs obtained in Examples 9, 10 and 11 above, a CF of a reflective liquid crystal display was manufactured by a conventional method, and a reflective liquid crystal display device was manufactured. These CFs are reasonably and economically manufactured, and are manufactured by a manufacturing method that can cope with an increase in the size of a liquid crystal display, so that it is inexpensive even for a reflective large liquid crystal display as well as a normal reflective liquid crystal display. Can be provided.

  According to the present invention, a pixel pattern of CF is printed using a center impression type (center drum type) printing machine, and particularly through a fixed mask having holes corresponding to the pixel pattern. CF with excellent performance in image characteristics such as pixel fineness and sharpness is obtained, and the resolution and positional accuracy, which are inevitable defects of the normal printing method as described above, are insufficient. Is solved.

The figure explaining the basic structure of the center impression type (center drum type) printing machine useful for implementing the manufacturing method of this invention.

Explanation of symbols

1: Center drum 2: Printing unit

Claims (28)

  A pixel pattern of a color filter consisting of three primary color pixels of red, green and blue or three primary colors of yellow, magenta and cyan is printed on a flexible plastic film by a center impression type printing machine. A method for producing a color filter, comprising:   The method for producing a color filter according to claim 1, wherein the plastic film having flexibility is a plastic film for transfer or attachment, and the pixel pattern printed on the film is transferred or attached to the color filter substrate.   The method for producing a color filter according to claim 1, wherein the mask is peeled off after the pixel pattern is printed through a hole mask having a positive-negative relationship with the pixel pattern.   The method for producing a color filter according to claim 1, wherein the center impression type printing machine comprises a center drum and 3 to 10 printing units installed in a satellite shape around the center drum.   4. The color filter according to claim 3, wherein the hole mask is a mask in which holes having a negative-positive relationship with respect to the pixel pattern are formed by a laser ablation method after forming a mask film on the plastic film. Manufacturing method.   The method for producing a color filter according to claim 3, wherein the hole mask is a mask obtained by printing a film in a region other than the pixel pattern to be formed on the plastic film.   The method for producing a color filter according to claim 3, wherein the pore mask includes an adhesive layer, and is fixed onto the plastic film via the adhesive layer.   The pore mask is (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, Ethylene-vinyl acetate- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer and a soluble salt comprising an ammonium salt or an amine salt thereof; (meth) acrylic acid ester -(Alkoxy) polyethylene glycol (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid ester- (alkoxy) polyethylene glycol (meth) acrylic acid ester copolymer, styrene- (alkoxy) polyethylene glycol (meth) Acrylate ester copolymer; methylcellulose, hydroxy From ethyl cellulose, hydroxypropyl cellulose, cellulose acetate phthalate; vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-ethylene copolymer; hydrophilic polyurethane, hydrophilic polyester; and ethylene oxide-alkylene (C3, C4) oxide copolymer The manufacturing method of the color filter of Claim 3 currently formed from the material chosen from the group which consists of.   The hole mask is formed of a plastic film made of a material selected from the group consisting of polyester, nylon, vinyl alcohol copolymer, polyvinyl butyral, polyimide, polyamideimide, cellulose acetate, polyethylene, and polypropylene. Manufacturing method of color filter.   The method for producing a color filter according to claim 3, wherein the hole forming mask contains a thermal energy ray-absorbing component and / or a self-combustible resin component.   The method for producing a color filter according to claim 10, wherein the thermal energy ray absorbing component is carbon black and / or an infrared absorbing compound.   The method for producing a color filter according to claim 10, wherein the self-combustible resin component is nitrocellulose.   The color filter according to claim 1, wherein the center impression type printing machine is of a type using a printing system selected from the group consisting of a flexographic printing system using a printing plate having a pixel pattern, a gravure printing system and an offset printing system. Production method.   The center impression type printing machine consists of liquid ink jet printing method, dispenser injection printing method, coating needle under-drop printing method, electrostatic liquid printing method, thermal transfer printing method, electrostatic powder printing method and solid ink jet printing method. The method for producing a color filter according to claim 1, wherein the color filter is of a type using a printing method selected from.   The ink used for the manufacturing method of the color filter of any one of Claims 1-14 characterized by including a pigment | dye and a binder.   The ink according to claim 15, which is an organic solvent-based ink, water-based ink, solvent-free ink, or heat-meltable solid ink.   The ink according to claim 15, wherein the pigment is a pigment.   The pigment is a pigment used to form red (R), green (G) or blue (B) pixels; I. Pigment Red 9, 97, 168, 177, 216, 224, 226, 242 and 254, a red pigment comprising C.I. I. A green pigment comprising CI Pigment Green 7 and 36; I. Pigment Blue 15: 6, 60, a blue pigment comprising C.I. I. Pigment Violet 23, a violet (V) pigment comprising subphthalocyanine, C.I. I. Pigment Yellow 20, 24, 83, 93, 109, 110, 113, 114, 117, 125, 138, 139, 150, 154, 180, 185, and the above-described red pigment and yellow The ink according to claim 17, which is selected from the group consisting of a coprecipitated pigment with a pigment, a coprecipitated pigment with a green pigment and a yellow pigment, and a solid solution pigment and a mixed crystal pigment of these pigments.   The pigment is a pigment used to form yellow (Y), magenta (M) or cyan (C) pixels; I. Pigment Yellow 62, 74, 93, 128, 155, 185, a yellow pigment, C.I. I. Pigment Red 122, 146 and C.I. I. A magenta pigment comprising a violet pigment comprising CI Pigment Violet 19; I. A cyan pigment composed of CI Pigment Blue 15: 3, a coprecipitation pigment of yellow pigment and cyan pigment, a coprecipitation pigment of red pigment and violet pigment, and a coprecipitation pigment of cyan pigment and yellow pigment, and their The ink according to claim 17, which is a solid solution pigment or mixed crystal pigment.   The pigment is kneaded and ground with a water-soluble salt and a water-soluble organic solvent in a kneader, and the pigment ground mass obtained by refining the average particle size of the pigment to 10 to 130 nm is washed with water and filtered. The ink according to claim 17, which is an aqueous filter cake of a finer pigment obtained in the above manner.   The ink according to claim 17, wherein the pigment is a fine powder pigment obtained by drying and pulverizing an aqueous filter cake of the pigment.   The ink according to claim 17, wherein the pigment is a processed pigment obtained by mixing and coprecipitating an aqueous filter cake of the pigment with an easily dispersible polymer.   The ink according to claim 17, wherein the pigment is a processed pigment obtained by kneading the fine powder of the pigment with an easily dispersible polymer.   Random, block and graft copolymers in which the binder may have reactive groups, hydrophobic groups and / or hydrophilic groups; may have reactive groups, hydrophobic groups and / or hydrophilic groups 18. The ink according to claim 17, wherein the ink is a film-forming substance selected from the group consisting of an oligomer and a monomer, oligomer and / or polymer having an addition polymerizable unsaturated double bond or addition condensable epoxy group.   The ink according to claim 17, wherein the pigment has an average particle diameter of 10 to 130 nm.   A color filter formed by the method according to claim 1.   27. An image display device comprising the color filter according to claim 26. An information transmission device equipped with the image display device according to claim 27.

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