JP4648051B2 - Flexible color filter substrate and manufacturing method thereof - Google Patents

Description

The present invention relates to a method for manufacturing a color filter substrate used for a liquid crystal display device or the like, and more particularly to a method for manufacturing a thin and light color filter substrate using a plastic film substrate .

  In recent years, in order to reduce the thickness and weight of display devices, plastic films are being used as substrates instead of conventional glass substrates. As the plastic film, polycarbonate, polyethersulfone or the like is used, but these plastics have gas permeability alone. For this reason, it is necessary to use a gas barrier layer in combination with the plastic film in order to prevent display failure of the display device due to the intrusion of air or water vapor.

  The types of gas barrier layers include those formed by applying a polymer solution such as polyvinyl alcohol and poly (ethylene vinyl alcohol), and those obtained by depositing an inorganic thin film of silicon oxide or alumina by vapor deposition, sputtering, CVD, or the like. Proposed. Furthermore, it is known that barrier properties are improved by overcoating with a resin on a barrier layer made of an inorganic substance.

  On the other hand, it is proposed that a color filter uses a thermosetting resin or a photocurable resin as a resin used for the color filter in order to improve heat resistance and the like (see, for example, Patent Documents 1 to 5).

Among the color filters shown in Patent Documents 1 to 5, when the image receiving layer and the colored layer are thermosetting resins, the image receiving layer and the colored layer are cured by heating. The dimensional change may occur, and there is a possibility that the light shielding layer and the colored layer may be misaligned. Further, when the image receiving layer and the colored layer are photocurable resins, the color of the colored layer may change due to the influence of the remaining photopolymerization initiator.
JP-A-8-220335 JP 2001-66413 A JP 2001-66415 A JP 2002-182028 A JP 2002-286925 A

The present invention has been made in view of the above circumstances, and can reduce the thickness and weight of the display device, has excellent adhesion and gas barrier properties of the colored layer, has no color change of the colored layer, and has dimensional stability. and to provide an excellent method for producing a flexible color filter substrate.

In order to solve the above-mentioned problems, a first aspect of the present invention is a step of forming a patterned light-shielding layer on the gas barrier layer of a base material having a gas barrier layer on at least one surface of a plastic film, and the patterned light-shielding layer is formed Forming an image receiving layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the gas barrier layer, an opening of at least the patterned light shielding layer on the image receiving layer A step of forming a colored layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam in a portion corresponding to the above, and irradiating the image receiving layer and the colored layer with an electron beam And a method for producing a flexible color filter substrate, comprising the step of collectively curing .

According to a second aspect of the present invention, an image receiving material comprising a (meth) acrylic acid ester derivative having at least two functional groups that is cured by irradiation with an electron beam on the gas barrier layer of a substrate having a gas barrier layer on at least one surface of a plastic film. A step of forming a layer, a step of forming, on the image receiving layer, a colored layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by electron beam irradiation, and the image receiving layer and the colored layer. Provided is a method for producing a flexible color filter substrate, comprising: a step of irradiating with an electron beam and curing at once; and a step of forming a patterned light-shielding layer in a gap between the patterned colored layers. To do.

According to a third aspect of the present invention, an image receiving material comprising a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the gas barrier layer of a base material having a gas barrier layer on at least one surface of a plastic film. A step of forming a layer, a step of forming a colored layer containing a (meth) acrylic acid ester derivative having two or more functional groups which is cured by irradiation with an electron beam on the image receiving layer, and a gap between the patterned colored layers Irradiating an electron beam to the step of forming a patterned light-shielding layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by electron beam irradiation, and the image receiving layer, the colored layer, and the patterned light-shielding layer. And a method for producing a flexible color filter substrate, comprising the step of collectively curing.
In the manufacturing method of the flexible color filter substrate according to the first to third aspects of the present invention configured as described above, the base material desirably has a total light transmittance of 80% or more. .

  The plastic film desirably has a linear expansion coefficient of 40 ppm / ° C. or lower at 30 ° C. to 150 ° C. Moreover, it is desirable to use a cross-linked resin as the plastic film. In this case, examples of the crosslinkable resin include an epoxy resin and an acrylic resin. In addition, as a plastic film, what consists of resin and an inorganic substance, for example, the composite material of resin and an inorganic substance, can also be used.

  The gas barrier layer can be mainly composed of an inorganic substance, for example, a compound containing at least one selected from the group consisting of Si, Ta, and Al. In this case, examples of the compound include oxides, nitrides, and oxynitrides.

  It is desirable that the image receiving layer and the colored layer contain a (meth) acrylic acid ester derivative having two or more functional groups that are cured by electron beam irradiation.

  It is desirable that the patterned light-shielding layer be cured by electron beam irradiation.

  In the flexible color filter substrate as described above, the adhesion between adjacent layers of the plastic film, gas barrier layer, patterned light-shielding layer, image receiving layer, and colored layer is a cross-cut test based on JIS 5600-5-6. Desirably, the result is category 0 or category 1.

  The substrate may have an undercoat layer between the plastic film and the gas barrier layer. In this case, the adhesion between adjacent layers of the plastic film, the undercoat layer, the gas barrier layer, the patterned light-shielding layer, the image receiving layer, and the colored layer is classified as 0 or 0 according to the cross-cut test result based on JIS 5600-5-6. Class 1 is desirable.

The flexible color filter substrate described above desirably has a water vapor transmission rate of 0.2 g / m ² · 24 hr or less.

The manufacturing method of the flexible color filter substrate according to the first to third aspects of the present invention configured as described above can be performed by roll-to-roll.

  According to the present invention, it is possible to reduce the thickness and weight of a display device, and it is excellent in adhesion and gas barrier properties of a colored layer, and there is no color change of the colored layer and excellent in dimensional stability. A substrate can be easily obtained at low cost.

  The best mode for carrying out the invention will be described below.

  A flexible color filter substrate according to an embodiment of the present invention is formed by sequentially forming a gas barrier layer, a patterned light-shielding layer, an image receiving layer, and a colored layer on a plastic film, or a gas barrier layer on a plastic film, The image receiving layer, the colored layer, and the patterned light shielding layer are sequentially formed, and the image receiving layer and the colored layer, or the image receiving layer, the colored layer, and the patterned light shielding layer are collectively cured by irradiation with an electron beam.

  In such a flexible color filter substrate according to an embodiment of the present invention, the gas barrier layer, the patterned light-shielding layer, and the image receiving layer are in direct contact with each other on the plastic film. Is good.

  In addition, by applying the colored layer forming ink on the ink image receiving layer and forming the colored layer by the ink jet printing method, the components of the colored layer forming ink are absorbed by the ink image receiving layer, and between the ink image receiving layer and the colored layer. Therefore, the adhesion between the ink image-receiving layer and the colored layer is improved.

  Furthermore, as the image-receiving layer and the colored layer, or as the image-receiving layer, the colored layer and the patterned light-shielding layer, a material that is cured with an electron beam is used, and these are cured collectively by irradiation with an electron beam. It is possible to obtain a color filter substrate having excellent characteristic stability without causing dimensional change or color change that occurs when a curable or photo-curable material is used.

  Hereinafter, a flexible color filter substrate according to an embodiment of the present invention will be described in detail.

  The plastic film used for the flexible color filter substrate according to an embodiment of the present invention preferably has a total light transmittance of 80% to 100%. Examples of such plastic film materials include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polycarbonate, polysulfone, polyethersulfone, polycycloolefin, acrylic crosslinkable resin, epoxy crosslinkable resin crosslinkable resin, Examples thereof include resins such as saturated polyester-based crosslinkable resins. Moreover, it is preferable to use a resin and an inorganic substance in combination since the linear expansion coefficient can be reduced. Preferably, when the linear expansion coefficient is 40 ppm / ° C. or less, more preferably 0.1 to 30 ppm / ° C., warpage during the heating process due to a difference in linear expansion coefficient from the inorganic thin film can be suppressed, which is preferable. Examples of inorganic substances in this case are silica, alumina, glass and the like. These inorganic substances are preferably used in the form of particles, and the average particle diameter is preferably 0.01 μm to 10 μm.

  For example, in the case of a roll substrate having a width of 0.1 m and a length of 10 m, the thickness of the plastic film can be set to 10 μm to 300 μm. If the thickness is outside the above range, processing by a roll-to-roll process tends to be difficult.

In the flexible color filter substrate according to the embodiment of the present invention, an undercoat layer can be provided between the plastic film and the gas barrier layer. Depending on the types of the plastic film and the gas barrier layer, the adhesion of the gas barrier layer may be further improved by using an undercoat. Examples of preferred undercoat layers include acrylic crosslinkable resins and epoxy crosslinkable resins .

  Preferred combinations of plastic film, undercoat, and gas barrier layer include, for example, polyethersulfone / acrylic crosslinkable resin / silicon oxide, acrylic crosslinkable resin / acrylic crosslinkable resin / silicon oxide, and epoxy crosslinkable resin. / Epoxy crosslinkable resin / silicon aluminum oxynitride and the like.

  The thickness of the undercoat layer can be, for example, 0.1 μm to 10 μm. If it is less than 0.1 μm, the effect of improving the adhesion of the gas barrier layer tends not to be obtained, and if it exceeds 10 μm, flexibility tends to be lowered.

  Examples of inorganic materials that can be used as a gas barrier layer in a flexible color filter substrate according to an embodiment of the present invention include Si, Al, In, Sn, Zn, Ti, Cu, Ce, Mg, La, Cr, Examples thereof include an oxide, nitride, oxynitride or halide containing at least one selected from Ca, Zr, and Ta as a main component.

  The gas barrier layer may be one layer or two or more layers, and may be continuously formed.

  Further, the thickness of the gas barrier layer can be set to, for example, 20 nm to 200 nm. When the thickness is less than 20 nm, the gas barrier effect tends not to be obtained, and when the thickness exceeds 200 nm, the flexibility tends to decrease.

  The inorganic material that can be used as the gas barrier layer is preferably an oxide, nitride, or oxynitride containing one or more selected from Si, Ta, and Al. When these inorganic materials are used, there is an advantage that it is easy to achieve both gas barrier properties and transparency.

  Such a gas barrier layer can be produced by a PVD method such as vapor deposition, ion plating or sputtering, a chemical vapor deposition method such as plasma CVD, or a sol-gel method.

  The gas barrier layer deposition process can be applied to either single wafers or roll-to-roll. Since film formation is performed on a plastic film, it is preferable to perform roll-to-roll because productivity is improved.

The flexible color filter substrate according to an embodiment of the present invention preferably has a water vapor transmission rate of 0 to 0.2 g / m ² · 24 hours as a gas barrier property. If the water vapor transmission rate is larger than 0.2 g / m ² · 24 hours, bubbles tend to be mixed into the display cell under wet heat conditions, which causes a defect.

  In the flexible color filter substrate according to one embodiment of the present invention, the patterned light-shielding layer is provided between the gas barrier layer and the image receiving layer or on the colored layer. The pattern shape is a lattice shape or a stripe shape. The patterned light-shielding layer is formed in the gap between the patterns of the colored layer so as to surround each pattern of the colored layer, thereby preventing color mixing of the display colors of the colored layer in the display device and increasing the contrast of the image. be able to. In addition, since the patterned light shielding layer is formed partially rather than on the entire surface, at least a part of the gas barrier layer and the ink image receiving layer are in direct contact with each other even if the patterned light shielding layer is provided.

  Good adhesion can be obtained by providing a patterned light-shielding layer between the gas barrier layer and the ink image-receiving layer. Particularly, when the patterned light-shielding layer is a material that can be continuously formed with the gas barrier layer, such as a metal film, the manufacturing cost can be reduced. It becomes possible.

  As a material for forming the patterned light-shielding layer, a black resin composition containing a black light-shielding material, a resin, and a solvent as main components and optionally blended with a dispersant or the like can be used. Furthermore, a photopolymerizable monomer, a photopolymerization initiator, or the like can be mixed to suitably use a black resin composition having photosensitivity.

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

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

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

  By applying the photosensitive black resin composition described above and patterning by photolithography, a patterned light-shielding layer can be formed.

  As another light shielding layer material, a deposited film or a sputtering film of metal Cr or a Cr-based alloy can be used. The light shielding layer made of metal Cr or Cr-based alloy has excellent corrosion resistance and light shielding properties.

  As a method for forming the patterned light-shielding layer, a resist pattern is formed on the light-shielding layer formed by vapor deposition or sputtering, and a resist pattern is formed by photolithography, and this is used as a mask to form a lattice-shaped pattern having a minute opening portion. A method for forming a film may be mentioned.

  Furthermore, since the reflected light from the outside reduces the contrast of the displayed image when the reflectance of the light shielding layer is high, a compound thin film such as CrO or CrN is formed between the substrate and the light shielding layer in order to make the image easier to see. It is also possible to form a low reflection film.

  Alternatively, as the material for forming the patterned light shielding layer, an electron beam curable material containing an electron beam curable compound can be used.

  As the electron beam curable compound, a monomer, oligomer, prepolymer or the like having an ethylenically unsaturated double bond can be used. Specific examples of the electron beam curable compound include, for example, 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate. These compounds can be used alone or in admixture of two or more.

  The thickness of the patterned light shielding layer is preferably 0.5 μm to 3.0 μm, for example, when made of a black resin composition. If the thickness is less than 0.5 μm, it is difficult to obtain a sufficient light-shielding property, and if it exceeds 3.0 μm, the surface smoothness when forming the color filter tends to be lowered.

  Alternatively, when the patterned light shielding layer is made of, for example, chromium metal or a chromium-based alloy, the thickness is preferably 0.05 μm to 0.5 μm. If it is less than 0.05 μm, it is difficult to obtain sufficient light shielding properties, and if it exceeds 0.5 μm, flexibility tends to be lowered.

  In the flexible color filter substrate according to one embodiment of the present invention, an ink image receiving layer is provided as a base of the colored layer. Therefore, the material for forming the colored layer can be prepared as an inkjet ink and applied to an inkjet printer, and the colored layer can be easily formed on the ink image-receiving layer. In the inkjet printing technique, the colored layer can be formed only by the step of applying the ink on the ink image-receiving layer using at least an inkjet printer. In the photolithography method, in addition to the colored layer application step, the exposure step, and In order to obtain a colored layer of three colors that requires a development step, etc., these steps are repeated three more times. Therefore, when an inkjet printing method is used as compared with a photolithographic method, the steps necessary for forming a colored layer The number can be greatly simplified.

  The ink image-receiving layer used in the flexible color filter substrate according to one embodiment of the present invention is curable by irradiation with an electron beam, and is an ink for a color filter forming ink applied to an inkjet printing apparatus. It has the property of absorbing the solvent in it and imparting good printability. For this reason, at least a part of the ink image receiving layer of the color filter substrate becomes a colored layer by applying the color filter forming ink.

  The ink image-receiving layer can be formed using, for example, a coating liquid composed of an electron beam curable compound, a solvent, and, if necessary, organic and inorganic fine particles.

  The material constituting the ink image-receiving layer is one that is cured by electron beam irradiation, is transparent, has excellent fixability of the coloring material in the received ink, and has no discoloration or discoloration. Performance such as resistance is required.

  As the electron beam curable compound contained in the ink image-receiving layer, a monomer, oligomer, prepolymer or the like having an ethylenically unsaturated double bond can be used. Specific examples of the electron beam curable compound include, for example, 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate. These compounds can be used alone or in admixture of two or more.

  In order to increase the ink absorbability, it is also effective to contain fine particles (fillers) in the ink image-receiving layer within a range that does not impair the transparency. Examples of the filler include fine powder silicic acid for inorganic fine particles, and acrylic resin, styrene resin, urea formaldehyde resin, benzoguanamine resin, silicone resin, and fluorine resin for organic fine particles. From the viewpoint of transparency, an acrylic resin is preferable. The amount of filler added is preferably 1 to 10% by weight with respect to 100% by weight of the ink image-receiving layer.

  The solvent used in the coating solution for the ink image-receiving layer is appropriately selected and used from the viewpoints of the coating property and dispersion stability of the image-receiving layer composition. Water, ethyl alcohol, isopropyl alcohol, toluene Xylene, ethyl cellosolve, ethyl cellosolve acetate, diclime, cyclohexanone and the like.

  The thickness of the ink image receiving layer can be set to 0.3 μm to 10 μm, for example. When the thickness is less than 0.3 μm, the printability tends to decrease due to the decrease in solvent absorbability. When the thickness exceeds 10 μm, the printability tends to decrease as the solvent absorbability increases.

  The colored layer used in one embodiment of the present invention is formed by applying a colored layer-forming ink that can be cured with an electron beam and irradiating it with an electron beam. For example, a coloring pigment, an electron beam curable compound, a solvent, and optionally a dispersing agent can be blended in the colored layer forming ink curable with an electron beam.

  Specific examples of the color pigment include Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 215, 216, 208, 216, 217, 220, 223, 224, 226, 227, 228, 240, Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64, Pigment Green 7, 36, Pigment Red 20, 24, 86, 81, 83, 93 , 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, 185, Pigment Orange 36, Pigment Violet 23, and the like. Further, these pigments can be used alone or in combination of two or more in order to obtain a desired hue.

  As the electron beam curable compound, a monomer, oligomer, prepolymer or the like having an ethylenically unsaturated double bond can be used. Specific examples of the electron beam curable compound include, for example, 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate. These compounds can be used alone or in admixture of two or more.

  The solvent used for the electron beam curable colored layer forming ink is required to have stability over time, drying property, etc. in addition to solubility, and is appropriately selected in relation to the dye and the electron beam curable compound. Examples of such a solvent include 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether, 2- (2 -Ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol, and diethylene glycol dimethyl ether are necessary. Depending on the situation, one kind or a mixture of two kinds can be used.

  A dispersant can be used to improve the dispersibility of the dye. Examples of the dispersant include nonionic surfactants such as polyoxyethylene alkyl ethers, and ionic surfactants such as sodium alkylbenzene sulfonate, poly fatty acid salts, fatty acid salt alkyl phosphates, tetraalkyl ammonium salts, and the like. In addition, organic pigment derivatives, polyester, and the like can be given. A dispersing agent can be used individually or in mixture of 2 or more types.

  In the production of the color filter substrate according to an embodiment of the present invention, the image receiving layer and the colored layer, or the image receiving layer, the colored layer, and the patterned light shielding layer are collectively cured by irradiation with an electron beam. Examples of the electron beam irradiation apparatus include curtain beam type, area beam type, broad beam type, scanning beam type, vacuum tube type and the like. The acceleration voltage of the electron beam is preferably 150 kV or less, more preferably 30 to 100 kV, and the irradiation amount of the electron beam is preferably 10 Mrad or less, more preferably 1 to 5 Mrad.

  In addition, the color filter substrate according to the embodiment of the present invention can further include an overcoat layer on the colored layer for the purpose of improving the durability after the pixels are formed.

  In the color filter substrate according to one embodiment of the present invention, the adhesion between the plastic film-barrier layer and the barrier layer-ink image receiving layer is classified as 0 or 1 in the cross-cut test based on JIS 5600-5-6. It is preferable that

  Examples of the present invention and comparative examples will be shown below to describe the present invention more specifically.

Example 1
A manufacturing process of the color filter substrate according to the first embodiment of the present invention will be described with reference to FIG.

  First, using a coating machine equipped with a coater head, a drying furnace, and an ultraviolet irradiation device on both surfaces of a plastic film 1 made of polyethersulfone having a thickness of 100 μm, it is composed of a polyfunctional acrylate resin, a photoinitiator, and a solvent. After applying the liquid and drying the solvent, the film was cured by irradiating with ultraviolet rays to form undercoat layers 2a and 2b having a thickness of 5 μm as shown in FIG. Thus, the total light transmittance of the plastic film 1 on which the undercoat layers 2a and 2b were formed was 90%, and the linear expansion coefficient from 30 ° C. to 150 ° C. was 55 ppm. Moreover, when the adhesiveness of undercoat layer 2a, 2b was evaluated by the crosscut test based on JIS5600-5-6, it was classification 0 and was favorable.

Next, as shown in FIG. 1B, one of the undercoat layers is formed by a reactive sputtering method using oxygen as a reactive gas, using Si as a target, by a sputtering roll coater that performs DC sputtering film formation. on the 2a, forming a thickness 50nm of SiO _{x (x} = 1.8), and the gas barrier layer 3. When the adhesion of the gas barrier layer 3 was evaluated in the same manner as described above, it was classified as 0 and good.

  Next, on the gas barrier layer 3, using a continuous coating machine equipped with a coater head and a drying furnace, a photosensitive light-shielding layer material in which carbon black is dispersed in a photocurable acrylic resin has a thickness after drying of 1 to 1. It was continuously applied by roll-to-roll so as to be 2 μm. Subsequently, using a continuous patterning apparatus including an exposure apparatus and a developing apparatus, patterning exposure is performed through a photomask, development is performed, and then heat curing is performed at 150 ° C. for 30 minutes in a drying furnace. ), A patterned light shielding layer 4 was formed. When the adhesion was evaluated in the same manner as described above, it was classified as 0 and good.

  Thereafter, as shown in FIG. 1 (d), the electron beam curable acrylic copolymer is dried on the gas barrier layer 3 on which the patterned light-shielding layer 4 is formed in this manner, using the coating machine. The ink image receiving layer 5 was formed by coating so that the subsequent film thickness was 2 to 3 μm. When the adhesion of the ink image-receiving layer 5 was evaluated in the same manner as described above, it was classified as Class 0 and was good.

  Next, on the portion of the ink image-receiving layer 5 corresponding to the opening of the patterned light-shielding layer 4, red (R), green (G), and blue (B) electron beam curable colored inks are used, and 30 pl. After forming the colored layers of R, G, and B by an ink jet method using an ink jet printing apparatus equipped with an ink jet head having a nozzle pitch of 100 dpi and 256 nozzle arrangement, the film is dried at 100 ° C. for 5 minutes, and FIG. As shown in e), a color filter layer 6 was formed.

  Thereafter, the image receiving layer 5 and the color filter layer 6 were collectively cured with an electron beam to prepare a flexible color filter substrate. When the adhesion of the color filter layer 6 was evaluated in the same manner as described above, it was classified as 0 and was good.

A top view of the flexible color filter substrate thus prepared is shown in FIG. This flexible color filter substrate had a linear expansion coefficient of 55 ppm at 30 ° C. to 150 ° C. Further, when the water vapor transmission rate at 40 ° C. and 90% RH was measured based on the JISK7129B method, it was 0.07 g / m ² · 24 hr. Moreover, as a result of conducting a heat resistance test at 150 ° C. for 10 hours, it was confirmed that the color filter layer 6 had good resistance without any change in density before and after the test of the color filter layer 6.

Example 2
A manufacturing process of the color filter substrate according to the second embodiment of the present invention will be described with reference to FIG.

  First, a film film forming apparatus including a solution in which 30% by weight of a polyfunctional acrylate resin, 20% by weight of amorphous glass filler, and 50% by weight of propylene glycol monomethyl ether are uniformly dispersed is provided with a die coater, a stainless steel endless belt, and a drying furnace. Cast on a stainless steel endless belt, heated to 150 ° C in a drying oven, dried and cured, then peeled off continuously from the endless belt, and further heated and cured to 170 ° C in a continuous drying oven. A plastic film having a width of 30 cm, a length of 100 m, and a thickness of 100 μm was obtained. The total light transmittance of this plastic film was 90%.

  Using a coating machine having a coater head, a drying furnace, and an ultraviolet irradiation device on both surfaces of the film 1, a liquid composed of a polyfunctional acrylate resin, a photoinitiator, and a solvent is applied, and after the solvent is dried, ultraviolet rays are applied. Irradiated and cured, and undercoat layers 2a and 2b were formed as shown in FIG. When the adhesion of the undercoat layers 2a and 2b was evaluated by a cross-cut test in the same manner as described above, it was classified as 0 and was good.

Next, as shown in FIG. 1B, a sputtering roll coater that performs DC sputter film formation is a reactive sputtering method using oxygen as a reactive gas, and Si is used as a target on the undercoat 2a. A gas barrier layer 3 was formed by depositing SiO _x (x = 1.8) having a thickness of 50 nm. When the adhesion of the gas barrier layer 3 was evaluated in the same manner as described above, it was classified as 0 and good.

  Next, on the gas barrier layer 3, using a continuous coating machine equipped with a coater head and a drying furnace, a photosensitive light-shielding layer material in which carbon black is dispersed in a photocurable acrylic resin has a thickness after drying of 1 to 1. It was continuously applied by roll-to-roll so as to be 2 μm. Subsequently, using a continuous patterning apparatus including an exposure apparatus and a developing apparatus, patterning exposure is performed through a photomask, development is performed, and then heat curing is performed at 150 ° C. for 30 minutes in a drying furnace. ), A patterned light shielding layer was formed. When the adhesion was evaluated in the same manner as described above, it was classified as 0 and good.

  Thereafter, as shown in FIG. 1 (d), the electron beam curable acrylic copolymer is dried on the gas barrier layer 3 on which the patterned light-shielding layer 4 is formed in this manner, using the coating machine. The ink image receiving layer 5 was formed by coating so that the subsequent film thickness was 2 to 3 μm. When the adhesion of the ink image-receiving layer 5 was evaluated in the same manner as described above, it was classified as Class 0 and was good.

  Next, on the portion of the ink image-receiving layer 5 corresponding to the opening of the patterned light-shielding layer 4, red (R), green (G), and blue (B) electron beam curable colored inks are used, and 30 pl. 1, by forming an R, G, B pattern-like colored layer by an inkjet method using an inkjet printing apparatus equipped with an inkjet head having a nozzle pitch of 100 dpi and 256 nozzle arrangement, and drying at 100 ° C. for 5 minutes. As shown in (e), the color filter layer 6 was formed.

  Thereafter, the image receiving layer and the color filter layer 6 were collectively cured with an electron beam to prepare a flexible color filter substrate. When the adhesion of the color filter layer 6 was evaluated in the same manner as described above, it was classified as 0 and was good.

The thus-prepared flexible color filter substrate had a linear expansion coefficient of 27 ppm at 30 ° C. to 150 ° C. Moreover, based on JISK7129B method, when the water-vapor-permeation rate at 40 degreeC 90% RH was measured, it was 0.06g / m < ² > * 24hr. Further, as a result of a heat resistance test at 150 ° C. for 10 hours, the color filter layer 6 was confirmed to have good resistance without any change in density before and after the test of the color filter layer 6.

Example 3
A manufacturing process of the color filter substrate according to the third embodiment of the present invention will be described with reference to FIG.

  First, a solution in which 32% by weight of an alicyclic epoxy resin, 18% by weight of a fine silica filler having a particle diameter of 50 nm or less, and 50% by weight of a solvent are uniformly dispersed is formed into a film comprising a die coater, a stainless steel endless belt, and a drying furnace. Cast on the stainless steel endless belt of the membrane device, heat to 150 ° C in a drying oven, dry and cure, then peel continuously from the endless belt, and then heat cure to 170 ° C in a continuous drying oven. Then, a plastic film having a width of 30 cm, a length of 100 m, and a thickness of 100 μm was obtained. The total light transmittance of this plastic film was 88%.

Next, as shown in FIG. 3A, by using a sputtering roll coater including two film forming chambers, an RF sputtering chamber and a DC sputtering chamber, first, Ta ₂ O ₅ is used as a target by RF sputtering, A TaO _x (x = 2.2) film having a thickness of 50 nm is formed on the plastic film 11 to form the gas barrier layer 12, and then a chromium film having a thickness of 150 nm is formed in the DC sputtering chamber, and the light shielding layer 13. Formed. When the adhesion between the gas barrier layer 12 and the light shielding layer 13 was evaluated in the same manner as described above, it was classified as 0 and was good.

  This film was cut into a length of 40 cm and patterned by a photolithography process to remove the chromium film other than the portion that needs to be shielded from light, thereby forming a patterned light-shielding layer 14 as shown in FIG.

  Next, using the coating machine, the electron beam curable acrylic copolymer was applied on the patterned light-shielding layer 14 so that the film thickness after drying was 2 to 3 μm, as shown in FIG. Thus, the ink image receiving layer 15 was formed. When the adhesion of the ink image-receiving layer 15 was evaluated in the same manner as described above, it was classified as 0 and good.

  Thereafter, red (R), green (G), and blue (B) electron beam curable colored inks are used on the ink image receiving layer 15 corresponding to the openings of the patterned light shielding layer 14, and the nozzle pitch is 30 pl. An R, G, and B patterned colored layer is formed by an inkjet method using an inkjet printing apparatus equipped with an inkjet head having an array of 100 dpi and 256 nozzles, and then dried at 100 ° C. for 5 minutes. As shown, a color filter layer 16 was formed.

  Finally, the image receiving layer and the colored layer were collectively cured with an electron beam to prepare a flexible color filter substrate. When the adhesiveness of the color filter layer 16 was evaluated in the same manner as described above, it was classified as 0 and satisfactory.

The linear color expansion coefficient at 30 ° C. to 150 ° C. of the flexible color filter substrate thus prepared was 30 ppm. Moreover, it was 0.02 g / m < ² > * 24hr when the water-vapor-permeation rate at 40 degreeC90% RH was measured based on JISK7129B method. Further, as a result of the heat resistance test at 150 ° C. for 10 hours, it was confirmed that the color filter layer 16 had good resistance without any change in concentration before and after the test.

Example 4
A manufacturing process of the color filter substrate according to the fourth embodiment of the present invention will be described with reference to FIG.

  First, a polyfunctional acrylate resin is soaked in glass fiber, and then continuously cured by an ultraviolet curing device. A plastic film having a resin weight of 60% by weight, glass fiber 40% by weight, width 30 cm, length 100 m, and thickness 100 μm is obtained. Obtained. The total light transmittance of this plastic film was 90%.

  Next, as shown in FIG. 4A, an SiAlON film having a film thickness of 50 nm is formed on the plastic film 21 by using a sputtering roll coater having an RF sputtering film forming chamber and using SiAlON as a target by RF sputtering. A gas barrier layer 22 was formed.

  Next, on the gas barrier layer 22, using a continuous coating machine having a coater head and a drying furnace, an electron beam curable acrylic copolymer was applied so that the film thickness after drying was 2 to 3 μm. As shown in FIG. 4B, an ink image receiving layer 23 was formed. When the adhesion of the ink image-receiving layer 23 was evaluated in the same manner as described above, it was classified as Class 0 and was good.

  After that, an ink jet equipped with an ink jet head having 30 pl, nozzle pitch of 100 dpi, and 256 nozzle arrangement using red (R), green (G), and blue (B) electron beam curable colored inks on the image receiving layer 23. A patterned colored layer of each of R, G, and B was formed by an inkjet method using a printing apparatus, and then dried at 100 ° C. for 5 minutes to form a color filter layer 24 as shown in FIG.

  Next, the image receiving layer 23 and the color filter layer 24 were collectively cured with an electron beam.

  Next, a continuous light-shielding layer material in which carbon black is dispersed in a photocurable acrylic resin is continuously applied so that the film thickness after drying becomes 1 to 2 μm, and a continuous patterning device having an exposure device and a developing device is provided. Then, patterning exposure is performed through a mask, development is performed, and then heat curing is performed at 150 ° C. for 30 minutes in a drying furnace. As shown in FIG. 4D, between the R, G, and B pixels. A patterned light-shielding layer 25 was formed on the substrate, and a flexible color filter substrate was prepared. When the adhesion of the color filter layer 24 was evaluated in the same manner as described above, it was classified as 0 and satisfactory.

The linear color expansion coefficient at 30 ° C. to 150 ° C. of the flexible color filter substrate thus prepared was 18 ppm. Further, when the water vapor transmission rate at 40 ° C. and 90% RH was measured based on the JISK7129B method, it was 0.05 g / m ² · 24 hr. Furthermore, as a result of conducting a heat resistance test at 150 ° C. for 10 hours, it was confirmed that the color filter layer 24 had good resistance with no change in density before and after the test.

Comparative Example 1
As in Example 1, it was deposited an undercoat layer on both surfaces of the plastic film made of polyether sulfone having a thickness of 100 [mu] m, forming a thickness 50nm of SiO _{x (x} = 1.8) on it, A gas barrier layer was formed.

  Next, a photosensitive light-shielding layer material in which carbon black is dispersed in a photocurable acrylic resin on a gas barrier layer using a continuous coating machine having a coater head and a drying furnace has a thickness of 1 to 2 μm after drying. As described above, after continuous application by roll-to-roll, patterning exposure using a continuous patterning apparatus having an exposure apparatus and a developing apparatus, development is performed, and then, at 150 ° C. in a drying furnace, 30 ° C. Heat curing for minutes was performed to form a patterned light shielding layer. When the adhesion of the patterned light-shielding layer was evaluated in the same manner as described above, it was classified as 0 and satisfactory.

  Next, on the gas barrier layer, the above-mentioned coating machine was used to apply the thermosetting acrylic copolymer so that the film thickness after drying was 2 to 3 μm, thereby forming an ink image receiving layer. When the adhesion of the ink image-receiving layer was evaluated in the same manner as described above, it was classified as Class 0 and was good.

  Thereafter, red (R), green (G), and blue (B) thermosetting colored inks are used on the portion of the ink image-receiving layer corresponding to the opening of the patterned light-shielding layer, 30 pl, nozzle pitch 100 dpi. After forming an R, G, B pattern-like colored layer by an inkjet method using an inkjet printing apparatus equipped with an inkjet head with 256 nozzle arrays, a color filter layer is formed by drying at 220 ° C. for 30 minutes and thermosetting. Thus, a flexible color filter substrate was prepared.

  When the adhesion of the color filter layer was evaluated in the same manner as described above, it was classified as Class 0 and was satisfactory. However, application of heat to cure the ink image receiving layer and the color filter layer caused thermal expansion of the substrate, resulting in displacement of the color filter.

Comparative Example 2
As in Example 2, was deposited an undercoat layer on both surfaces of a plastic film made of epoxy resin and silica filler, forming a film thickness 50nm of SiO X _{(x =} 1.8) on it, a gas barrier layer Formed.

  Next, using a continuous coating machine having a coater head and a drying furnace on the gas barrier layer, a photosensitive light-shielding layer material in which carbon black is dispersed in a photocurable acrylic resin has a thickness of 1 to 2 μm after drying. As described above, after continuous application by roll-to-roll, patterning exposure using a continuous patterning apparatus having an exposure apparatus and a developing apparatus, development is performed, and then, at 150 ° C. in a drying furnace, 30 ° C. Heat curing for minutes was performed to form a patterned light shielding layer. When the adhesion of the patterned light-shielding layer was evaluated in the same manner as described above, it was classified as 0 and was good.

  Next, on the gas barrier layer, using the above-mentioned coating machine, a photocurable acrylic copolymer containing a photopolymerization initiator is applied so that the film thickness after drying becomes 2 to 3 μm, and the ink image receiving layer Formed. When the adhesion of the ink image-receiving layer was evaluated in the same manner as described above, it was classified as Class 0 and was good.

  Thereafter, red (R), green (G), and blue (B) photocurable coloring inks are used on the portion of the ink image-receiving layer corresponding to the opening of the patterned light-shielding layer, and 30 pl and a nozzle pitch of 100 dpi are used. A color filter layer composed of R, G, and B patterned colored layers was formed by an ink jet method using an ink jet printing apparatus equipped with an ink jet head in which 256 nozzles were arranged.

  Next, after drying at 100 ° C. for 5 minutes, UV irradiation was performed, and the image receiving layer and the colored layer were collectively cured to prepare a flexible color filter substrate. When the adhesion of the color filter layer was evaluated in the same manner as described above, it was classified as 0 and good, but as a result of a heat test at 150 ° C. for 10 hours, the concentration of the colored part before and after the test changed significantly. Occurred.

  As described above, in Examples 1 to 4, good flexible color filter substrates could be obtained. On the other hand, in the comparative example 1, since the color filter layer was cured not by electron beam curing but by thermal curing, a displacement error occurred due to thermal expansion of the plastic film. In Comparative Example 2, since a plastic film having a small coefficient of thermal expansion was used, misalignment could be prevented. However, since UV curing was performed, the remaining photoinitiator changed the color in the subsequent heating step. There has occurred.

  The flexible color filter substrate according to the present invention can be suitably used for a flat panel display such as a liquid crystal display or an organic EL display, and is particularly useful for producing a flexible ultra-thin display.

It is sectional drawing which shows the manufacturing process of the flexible color filter substrate which concerns on the 1st Example of this invention. 1 is a top view of a flexible color filter substrate manufactured according to a first embodiment of the present invention. It is sectional drawing which shows the manufacturing process of the flexible color filter substrate which concerns on the 3rd Example of this invention. It is sectional drawing which shows the manufacturing process of the flexible color filter board | substrate which concerns on the 4th Example of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1,11,21 ... Plastic film, 2a, 2b ... Undercoat layer, 3, 12, 22 ... Gas barrier layer, 4, 14, 25 ... Pattern light shielding layer, 13 ... Light shielding Layers 5, 15, 23... Ink image receiving layer, 6, 16, 24... Color filter layer.

Claims (18)

Forming a patterned light-shielding layer on the gas barrier layer of the substrate having a gas barrier layer on at least one side of the plastic film;
Forming an image receiving layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the gas barrier layer on which the patterned light shielding layer is formed;
Forming a colored layer containing a (meth) acrylic acid ester derivative having at least two functional groups that is cured by irradiation with an electron beam in a pattern on at least a portion of the image receiving layer corresponding to the opening of the patterned light shielding layer And a step of irradiating the image receiving layer and the colored layer with an electron beam and curing them collectively. A method for producing a flexible color filter substrate, comprising: Forming an image receiving layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the gas barrier layer of the base material having a gas barrier layer on at least one surface of the plastic film;
Forming a colored layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the image-receiving layer in a pattern;
A step of irradiating the image receiving layer and the colored layer with an electron beam and curing them at once; and a step of forming a patterned light-shielding layer in the gap between the patterned colored layers;
A method for producing a flexible color filter substrate, comprising: Forming an image receiving layer containing a (meth) acrylic acid ester derivative having two or more functional groups that is cured by irradiation with an electron beam on the gas barrier layer of the substrate having a gas barrier layer on at least one surface of the plastic film;
Forming a colored layer containing a (meth) acrylic acid ester derivative having two or more functional groups which is cured by irradiation with an electron beam on the image receiving layer in a pattern;
A step of forming a patterned light-shielding layer containing a (meth) acrylic ester derivative having two or more functional groups that is cured by electron beam irradiation in the gap between the patterned colored layers; and the image receiving layer, the colored layer, and the patterned light-shielding A method for producing a flexible color filter substrate, comprising: a step of irradiating a layer with an electron beam and simultaneously curing the layer. The method for producing a flexible color filter substrate according to any one of claims 1 to 3, wherein the method is performed in a roll-to-roll manner. The method for producing a flexible color filter substrate according to claim 1, wherein the base material has a total light transmittance of 80% or more. The said plastic film has a linear expansion coefficient of 40 ppm / degrees C or less in 30 to 150 degreeC, The manufacturing method of the flexible color filter substrate in any one of Claims 1-3 characterized by the above-mentioned. The method for manufacturing a flexible color filter substrate according to claim 6, wherein the plastic film is made of a crosslinked resin. The method for producing a flexible color filter substrate according to claim 7, wherein the crosslinkable resin is made of an epoxy resin or an acrylic resin. The method for producing a flexible color filter substrate according to claim 1, wherein the plastic film is made of a resin and an inorganic substance. The method for producing a flexible color filter substrate according to claim 1, wherein the gas barrier layer is made of an inorganic substance. The method for manufacturing a flexible color filter substrate according to claim 10, wherein the gas barrier layer contains a compound containing at least one selected from the group consisting of Si, Ta, and Al as a main component. The method for producing a flexible color filter substrate according to claim 11, wherein the compound is selected from the group consisting of an oxide, a nitride, and an oxynitride. Regarding the adhesion between adjacent layers of the plastic film, gas barrier layer, patterned light-shielding layer, image receiving layer and colored layer, the cross-cut test result based on JIS 5600-5-6 is classified as Class 0 or Class 1. The method for producing a flexible color filter substrate according to any one of claims 1 to 12. The method for producing a flexible color filter substrate according to claim 1, wherein the base material has an undercoat layer between the plastic film and the gas barrier layer. The adhesion between the plastic film, the undercoat layer, the gas barrier layer, the patterned light-shielding layer, the image receiving layer, and the colored layer adjacent to each other is determined according to a crosscut test result based on JIS 5600-5-6 as classification 0 or classification 1. The method for producing a flexible color filter substrate according to claim 14, wherein: 0.2g / m ² The method for producing a flexible color filter substrate according to any one of claims 1 to 15, which has a water vapor transmission rate of 24 hr or less. The method for producing a flexible color filter substrate according to claim 1, wherein an undercoat layer is provided between the plastic film and the gas barrier layer.   The combination of the plastic film, the undercoat layer, and the gas barrier layer is polyethersulfone / acrylic crosslinkable resin / silicon oxide, acrylic crosslinkable resin / acrylic crosslinkable resin / silicon oxide, or epoxy crosslinkable. 18. The method for producing a flexible color filter substrate according to claim 17, wherein the method is resin / epoxy crosslinking resin / silicon aluminum oxynitride.

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