JP2006162848A - Color filter for display device, color filter member, and method of manufacturing color filter for display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the reliability of a color filter by suppressing the variance of dimensions in a manufacturing process of a color filter layer. <P>SOLUTION: The color filter for display devices, which has the color filter layer formed on a plastic film by heat treatment, has barrier layers on both sides of the plastic film, and the thickness of each barrier layer is within a range from 30nm to 200nm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a color filter for a display device such as a liquid crystal display device, and more particularly to a color filter for a display device using a plastic film as a base material. The present invention also relates to a color filter member using such a color filter for a display device. The present invention also relates to a method for manufacturing such a color filter for a display device.

  Flat panel displays such as liquid crystal display devices and organic electroluminescence (organic EL) display devices are widely used as thin and space-saving display devices. Among these display devices, most of those that perform color display (particularly most of liquid crystal display devices) are colored by RGB color filters corresponding to pixels formed using a glass substrate. A substrate on which three primary color patterns are formed is generally called a color filter.

In recent years, it has been proposed to use a plastic film as a substrate in place of glass in order to further reduce the thickness and weight of a display device for a portable device such as a mobile phone (Patent Document 1). As types of plastic films, in addition to thermoplastic films such as polyethylene terephthalate, polycarbonate, and polyethersulfone, crosslinkable resins such as epoxy resins have been proposed.
JP 2000-284303 A

By the way, when manufacturing a color filter using a plastic film, the following is a problem.
First, when a colored resist is used at the time of manufacturing a color filter, patterning by photolithography is performed through exposure processing, development processing, and baking processing. It is necessary to perform this step three times for each of the red, green, and blue colored portions, or at least four times when a resin black matrix is formed between the colored portions in addition to these colored portions. Among the above steps, the plastic film after the exposure process in the development process is immersed in an alkaline developer. At this time, the plastic film is impregnated with an alkaline aqueous solution, resulting in a dimensional change of the plastic film, and a glass substrate. There is a problem that the dimensional accuracy deviates from the design value compared to when it is used.

  Secondly, the plastic film has no gas barrier property as compared with the glass substrate, and there is a problem that the life of the plastic film is shortened by deteriorating the liquid crystal or the organic EL due to the contact of gas such as water vapor or oxygen.

  Therefore, the present invention has an object to provide a color filter for a display device designed to suppress a decrease in reliability due to various causes during use, and a color filter member using the color filter for the display device. An object of the present invention is to provide a method for manufacturing such a color filter for a display device.

The color filter for a display device according to the present invention is a color filter for a display device having a color filter layer formed by heat treatment on a plastic film.
The plastic film has barrier layers on both sides, and the thickness of each barrier layer is in the range of 30 nm to 200 nm.

  With this configuration, the barrier layers provided on both surfaces of the plastic film prevent impregnation of the developer during each development step in the photolithography technique used when forming the color filter layer, thereby preventing the plastic film from being impregnated. Dimensional change is prevented and dimensional accuracy is improved. Thereby, high-detail pattern formation becomes possible. In addition, the barrier layer can be made thick enough to exhibit barrier properties, and can be made thick enough to suppress stresses so as not to cause warping or cracking of the substrate. Improves.

Further, in this color filter for display device, the water vapor transmission rate of the plastic film having the barrier layers on both sides is set to 0.02 g / (m ² · 24 hr) (according to the measurement method according to JIS K 7129B) or less. Good.
Thereby, the gas barrier property with respect to water vapor | steam can be provided to the barrier layer provided in both surfaces of the plastic film, and it does not shorten the lifetime of the liquid crystal used as a display apparatus, or organic EL.

In the color filter for display device, an overcoat layer may be provided on the surface of at least one barrier layer.
By providing the overcoat layer, scratches on the barrier layer that may enter during handling can be reduced.

In the color filter for display device, the linear expansion coefficient of the plastic film at 30 ° C. to 150 ° C. may be 0 ppm / ° C. or more and 40 ppm / ° C. or less.
Thereby, the dimensional change of a plastic film is prevented at the time of each heating process in the photolithography technique used when forming a color filter layer, and dimensional accuracy improves. As a result, a highly detailed pattern can be formed, and the reliability of the color filter is improved.

  In addition, the color filter member according to the present invention is a color filter member including any one of the color filters for display devices described above, wherein a transparent conductive film is formed on the surface of the color filter layer continuously imposed on the plastic film. And a column spacer, or a transparent electrode, a protective film, and a column spacer.

  In general, spacers often disturb the alignment of liquid crystals and cause alignment defects. For this reason, unnecessary light transmission occurs due to this alignment defect during black display. Normally used bead type spacers are randomly distributed over the entire surface of the color filter, and therefore, the contrast is lowered due to the alignment defects generated by the spacers distributed on the light transmitting portion of the color filter.

  On the other hand, since the column spacer can be provided in a portion where light is shielded by the black matrix, it is possible to prevent a decrease in contrast that may occur when a bead type spacer is used. Normally, a user who purchases a color filter forms a column spacer through a photolithography process as necessary. However, a special color filter can be provided on a color filter formed by photolithography in the same manner as the column spacer. Even without providing a simple process, it is possible to save the user the trouble of providing the column spacer. Further, the transparent electrode is formed before the column spacer is formed in order to avoid a short circuit between the upper and lower substrates.

Further, the method for producing a color filter for a display device according to the present invention is a method for producing a color filter for a display device having a color filter layer formed by heat treatment on a plastic film.
A first step of forming barrier layers on both sides of the plastic film so that the thickness of each barrier layer is in the range of 30 nm to 200 nm,
And a second step of forming the color filter layer.

  Thus, the barrier layer is provided on the plastic film in the first step, and the color filter layer is provided on the plastic film in the second step. In the color filter thus obtained, the photolithography technique used for forming the color filter layer is used. During each development step, barrier layers provided on both sides of the plastic film prevent impregnation of the developer, thereby preventing dimensional change of the plastic film and improving dimensional accuracy. Thereby, high-detail pattern formation becomes possible. In addition, the barrier layer can be made thick enough to exhibit barrier properties, and can be made thick enough to suppress stresses so as not to cause warping or cracking of the substrate. Improves.

In this method of manufacturing a color filter for a display device,
In the first step,
Forming a first barrier layer on one side of the plastic film in a sputtering apparatus;
Forming an overcoat layer on the surface of the first barrier layer;
A second barrier layer may be formed on the surface of the plastic film opposite to the surface on which the overcoat layer and the first barrier layer are formed by the sputtering apparatus.

  Accordingly, an overcoat layer that reduces scratches on the barrier layer that may enter during handling can be provided, and the barrier layer and the overcoat layer can be formed on the opposite surface by forming the barrier layer and the overcoat layer in the above order. When the film is unwound in a vacuum when the barrier layer is formed, the barrier layer can be protected to prevent the formation of cracks.

In the method for producing a color filter for display device, in the first step, the surface of the first barrier layer may be corona-treated after the first barrier layer is formed and before the overcoat layer is formed.
By doing in this way, the adhesiveness of a barrier layer and an overcoat layer can be improved.

In this method of manufacturing a color filter for a display device,
In the first step,
The barrier layer is continuously formed roll-to-roll by using a roll film forming apparatus provided with at least a roll unwinding device, a film forming device, and a roll winding device on both surfaces of a plastic film formed into a long roll. You may make it do.
Thereby, a plastic film can be obtained by roll-to-roll, and productivity improves compared with the former which has obtained the plastic film in the cut sheet form.

Furthermore, in the manufacturing method of the color filter for the display device,
In the second step,
Using a transfer material in which a colored ionizing radiation curable resin layer is formed on a transfer substrate plastic, the colored ionizing radiation curable resin layer of the transfer material faces the plastic film so that the transfer is performed on the plastic film. A process of thermo-compression bonding the material;
The transfer material is exposed to the layer of colored ionizing radiation curable resin left after peeling the transfer base plastic from the pressure-transferred transfer material through a photomask, or after exposure to the layer of colored ionizing radiation curable resin. Including a continuous process of peeling the base plastic and developing to form a colored pattern,
Repeat the above steps for each hue using a transfer material on which a colored ionizing radiation curable resin layer having a different hue is formed so that the color filter layer is formed by a roll-to-roll process. Also good.

In the manufacturing method of the color filter for display device,
In the second step, the color filter is
A step of laminating a protective film after directly forming a colored ionizing radiation curable resin layer on the plastic film;
After exposing the colored ionizing radiation curable resin layer remaining after peeling off the protective film through a photomask, or after exposing the colored ionizing radiation curable resin layer after exposure to the colored ionizing radiation curable resin layer, developing and coloring A continuous process of forming a pattern of
The above-described steps may be repeated for the colored ionizing radiation curable resin layers having different hues, and the color filter layer may be formed by a roll-to-roll process.

In the manufacturing method of the color filter for display device,
In the second step,
A layer of colored ionizing radiation curable resin is directly applied and formed on the plastic film, and the colored ionizing radiation curable resin layer is exposed through a photomask and developed to form a colored pattern. The color filter layer may be formed by a roll-to-roll process by repeating the continuous steps for layers of colored ionizing radiation curable resin having different hues.

  According to these color filter manufacturing methods for display devices, a colored layer can be effectively formed on a plastic film obtained by roll-to-roll. In addition, since the colored layer can be formed roll-to-roll, the colored layer forming process can be highly automated, and a color filter for a display device can be efficiently produced. .

  ADVANTAGE OF THE INVENTION According to this invention, the color filter designed so that the fall of the reliability by various causes at the time of use can be suppressed can be provided.

Hereinafter, embodiments of a color filter for a display device according to the present invention, a color filter member using the color filter, and a method for manufacturing the color filter for the display device will be described.
FIG. 1 is an enlarged plan view of a main part of the color filter for a display device according to the present embodiment. 2A is a cross-sectional view taken along the plane AA ′ in FIG. 1, and FIG. 2B is a cross-sectional view taken along the line BB ′ in FIG.

  The color filter 10 is provided with a black matrix pattern 16 and an RGB coloring pattern composed of a red pattern 18, a green pattern 20 and a blue pattern 22 on the main surface of the plastic film 12 having a barrier layer 14 formed on both sides, and further transparent. A column spacer 26 is provided in this order for securing a space between the electrode layer 24 and adjacent elements when stacked. Here, the transparent electrode layer 24 and the column spacer 26 have an arbitrary configuration and can be omitted as appropriate.

  Further, as shown in FIG. 1, the black matrix pattern 16 is provided in a lattice pattern on the plastic film 12, and each color pattern of the RGB coloring pattern is provided at the position of the square surrounded by the black matrix pattern 16. It has been. The column spacers 26 are provided on the intersections in the black matrix pattern 16 and / or on the black matrix pattern 16.

Here, the pattern of each color is arranged in a predetermined direction with a period of red, green, and blue.
FIG. 3 is a diagram showing one pitch of the colored pattern.
In FIG. 3, the black matrix pattern 16, the red pattern 18, the black matrix pattern 16, the green pattern 20, the black matrix pattern 16, and the blue pattern 22 are configured in this order from the end face of the blue pattern 22 to the end face of the next blue pattern 22. An example of one pitch is shown.

  The distance h for one pitch is appropriately determined depending on the required resolution and the like. For example, the distance h is determined in the range of 80 ppi to 200 ppi (corresponding to 320 μm to 125 μm), while the distance d between the colored patterns of each color is, for example, It is determined in the range of 5 to 10 μm. For example, when the distance h for one pitch is 126 μm, the width of the colored pattern of each color in the pitch direction can be 35 μm and the distance d can be 7 μm.

  Therefore, in the color filter manufacturing process, it is necessary to suppress an error in forming a colored pattern within several μm.

  Accordingly, a color filter for a display device that makes it possible to minimize an error in forming a colored pattern (patterning process) in such a manufacturing process is for a display device having a color filter layer formed by heat treatment on a plastic film. A color filter having barrier layers on both sides of a plastic film.

  Examples of the resin used for the plastic film include thermoplastic resins, crosslinkable resins, and multilayer films thereof. In particular, when a crosslinkable resin is used, deformation when stress such as tension is applied during heating is reduced.

  Examples of the crosslinkable resin include a photocrosslinkable resin and a heat crosslinkable resin. In addition, a polyfunctional acrylate resin, an acrylic resin, or the like can be used as the photocrosslinkable resin, and an epoxy resin can be used as the thermally crosslinkable resin. When these resins are used, the processing method and the resin characteristics The compatibility of becomes better.

  Moreover, the linear expansion coefficient in 30 to 150 degreeC of a plastic film can be 0 ppm / degrees C or more and 40 ppm / degrees C or less. In this case, dimensional deviation due to temperature variations during the patterning process can be kept small. A plastic film having a linear expansion coefficient in this range can be obtained by including an inorganic substance in the crosslinkable resin.

  Examples of the inorganic material include silica, glass and other silicon oxide as a main component, and metal oxides such as alumina, zirconia and titania. Although not necessarily limited thereto, silicon dioxide is mainly used. When used as a component, the difference in refractive index between the inorganic substance and the resin is small, and it becomes easy to obtain good transparency. Further, the surface of these inorganic substances may be surface-treated with acrylic silane or the like.

  The plastic film used in the present invention preferably has a total light transmittance of 80% or more. In particular, when the resin is used by including an inorganic substance, the particle size of the inorganic substance in the plastic film is 100 nm or less, or the difference in refractive index between the crosslinkable resin and the inorganic substance in the plastic film is ± 0.005. By making it within the range, it becomes easy to obtain a film having a light transmittance of 80% or more.

  Furthermore, as a plastic film used for this invention, the glass transition temperature can use what is 200 degreeC or more. When a plastic film having such a glass transition temperature of 200 ° C. or higher is used, the problem of thermal deformation during post-baking of the color filter layer is less likely to occur as will be described later.

  Moreover, in this invention, it can also be set as the structure which has an undercoat layer on the surface of a plastic film. By providing the undercoat layer, when a barrier layer is formed on the plastic film, the adhesion of the barrier layer to the plastic film can be further improved. Examples of such an undercoat layer include acrylic crosslinkable resins and epoxy crosslinkable resins, but are not particularly limited thereto.

  Plastic films generally transmit gases such as oxygen and water vapor, but when applied to, for example, liquid crystal displays and organic EL displays such as color filters for display devices using glass substrates, the gas permeability is very high. It is necessary to be low, and by providing the barrier layer on the surface, it is possible to provide the properties required for such a color filter for a display device. In this case, the barrier layer can be an inorganic thin film with little change in transmittance due to temperature and humidity.

  Here, the material of the inorganic thin film that can be used as the barrier layer is at least one selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Mg, La, Cr, Ca, Zr, and Ta. Including, but not limited to, oxides, nitrides, oxynitrides or halides containing as a main component, one or more selected from Si, Ta, and Al are included. Those mainly composed of oxide, nitride or oxynitride are particularly preferred. The inorganic barrier layer may be one layer or two or more layers.

  The thickness of this barrier layer is in the range of 30 nm to 200 nm, preferably 50 nm to 150 nm. Further, when the thickness of the barrier layer provided on one surface of the plastic film is r1, and the thickness of the barrier layer provided on the other is r2, r1 / r2 is 0.5 to 2.0, preferably 0. It may be in the range of 7 to 1.4.

  By providing barrier layers of a predetermined thickness on both sides of the plastic film in this way, the barrier layers provided on both sides of the plastic film during each development step in the photolithography technique used when forming the color filter layer Prevents impregnation of the developer, thereby preventing dimensional change of the plastic film and improving dimensional accuracy. Thereby, high-detail pattern formation becomes possible.

  In addition, the barrier layer in this range can be made thick enough to exhibit barrier properties, and can be made thick enough to suppress warping, cracking, etc. of the substrate. Improves.

  Moreover, since the thickness of each barrier layer will be substantially equalized by making ratio of both thickness into said range, the formation conditions of both barrier layers can be made substantially the same.

  In the plastic film provided with the barrier layer, the dimensional change when immersed in water at 23 ° C. for 30 minutes may be 50 ppm or less in any direction. Thereby, even if this plastic film is immersed in a developing solution in the development process in the photolithography technique used when providing the color film layer, the dimension does not change. Thereby, the original design dimension of the obtained color filter is maintained, and the dimensional accuracy is improved.

Further, the water vapor transmission rate of the plastic film provided with the barrier layer measured by a measuring method according to JIS K 7129 is 0.02 g / m ² · 24 hr or less, preferably 0.01 g / m ² · 24 hr or less. is there.
Thereby, the gas barrier property with respect to water vapor | steam can be provided to the barrier layer provided in both surfaces of the plastic film, and it does not shorten the lifetime of the liquid crystal used as a display apparatus, or organic EL.

  Further, as shown in FIGS. 2A and 2B, an overcoat layer 15 may be provided on the surface of the barrier layer 14. Examples of the resin used for the overcoat layer 15 include a photocurable resin and a thermosetting resin. Examples of the photocurable resin include epoxy acrylate, urethane acrylate, isocyanuric acid ethylene oxide (EO) modified acrylate, and pentane. An acrylate monomer such as erythritol acrylate, trimethylolpropane acrylate, ethylene glycol acrylate, polyester acrylate, norbornene acrylate can be used, and it is preferable to use a monomer having a bifunctional or higher acryloyl group as a main component. Since the overcoat layer 15 has a structure that is preferably provided in the manufacturing process as described later, it is not limited to the barrier layer on the side opposite to the color filter layer, and may be provided on the barrier layer on the color filter layer side. The overcoat layer may be provided only on the surfaces of both barrier layers. In addition, since an overcoat layer is arbitrary structures, it does not interfere even if it is unnecessary in a manufacturing process.

Moreover, as a thermosetting resin, an epoxy resin, a urethane resin, an unsaturated polyester resin, a melamine resin, etc. can be used.
Thus, by providing the overcoat layer, it is possible to reduce scratches on the barrier layer that may enter during handling.

  Moreover, the manufacturing method of the color filter for display apparatuses of this invention includes the 1st process of forming a barrier layer on both surfaces of a plastic film, respectively, and the 2nd process of forming a color filter layer.

  First, as a pretreatment, the plastic film is heat-treated. In this step, the heat treatment time of the plastic film is shorter when the temperature is higher by 30 ° C. or higher than when the temperature is higher by about 10 ° C. than the heating temperature when forming the color filter. This is preferable because of the effect of suppressing dimensional changes.

  Here, the heat treatment of the plastic film can be performed in a heating furnace such as a hot air oven, an infrared furnace, or a hot plate. Further, when this heat treatment is performed under conditions excluding oxygen, such as a vacuum atmosphere or a nitrogen substitution atmosphere, it is preferable because coloring of the plastic film due to air oxidation or the like and prevention of strength reduction can be prevented.

FIG. 4 is a diagram schematically illustrating a configuration of an example of the heat treatment apparatus.
In this heat treatment apparatus 40, a plastic film 48 (corresponding to the plastic film 12 in FIG. 2) unwound from a roll unwinding apparatus 42 in which a roll-shaped plastic film is set to be unwindable is heated with a heater 56. After being conveyed to the furnace 44 and heat-treated at a temperature equal to or higher than the predetermined temperature, it is wound up by a roll winding device 46.

  Here, in order to make the plastic film 48 stretch in the heating furnace 44, nip rolls 50 and 54 are provided at the unwinding port and the winding port, respectively, so that the tension of the plastic film 48 can be controlled. It has become. Further, a tension measuring roll 52 is also provided on the side of the unwinding port of the heating furnace 44, and the operation of the nip rolls 50 and 54 is controlled according to the result of the tension measurement, thereby enabling feedback control of the tension of the plastic film 48.

  Thus, when using a heat treatment apparatus equipped with a roll unwinding device, a heating furnace, and a roll winding device, the heat treatment can be performed continuously in a roll-to-roll manner, thereby increasing the production efficiency. Can do.

Subsequently, a barrier layer 14 is formed on the plastic film 12 (FIG. 5A) heat-treated at a predetermined temperature (FIG. 5B).
Such a barrier layer can be produced by a physical vapor deposition (PVD) method such as vapor deposition, ion plating, or sputtering, a chemical vapor deposition method such as plasma CVD (chemical vapor deposition), or a sol-gel method. It is preferable because a dense film, that is, a film having a good barrier property, particularly a gas barrier property is easily obtained.

  After providing a first barrier layer on one surface of the plastic film, an overcoat layer is provided on the surface of the first barrier layer, and then a second barrier layer is provided on the other surface of the plastic film. Is preferred. The overcoat layer may be provided on the surface of the second barrier layer.

  In addition, the overcoat layer is formed by performing coating, drying, and curing with a continuous coating apparatus including a roll unwinding device, a coater head, a drying furnace, a UV irradiation device, a roll winding device, and the like. Can be provided.

  Accordingly, an overcoat layer that reduces scratches on the barrier layer that may enter during handling can be provided, and the barrier layer and the overcoat layer can be formed on the opposite surface by forming the barrier layer and the overcoat layer in the above order. When the film is unwound in a vacuum when the barrier layer is formed, the barrier layer can be protected to prevent the formation of cracks.

  Further, after the first barrier layer is formed and before the overcoat layer is formed, the surface of the first barrier layer may be subjected to corona treatment. In this case, the adhesion between the barrier layer and the overcoat layer is improved. be able to.

  Either the single wafer or the roll-to-roll process can be applied to the film formation process of the first and second barrier layers. Since film formation is performed on a plastic film, roll-to-roll is preferable because productivity is improved.

  In addition to preventing moisture from entering the plastic film in the development process described below, the color filter made on a plastic substrate having a high barrier property with a water vapor permeability of 0.02 g / (m2 · day) or less. Further, it is possible to prevent air bubbles from being mixed into the liquid crystal layer of the liquid crystal display.

  Further, as described above, the thickness of the barrier layer is in the range of 30 nm to 200 nm, preferably 50 nm to 150 nm. Further, when the thickness of the barrier layer provided on one surface of the plastic film is r1, and the thickness of the barrier layer provided on the other is r2, r1 / r2 is 0.5 to 2.0, preferably 0. It may be in the range of 7 to 1.4.

  Subsequently, a color filter layer is formed on the surface of the plastic film on which the barrier layer is formed. In the following, an embodiment for forming a color pattern with a black matrix and RGB colorants in the step of forming a color filter layer will be described.

  An example in which an overcoat layer is also formed on the surface of the first barrier layer and a color filter layer is provided on the surface of the barrier layer where the overcoat layer is not formed is shown. A layer may be provided.

  In the present invention, the black matrix and the RGB colored pattern can be formed by photolithography. In this embodiment, it can be performed in a single sheet (cut sheet form) or in a roll-to-roll continuous process. In particular, when it is carried out in a roll-to-roll continuous process, productivity is high.

  Here, the black matrix and the colorant are either a photosensitive resin composition, a black matrix forming coating composition and a coloring pattern forming coating composition, which are directly applied onto a plastic film and patterned and heat cured, These coating compositions can be separately applied in advance on a base film and dried to form a dry film, which is laminated on a plastic film serving as a substrate, transferred, patterned, and thermally cured.

Here, as the photosensitive resin composition, a radiation sensitive composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Can be mentioned.
The colorant (A) is a material for color-displaying each colored pattern or shielding the black matrix pattern when the color filter is irradiated with transmitted light. Examples of the coloring material include a red organic pigment and a green organic material. Examples of pigments, blue organic pigments, and light-shielding materials include carbon black pigments.
The alkali-soluble resin (B) is a material that dissolves during development to remove the layer of the photosensitive resin composition, and examples thereof include a benzyl methacrylate / methacrylic acid copolymer.
The polyfunctional monomer (C) is a material for polymerizing a layer of the photosensitive resin composition at the time of exposure to form an insoluble pattern at the time of development. For example, dipentaerythritol hexa An acrylate is mentioned.
The photopolymerization initiator (D) is a material for polymerizing a polyfunctional monomer during exposure. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 Can be mentioned.
By using such a radiation sensitive composition, it is possible to form a high-resolution colored pattern and a black matrix pattern on a roll-to-roll, and to form a flexible pattern that follows the flexibility of the plastic film.

  Here, a mode in which a black matrix is laminated on a plastic film from a dry film will be described. The dry film for black matrix paint used here is a paint composition layer in which a black matrix-forming paint composition is applied on a base film 62 (FIG. 6A) in a wet state using a die coat and dried. After forming 64 (FIG. 6B), the cover film 66 can be laminated as shown in FIG. 6C.

  As a coating method of the coating composition, there are gravure coating, gravure reverse coating, slit reverse coating, micro gravure coating, comma coating, slide coating, spray coating, curtain coating and the like in addition to die coating.

  The thickness of the base film 62 is preferably 2.5 to 100 [mu] m, more preferably 6 [mu] m or more in order to improve the transportability of the film, and 50 [mu] m to increase the followability to the unevenness of the substrate to be transferred. The following is more preferable.

  The base film 62 is made of polyethylene terephthalate (PET), polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile, ethylene vinyl acetate copolymer (EVA), cellulose triacetate (TAC), polyethylene naphthalate, polycarbonate, Examples thereof include single films and multilayer films of synthetic resins such as polyphenylene sulfide, polyimide, polyvinyl chloride, polyethersulfone, polyamideimide, polyamide, and aromatic polyamide. Of these, polyethylene terephthalate is preferable because of its excellent transparency and smoothness.

  On the other hand, the thickness of the cover film 66 is preferably 2.5 to 100 μm, and more preferably 6 to 50 μm in consideration of the peelability from the base film 62. The cover film 66 is made of polyethylene terephthalate (PET), polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile, ethylene vinyl acetate copolymer (EVA), cellulose triacetate (TAC), polyethylene naphthalate, polycarbonate, polyphenylene. Examples thereof include synthetic resins such as sulfide, polyimide, polyvinyl chloride, polyethersulfone, polyamideimide, polyamide, and aromatic polyamide. Among them, polyethylene terephthalate is preferable because of its excellent transparency and smoothness.

  The cover film 66 is peeled in advance from the dry film thus obtained, and as shown in FIG. 7, the base film 62 is placed so that the coating composition layer 64 faces the barrier layer 14 on the plastic film 12 as the base material. Are laminated, and the layer of the photosensitive resin composition for forming the black matrix is subjected to heat and pressure treatment with a pressure and heating roller and continuously transferred to prepare a laminated original fabric 70.

  Here, for the heat and pressure treatment, a general pressure and heating roller can be used. Specifically, the film can be sandwiched between two upper and lower rolls, and the other roll is heated by one roll. It has a structure that receives pressure. A material whose surface is mainly covered with heat-resistant rubber is used for one roll, and a chromium roll-treated metal roll is used for the other. Thus, pressurization can be made uniform by using one as a rubber roll and the other as a metal roll.

  As a result of various experiments conducted by the inventors, it has been found that the upper roll is covered with heat-resistant rubber and is a heatable roll, and the lower roll is a metal roll, so that temperature control is performed more accurately and transfer quality is improved. I found it.

Further, the conditions of the pressure heat treatment are such that the roller pressure is 0.5 to 1 kg / cm ² , the heating temperature is 50 to 150 ° C., and the conveyance speed is 100 to 2000 mm / min, thereby improving the transfer quality. be able to. The reason for this is that if the roller pressure and heating temperature are low, the adhesion between the transfer layer and the substrate to be transferred becomes insufficient and defects in the transfer tend to occur, and conversely if it is high, the transfer layer, the non-transfer substrate and the base film For example, deformation or the like may occur due to the influence of heat pressure on the toner, resulting in a decrease in transfer quality. If the conveying speed is low, the throughput is lowered and the transfer quality is deteriorated due to heat pressure. If it is fast, the heat pressure is insufficient at the time of transfer, and the transfer is not performed accurately.

  Next, an exposure treatment is performed on the layer of the photosensitive resin composition, with the base film peeled off as necessary, on the heated and pressure-treated laminated original fabric.

  In addition, when the photosensitive resin composition, which is a black matrix forming coating composition, is applied directly on a plastic film, all of the above steps are omitted or a base film is laminated after application to create a laminated original fabric, You may perform an exposure process in the state which attached the base film on the layer of the photosensitive resin composition to this lamination | stacking original fabric.

  In the step of exposing to the photosensitive resin composition, an exposure unit having an exposure table for exposing light from a light source described later, and an unwinding device upstream to introduce the photosensitive resin composition into the exposure unit, The exposure apparatus having a winding device on the downstream side and further a pair of nip rolls on the inlet side and the outlet side is passed through the lamination raw material obtained above, and the continuous lamination raw material is driven by driving the nip roll pair. In the exposure section, the laminated original fabric is attracted and fixed on the exposure table, and the laminated original fabric is exposed by proxy exposure.

  It is preferable that the driving of the nip roller is stopped while the laminated raw material is adsorbed and fixed on the exposure table. In addition, with respect to the tension applied to the original fabric during conveyance, from the viewpoint that if the strength is weak, the meandering of the original fabric is likely to occur due to conveyance failure, and if the tension is strong, there is an influence of the elongation of the original fabric. The width is preferably 300 mm.

  In addition, the above-described raw material conveyance form is separate from the apparatus for performing the black matrix coating or the patterning process using the base film, the apparatus for performing the exposure / development process, and the baking apparatus described below. However, in the case of a continuous device configuration, the idea of winding in each device is not necessarily required.

  Here, the temperature of the exposure unit of the exposure apparatus is set to 20 ° C. ± 0.1 ° C. to 25 ° C. ± 0. It is preferable that the temperature is 1 ° C., while the humidity is 50% ± 1% to 65% ± 1%, considering the stability of each material and the hygroscopicity of the material at this temperature.

  Further, the interval (gap) between the base film of the laminated raw fabric or the photosensitive resin composition layer for forming the black matrix and the pattern (photomask) is automatically adjusted every time so as to be constantly constant. The gap amount in this case considers the resolution of the pattern to be formed. That is, if the gap amount is too large, the resolution decreases, and conversely, the resolution improves and adhesion of dust and dirt to the photomask increases. Therefore, 5 to 200 μm is preferable.

  In addition, the exposure position of the pattern of the laminated film is automatically detected from the distance from the end surface of the laminated film, and exposure is performed after automatic adjustment so that the photomask pattern position is a fixed distance from the laminated film according to the detection result. . At this time, it is preferable to create an alignment mark for aligning the exposure position when forming a color pattern for each color of RGB described later.

  Examples of the light source used in the exposure process include a high-pressure mercury lamp, a DEEP UV lamp, a metal halide lamp, a low-pressure mercury lamp, and a halogen lamp. When the above-described photosensitive resin composition for forming a black matrix is used. In particular, exposure using a wavelength of 350 to 450 nm is preferable from the viewpoint of sensitivity and resolution.

  Subsequently, development processing and post-baking processing are performed. The development process is performed by a developing device installed on the downstream side of the exposure machine. Specifically, the layered film after exposure is conveyed at a constant speed and the base film is peeled off while developing on the surface of the peeled plastic film. By discharging the liquid in a spray form at room temperature, a composite film in which a black matrix having a predetermined pattern is laminated on a plastic film can be obtained. In addition, when the exposure is performed with the base film attached, the developer is applied after the base film is peeled off and developed. Thereafter, the composite film is passed through a baking furnace while being conveyed at a constant speed in a continuous baking furnace, and subjected to baking treatment, whereby the resin pattern of the black matrix can be thermally cured. Here, the baking temperature is preferably 120 to 250 ° C., if the temperature is too low, thermal curing is insufficient, and if the temperature is high, the resin is yellowed.

  Here, the barrier layers provided on both surfaces of the plastic film can prevent impregnation of the developer into the plastic film when the plastic film is immersed in the developer after the exposure for forming the color pattern. It acts to suppress dimensional changes of the plastic film that may occur due to liquid impregnation. As a result, the dimensional accuracy of the plastic film is improved, and a highly detailed pattern can be formed. By using such a plastic film, the reliability of the color filter is improved.

FIG. 8A is a plan view of the plastic film on which the black matrix pattern obtained in this way is formed, and FIG. 8B is a cross-sectional view of the CC ′ plane in FIG. 8A. .
According to FIGS. 8A and 8B, the black matrix pattern 16 is formed on the barrier layer 14 of the plastic film 12 in a lattice shape.

  Subsequently, after forming a black matrix pattern, an RGB coloring pattern is formed. When the RGB coloring pattern is transferred using a dry film as described above, a dry film of a coloring material corresponding to each color of RGB can be formed in the same manner as in the case of the black matrix described above.

  For example, in order to pattern red (RED) in a black matrix, a plastic film having a black matrix formed thereon is prepared, and then a RED dry film having a cover film previously peeled off is applied to the coating composition layer on the plastic film side. Lamination is carried out so as to face each other, and a layer of a photosensitive resin composition for forming a colored pattern corresponding to RED is continuously transferred by a pressure heating roller to form a laminated original fabric. The transfer process of the colored pattern by the pressure heating roller can be performed by the same apparatus and conditions as the black matrix formation described above.

  Next, in the exposure process for the transferred RED coloring pattern, alignment is performed using an alignment mark patterned simultaneously with the black matrix. Thereafter, an exposure process, a development process, and a post-bake process are performed in the same manner as in the case of the black matrix, and a heat-cured colored pattern can be formed on the plastic film on which the black matrix is formed.

  In addition, it can carry out similarly to the case of black matrix formation also by apply | coating the photosensitive resin composition for colored pattern formation directly on the said plastic film with black matrix formation, and forming a colored pattern.

FIG. 9A is a plan view of the plastic film on which the black matrix pattern and the RED coloring pattern thus obtained are formed, and FIG. 9B is a DD ′ plane in FIG. 9A. FIG.
According to FIGS. 9A and 9B, red patterns 18 that are RED coloring patterns are formed at predetermined intervals in the square area surrounded by the black matrix pattern 16 formed in a lattice shape.

  Furthermore, GREEN and BLUE can be formed on the plastic film on which the black matrix and RED are formed by using these methods in the same manner or by arbitrarily combining them. A transparent overcoat layer may be provided on these layers. Furthermore, the order of forming the black matrix and the RGB colorant can be arbitrarily determined. Further, two or more layers may be continuously formed in a single roll-out-roll-to-roll process.

FIG. 10 is a cross-sectional view of the main part of the plastic film on which the black matrix pattern and the color patterns of each color of RGB thus obtained are formed.
According to FIG. 10, the red pattern 18, the green pattern 20, and the blue pattern 22 are periodically formed in each square area surrounded by the black matrix pattern 16 formed in a lattice shape.

  Further, a transparent conductive layer and a column spacer may be provided on the black matrix pattern and the RGB coloring pattern formed on the plastic film.

  The transparent conductive layer is formed by, for example, roll-to-roll sputtering or vapor deposition. Examples of the transparent electrode layer include a thin film formed of indium tin oxide (ITO), zinc oxide, tin oxide, indium zinc oxide (IZO), and the like, but the material is not limited thereto.

FIG. 11 is a cross-sectional view of the main part of the plastic film in which the transparent electrode layer 24 is formed on the black matrix pattern and the colored patterns of each color of RED thus obtained.
According to FIG. 11, the transparent electrode layer 24 is formed on the RGB colored pattern composed of the black matrix pattern 16, the red pattern 18, the green pattern 20, and the blue pattern 22.

  For example, the column spacer is formed by applying a column spacer material paint on a base film in a wet state using a die coater, drying, pre-baking after drying, and further using a dry film obtained by laminating a cover film. The transfer process, the exposure process, the development process and the post-bake process similar to those for the black matrix and the colorant are performed, and the black matrix and the color pattern (for example, RGB), and in some cases, the plastic film on which the transparent conductive layer is formed. Formed on the surface.

  Examples of the column spacer include a negative photosensitive resin such as an acrylic resin and a positive photosensitive resin such as a novolac resin.

  As the material of the base film, for example, PET can be used as described above. Examples of column spacer material paints include negative photosensitive resins such as acrylic resins, and positive photosensitive resins such as novolac resins. As the material of the cover film, for example, PET can be cited as described above. Moreover, as conditions of a prebaking process, 0.5 to 10 minutes are mentioned in the range of 50-120 degreeC.

  The color filter in which the column spacers are formed in this way is shown in FIGS. 1, 2A and 2B.

  As described above, according to this embodiment, a color filter can be accurately manufactured using a plastic film as a substrate. Thereby, a thin and light color display device using a plastic film as a substrate can be manufactured efficiently and inexpensively.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
(Formation of plastic film)
After impregnating glass fiber with polyfunctional acrylate resin, it is continuously cured with an ultraviolet curing device to obtain a plastic film (1) having a resin weight of 60%, glass fiber of 40%, width of 30 cm, length of 100 m, and thickness of 100 μm. It was. The linear expansion coefficient of this plastic film (1) at 30 ° C. to 150 ° C. was 18 ppm. The glass transition temperature of this plastic film (1) was 300 ° C. or higher when evaluated by tan δmax. The total light transmittance of this plastic film (1) was 90%.

(Formation of the first barrier layer)
This plastic film (1) is loaded into a sputter roll coater, and a film thickness of 60 nm is formed on the plastic film (1) using Si as a target by reactive sputtering using oxygen as a reactive gas by DC magnetron sputtering. SiOx (x = 1.8, by XPS) was formed, and this was used as the first barrier layer.

(Formation of overcoat layer)
In a continuous coating machine provided with a roll unwinding device, a micro gravure coater, a drying furnace, a UV irradiation device, and a roll winding device on the first barrier layer formed above, 100 parts by weight of an epoxy acrylate prepolymer, 200 diethylene glycol 200 A homogeneous mixed solution of parts by weight, 100 parts by weight of ethyl acetate, 2 parts by weight of benzene ethyl ether, and 1 part by weight of a silane coupling agent was applied with a micro gravure coater of a continuous coating machine and passed through a drying zone at 120 ° C. Thereafter, ultraviolet rays were irradiated to form an overcoat layer having a thickness of 5 μm.

(Formation of second barrier layer)
The plastic film (1) on which the overcoat layer is formed is rewound with a rewinder, and then loaded into a sputter roll coater to form a second barrier layer on the opposite side of the overcoat layer, and DC magnetron Using sputtering, reactive sputtering using oxygen as a reactive gas was performed to form SiOx (x = 1.8, using XPS) with a thickness of 60 nm on the opposite side of the first barrier layer using Si as a target. This was used as the second barrier layer.

When the water vapor permeability at 40 ° C. and 90% RH was measured for the plastic film (1) formed up to the second barrier layer as described above based on the measurement method defined in JIS K 7129B, 0.01 g / (m ² · 24 hr) or less.

(Formation of black matrix)
On the second barrier layer of the plastic film on which the first and second barrier layers are formed, a black matrix forming coating composition having the following composition is placed in a wet state with a die coater so as to have a thickness of 10 μm. After coating and drying, prebaking was performed for 2 minutes at a temperature of 90 ° C. to obtain a raw material with a coating film of a coating composition for forming a black matrix having a thickness of 2 μm.

(Black matrix forming coating composition)
Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27) 150 parts Dipentaerythritol hexaacrylate 80 parts Carbon black dispersion 150 parts Photopolymerization initiator (2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butanone-1) 2.5 parts propylene glycol monomethyl ether acetate 600 parts * All parts are based on mass

(Exposure process)
Pass the raw material with the coating film obtained above through the exposure device equipped with the unwinding device on the upstream side and the winding device on the downstream side, and drive the nip roller pair installed on the inlet side and outlet side of the exposure device. Then, a continuous raw material was conveyed. In this conveying state, the tension applied to the original fabric was 2 kg / 300 mm width.
The temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ± 0.1 ° C., and the relative humidity was adjusted to 60% ± 1%.

After the original film with the coating film was adsorbed and fixed on the exposure table, the gap (gap) between the original film surface and the pattern (photomask) was automatically adjusted to 100 μm. Further, the exposure position of the original fabric was automatically detected by detecting the distance from the end face of the original fabric, and the exposure was performed after automatic adjustment so that the photomask pattern position was a fixed distance from the original fabric. As a light source, a high-pressure mercury lamp was used, the exposure area was 200 mm × 200 mm, I-line (wavelength: 365 nm) was used, and exposure was performed at an illuminance of 15 mW / cm ² for 20 seconds to obtain an exposure amount of 300 mJ / cm ² . .

(Development and post-baking process)
The development processing was performed by installing a developing device downstream of the exposure machine. The original film after the exposure process was conveyed at a constant speed of 400 mm / min to obtain a composite film in which a black matrix having a predetermined pattern was laminated on a plastic film on which a second barrier layer was formed.

  The alignment mark formed of black matrix is measured with a dimension measuring machine (NEXIV VMR-6555 manufactured by Nikon) at a temperature of 23 ° C. ± 0.1 ° C. and a relative humidity of 60% ± 1%. As a result of measuring the dimensional change in the direction perpendicular to (TD), the dimension of the pattern actually formed on the plastic film with respect to the photomask dimension value MD: 100.000 mm and TD: 100.000 mm is: MD: 99.998 mm, TD: 100.001 mm.

Thereafter, post baking was performed at 200 ° C. for 30 minutes in a baking furnace, and the black matrix resin pattern was thermally cured.
When the obtained black matrix was measured under the same conditions (temperature; 23 ° C. ± 0.1 ° C., relative humidity; 60% ± 1%), the dimension of the pattern formed on the plastic film was MD: 99 998 mm, TD: 100.001 mm.

(Formation of RGB coloring pattern)
On the composite film on which the black matrix pattern is formed, a coating composition for forming a colored pattern having the following composition is applied using a die coater so that the thickness is 10 μm in a wet state, and after drying, the temperature is 90. Prebaking was performed for 2 minutes under the condition of ° C. to obtain a 2 μm-thick original film with a coating.

  The composition of the RED composition, which is a red coating composition, is shown below. When the red pigment is an arbitrary green pigment, a GREEN composition is obtained, and when a red pigment is used, a BLUE composition is obtained.

(Coloring pattern forming coating composition)
Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27) 50 parts Trimethylolpropane triacrylate 40 parts Red pigment (CIPigment Red 177) 90 parts Photopolymerization initiator (2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropanone-1) 1.5 parts, propylene glycol monomethyl ether acetate 600 parts * All parts are based on mass

(Exposure process)
Through the unwinding device on the upstream side and the exposure device provided with the winding device on the downstream side, the laminated raw material obtained above is passed, and the nip roller pair installed on the entrance side and the exit side of the exposure device is driven, A continuous laminated raw material was conveyed. In this conveying state, the tension applied to the laminated original fabric was 2 kg / 300 mm width.
The temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ± 0.1 ° C., and the relative humidity was adjusted to 60% ± 1%.

After the laminated original fabric was adsorbed and fixed on the exposure table, the gap (gap) between the surface of the original coating film and the pattern (photomask) was automatically adjusted to 100 μm. The exposure position of the stack is automatically detected to detect the distance from the end surface of the stack, and the photomask pattern position is automatically adjusted from the stack to a fixed distance, and then the alignment formed simultaneously with the black matrix formation. After performing alignment with the RED photomask using the mark, exposure was performed. As a light source, a high-pressure mercury lamp was used, the exposure area was 200 mm × 200 mm, I-line (wavelength: 365 nm) was used, and exposure was performed at an illuminance of 15 mW / cm ² for 20 seconds to obtain an exposure amount of 100 mJ / cm ² . .

(Development and post-baking process)
Development was performed by installing a developing device downstream of the exposure machine. The original film after the exposure process was conveyed at a constant speed of 400 mm / min to obtain a composite film in which the RED pattern was laminated at a predetermined position of the opening of the black matrix pattern on the composite film. Thereafter, post-baking was performed at 200 ° C. for 30 minutes in a baking furnace to thermally cure the RED resin pattern.

  GREEN and BLUE patterns were repeatedly formed in the same manner as in the above RED, and a color filter in which a black matrix and RGB colored patterns were formed on a plastic film on which a second barrier layer was formed was obtained.

  When the black matrix was measured under the same conditions as described above (temperature; 23 ° C. ± 0.1 ° C., relative humidity; 60% ± 1%) after the post-baking treatment of the BLUE pattern, it was formed on the plastic film. The dimension of the pattern was MD: 99.999 mm, TD: 100.002 mm.

  The dimensional change of the black matrix pattern is 10 ppm in the manufacturing process from the development of the first layer (black matrix layer) to the post-baking of the fourth layer (BLUE layer). Was 200 ppi (BM line width 7 μm, pitch 42 μm), and a color filter was formed without causing pixel shift.

(Dimensional change when immersed in water: black matrix (BM) + RGB pattern color filter (CF))
The obtained color filter was formed with a black matrix in the MD and TD directions under the conditions of temperature; 23 ° C. ± 0.1 ° C., relative humidity; 60% ± 1% using a dimension measuring machine (NEXIVVMR-6555 manufactured by Nikon). As a result of measuring the alignment mark, the pattern dimensions actually formed on the plastic film were MD: 99.999 mm, TD: 100, with respect to the photomask dimension values MD: 100.000 mm and TD: 100.000 mm. 0.002 mm.

  Thereafter, it was immersed in pure water at 23 ° C. for 30 minutes, and after lifting, water was removed by air blow. When the dimension of the alignment mark formed of the black matrix of this color filter was measured under the same conditions, the pattern dimensions were MD: 100.002 mm and TD: 100.005 mm.

  As a result, the dimensional change when immersed in water at 23 ° C. for 30 minutes was 30 ppm because the extension was about 3 μm per 100 mm.

(Formation of ITO electrode layer)
Next, this color filter is loaded into a sputter roll coater, and a black matrix and RGB colored patterns are formed by reactive sputtering using oxygen as a reaction gas by DC sputtering and using ITO (indium tin oxide) as a target. An ITO film having a thickness of 150 nm was formed on the color filter, and this was used as a transparent conductive film.

(Formation of column spacer)
(Preparation of dry film)
As a dry film for column spacer (CS) coating material, a die coater is used so that a CS material coating composition made of a negative photosensitive resin is deposited on a PET base film having a thickness of 25 μm and a thickness of 20 μm in a wet state. After coating and drying, prebaking was performed at a temperature of 90 ° C. for 2 minutes to obtain a thickness of 5 μm, and a PET cover film having a thickness of 25 μm was laminated thereon.

(Creation of laminated raw material)
On the composite film on which the black matrix and RGB coloring patterns obtained above and the ITO electrode layer were formed, a CS dry film from which the cover film had been peeled in advance was laminated so that the coating composition layer faced the plastic film side. The coating composition layer made of the photosensitive resin composition for forming the CS pattern is continuously transferred under the conditions of roller pressure: 5 kg / cm ² , roller surface temperature: 120 ° C., and speed: 800 mm / min. Then, a laminated raw material was created. At this time, the base film was not peeled off, and the process proceeded to the next exposure step with the base film attached on the layer of the photosensitive resin composition.
(Exposure process)
Through the unwinding device on the upstream side and the exposure device provided with the winding device on the downstream side, the laminated raw material obtained above is passed, and the nip roller pair installed on the entrance side and the exit side of the exposure device is driven, A continuous laminated raw material was conveyed. In this conveying state, the tension applied to the laminated original fabric was 2 kg / 300 mm width.
The temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ± 0.1 ° C., and the relative humidity was adjusted to 60% ± 1%.

After the laminated original fabric was adsorbed and fixed on the exposure table, the gap (gap) between the base film of the laminated original fabric and the pattern (photomask) was automatically adjusted to be 30 μm. In addition, the exposure position of the pattern of the laminated original fabric is automatically detected by detecting the distance from the end surface of the laminated original fabric, and automatically adjusting the position of the photomask pattern from the laminated original fabric to a certain distance according to the detection result. After alignment with the CS photomask using the alignment marks formed simultaneously with the matrix formation, exposure was performed. As a light source, a high-pressure mercury lamp was used, the exposure area was 200 mm × 200 mm, I-line (wavelength: 365 nm) was used, and exposure was performed at an illuminance of 15 mW / cm ² for 20 seconds to obtain an exposure amount of 300 mJ / cm ² . .

(Development and post-baking process)
The development process is performed by installing a developing device on the downstream side of the exposure machine, peeling the base film of the laminated raw material after exposure in the developing device, and transporting it at a constant speed of 400 mm / min. A composite film in which a CS pattern was formed at a predetermined position of the lattice pattern portion of the black matrix pattern on the composite film on which the matrix pattern and the RGB coloring pattern and the ITO electrode layer were formed was obtained. Thereafter, post-baking treatment was performed at 200 ° C. for 30 minutes in a baking furnace to heat cure the CS resin pattern.

  In this way, the black matrix and RGB coloring patterns were formed on the plastic film (1) on which the gas barrier layer was formed, and the ITO electrode layer and CS were formed on the pixel portion comprising the black matrix and RGB coloring patterns. A color filter member was obtained.

(Dimensional change when immersed in water: CF member of BM + RGB + ITO + column spacer (CS) pattern)
The obtained color filter member on which the ITO electrode layer and the CS pattern were formed was measured under the conditions of temperature: 23 ° C. ± 0.1 ° C., relative humidity; As a result of measuring the alignment mark formed of the black matrix in the MD and TD directions, the pattern dimensions actually formed on the plastic film with respect to the photomask dimension values MD: 100.000 mm and TD: 100.000 mm Were MD: 99.999 mm and TD: 100.002 mm.

  Thereafter, it was immersed in pure water at 23 ° C. for 30 minutes, and after lifting, water was removed by air blow. When the dimension of the alignment mark formed with the black matrix of this color filter was measured under the same conditions, the pattern dimensions were MD: 100.001 mm and TD: 100.004 mm.

  As a result, the dimensional change when immersed in water at 23 ° C. for 30 minutes was 20 ppm because the extension was about 2 μm per 100 mm.

(Example 2)
In Example 2, a barrier layer was provided on each side of the plastic film without forming an overcoat layer.

(Formation of plastic film)
After impregnating glass fiber with polyfunctional acrylate resin, it is continuously cured with an ultraviolet curing device to obtain a plastic film (1) having a resin weight of 60%, glass fiber of 40%, width of 30 cm, length of 100 m, and thickness of 100 μm. It was. The linear expansion coefficient of this plastic film (1) at 30 ° C. to 150 ° C. was 18 ppm. The glass transition temperature of this plastic film (1) was 300 ° C. or higher when evaluated by tan δmax. The total light transmittance of this plastic film (1) was 90%.

(Formation of the first barrier layer)
Next, this plastic film (1) is loaded into a sputter roll coater, and is formed on the plastic film (1) by DC magnetron sputtering using Si as a target by reactive sputtering using oxygen as a reactive gas. A film of SiOx (x = 1.8, by XPS) having a thickness of 60 nm was formed, and this was used as the first barrier layer.

(Formation of second barrier layer)
The plastic film (1) on which the first barrier layer is formed is rewound with a rewinder, and then loaded into a sputter roll coater to form a second barrier layer on the opposite side of the first barrier layer. Then, by DC magnetron sputtering, Si is used as a target by reactive sputtering using oxygen as a reactive gas, and SiOx (x = 1.8, XPS) having a thickness of 60 nm is opposed to the first barrier layer. Film formation was performed and this was used as the second barrier layer.

When the water vapor permeability at 40 ° C. and 90% RH was measured for the plastic film (1) formed up to the second barrier layer as described above based on the measurement method defined in JIS K 7129B, 0.01 g / (m ² · 24 hr).

Subsequently, the color filter was formed by the procedure described in Example 1, and the dimensional change of the black matrix was measured.
First layer (after development processing in black matrix formation) measurement results:
MD: 99.996mm, TD: 100.001mm
4th layer (after baking process in BLUE coloring pattern formation) measurement result (however, baking process heating condition: 200 ° C., 30 minutes):
MD: 100.000 mm, TD: 100.06 mm

  The dimensional change of the black matrix pattern is 50 ppm in the manufacturing process from the development of the first layer (black matrix layer) to the post-baking of the fourth layer (BLUE layer). At a resolution of 100 ppi (BM line width 20 μm, pitch 84 μm), a color filter was formed without causing pixel shift.

(Comparative Example 1)
In Comparative Example 1, the barrier layer was provided only on one side of the plastic film, and no overcoat layer was provided.

(Formation of plastic film)
After impregnating glass fiber with polyfunctional acrylate resin, it is continuously cured with an ultraviolet curing device to obtain a plastic film (1) having a resin weight of 60%, glass fiber of 40%, width of 30 cm, length of 100 m, and thickness of 100 μm. It was. The linear expansion coefficient of this plastic film (1) at 30 ° C. to 150 ° C. was 18 ppm. The glass transition temperature of this plastic film (1) was 300 ° C. or higher when evaluated by tan δmax. The total light transmittance of this plastic film (1) was 90%.

(Formation of barrier layer)
Next, this plastic film (1) is loaded into a sputter roll coater, and is formed on the plastic film (1) by DC magnetron sputtering using Si as a target by reactive sputtering using oxygen as a reactive gas. A film of SiOx (x = 1.8, by XPS) having a thickness of 60 nm was formed as a barrier layer.

When the water vapor transmission rate at 40 ° C. and 90% RH was measured for the plastic film (1) formed up to the barrier layer as described above based on the measurement method defined in JIS K 7129B, 0.05 g / (m ² · 24 hr )Met.

Subsequently, the color filter was formed by the procedure described in Example 1, and the dimensional change of the black matrix was measured.
First layer (after development processing in black matrix formation) measurement results:
MD: 99.995 mm, TD: 100.005 mm
4th layer (after baking process in BLUE coloring pattern formation) measurement result (however, baking process heating condition: 200 ° C., 30 minutes):
MD: 100.020 mm, TD: 100.030 mm

  The dimensional change of the black matrix pattern is 250 ppm in the manufacturing process from the development of the first layer (black matrix layer) to the post-baking of the fourth layer (BLUE layer), so that the resolution is 4 inches on the plastic film. The color filter formed with 100 ppi (BM line width 20 μm, pitch 84 μm) is misaligned with the black matrix pattern, creating a gap in the opening of the black matrix, and is effective as a color filter Could not be used.

(Dimensional change when immersed in water: BM + RGB pattern CF)
The obtained color filter was formed with a black matrix in the MD and TD directions under the conditions of temperature; 23 ° C. ± 0.1 ° C., relative humidity; 60% ± 1% using a dimension measuring machine (NEXIVVMR-6555 manufactured by Nikon). As a result of measuring the alignment marks, the pattern dimensions actually formed on the plastic film were MD: 100.020 mm, TD: 100, with respect to the photomask dimension values MD: 100.000 mm and TD: 100.000 mm. 0.03 mm.

  Thereafter, it was immersed in pure water at 23 ° C. for 30 minutes, and after lifting, water was removed by air blow. When the dimension of the alignment mark formed with the black matrix of this color filter was measured under the same conditions, the pattern dimensions were MD: 100.040 mm and TD: 100.050 mm.

  As a result, the dimensional change when immersed in water at 23 ° C. for 30 minutes was 200 ppm because the extension was about 20 μm per 100 mm.

(Formation of ITO and column spacers)
In the same procedure as in Example 1, an ITO electrode layer and a column spacer were formed on a color filter on which BM and RGB patterns were formed.

(Dimensional change when immersed in water: BM + RGB + ITO + CS pattern CF member)
The obtained color filter member on which the ITO electrode layer and the CS pattern were formed was subjected to a temperature measurement device (NEXIVVMR-6555 manufactured by Nikon) under conditions of temperature; 23 ° C. ± 0.1 ° C., relative humidity; 60% ± 1% As a result of measuring the alignment mark formed of the black matrix in the MD and TD directions, the pattern dimensions actually formed on the plastic film with respect to the photomask dimension values MD: 100.000 mm and TD: 100.000 mm Were MD: 100.020 mm and TD: 100.030 mm.

  Thereafter, it was immersed in pure water at 23 ° C. for 30 minutes, and after lifting, water was removed by air blow. When the dimension of the alignment mark formed with the black matrix of this color filter was measured under the same conditions, the pattern dimensions were MD: 100.040 mm and TD: 100.050 mm.

  As a result, the dimensional change when immersed in water at 23 ° C. for 30 minutes was 200 ppm because the extension was about 20 μm per 100 mm.

(Comparative Example 2)
(Formation of plastic film)
Using a coating machine having a coater head, a drying furnace, and an ultraviolet irradiation device on both sides of a plastic film made of polyethersulfone having a thickness of 100 μm, a liquid composed of a polyfunctional acrylate resin, a photoinitiator, and a solvent is applied. The solvent was dried and then cured by irradiating with ultraviolet rays to form an undercoat layer having a thickness of 5 μm. This was designated as a plastic film (2). The linear expansion coefficient of this plastic film (2) at 30 ° C. to 150 ° C. was 55 ppm. The glass transition temperature of this plastic film (2) was 224 ° C. as evaluated by tan δmax. The total light transmittance of this plastic film (2) was 90%.

(Formation of the first barrier layer)
Next, this plastic film (2) is loaded into a sputter roll coater, and DC magnetron sputtering is performed on the plastic film (2) using Si as a target by reactive sputtering using oxygen as a reactive gas. A film of SiOx (x = 1.8, by XPS) having a thickness of 60 nm was formed, and this was used as the first barrier layer.

(Formation of overcoat layer)
In a continuous coating machine provided with a roll unwinding device, a micro gravure coater, a drying furnace, a UV irradiation device, and a roll winding device on the first barrier layer formed above, 100 parts by weight of an epoxy acrylate prepolymer, 200 diethylene glycol 200 A homogeneous mixed solution of parts by weight, 100 parts by weight of ethyl acetate, 2 parts by weight of benzene ethyl ether, and 1 part by weight of a silane coupling agent was applied with a micro gravure coater of a continuous coating machine and passed through a drying zone at 120 ° C. Thereafter, ultraviolet rays were irradiated to form an overcoat layer having a thickness of 5 μm.

(Formation of second barrier layer)
The plastic film (2) on which the overcoat layer is formed is rewound with a rewinder, and then loaded into a sputter roll coater to form a second barrier layer on the surface opposite to the overcoat layer, and DC magnetron Using sputtering, reactive sputtering using oxygen as a reactive gas was performed to form SiOx (x = 1.8, using XPS) with a thickness of 60 nm on the opposite side of the first barrier layer using Si as a target. This was used as the second barrier layer.

When the water vapor transmission rate at 40 ° C. and 90% RH was measured for the plastic film (2) formed up to the second barrier layer as described above based on the measurement method defined in JIS K 7129B, 0.01 g / (m ² · 24 hr) or less.

Subsequently, the color filter was formed by the procedure described in Example 1, and the dimensional change of the black matrix was measured. In addition, only the post-baking conditions in each process were implemented at 180 degreeC and 30 minutes.
First layer (after development processing in black matrix formation) Measurement results MD: 99.950 mm, TD: 100.015 mm
4th layer (after baking treatment in BLUE coloring pattern formation) measurement results
(However, baking treatment heating conditions: 200 ° C., 30 minutes):
MD: 99.930 mm, TD: 100.060 mm
(MD: -200 ppm, TD: +450 ppm)

  In the manufacturing process from the development of the first layer (black matrix layer) to the post-baking of the fourth layer (BLUE layer), the dimensional change of the black matrix pattern is 200 ppm in the MD direction and 450 ppm in the TD direction. A color filter formed on a plastic film with a 4-inch size and a resolution of 100 ppi (BM line width 20 μm, pitch 84 μm) causes a color pattern misregistration with respect to the black matrix pattern, resulting in a gap in the opening of the black matrix. As a result, the color filter could not be used.

It is an enlarged plan view of the principal part of the color filter for display apparatuses which concerns on embodiment of this invention. 2A is a cross-sectional view taken along the plane AA ′ in FIG. 1, and FIG. 2B is a cross-sectional view taken along the line BB ′ in FIG. It is a figure which shows 1 pitch's worth of the coloring pattern in this embodiment. It is a figure which shows typically the structure of an example of the heat processing apparatus used by this embodiment. It is process sectional drawing which shows the manufacturing process of this embodiment. It is process sectional drawing which shows the manufacturing process of this embodiment. It is process sectional drawing which shows the manufacturing process of this embodiment. FIG. 8A is a plan view of a plastic film on which the black matrix pattern obtained in this embodiment is formed, and FIG. 8B is a cross-sectional view of the CC ′ plane in FIG. 8A. . FIG. 9A is a plan view of a plastic film on which the black matrix pattern and the RED coloring pattern obtained in this embodiment are formed, and FIG. 9B is a DD ′ plane in FIG. 9A. FIG. It is process sectional drawing which shows the manufacturing process of this embodiment. It is process sectional drawing which shows the manufacturing process of this embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Color filter 12 Plastic film 14 Barrier layer 15 Overcoat layer 16 Black matrix pattern 18 Red pattern 20 Green pattern 22 Blue pattern 24 Transparent electrode layer 26 Column spacer 62 Base film 64 Coating composition layer 66 Cover film

Claims (26)

In a color filter for a display device having a color filter layer formed by heat treatment on a plastic film,
A color filter for a display device, comprising a barrier layer on each side of the plastic film, wherein the thickness of each barrier layer is in the range of 30 nm to 200 nm. The color filter for a display device according to claim 1,
A color filter for a display device, wherein a dimensional change when immersed in water at 23 ° C. for 30 minutes is 50 ppm or less in an arbitrary direction. The color filter for a display device according to claim 1,
A color filter for a display device, characterized in that a water vapor permeability of a plastic film having both sides of the barrier layer is 0.02 g / (m ² · 24 hr) (according to a measuring method according to JIS K 7129B) or less. . The color filter for a display device according to claim 1,
A color filter for a display device, wherein an overcoat layer is provided on the surface of at least one of the barrier layers. In the color filter for display devices according to claim 4,
The color filter for a display device, wherein the overcoat layer is provided after corona treatment of the surface of the barrier layer. The color filter for a display device according to claim 1,
A color filter for a display device, wherein r1 / r2 is in the range of 0.5 to 2.0, where r1 and r2 are the thicknesses of the respective barrier layers. In the color filter for display devices according to claim 4,
The color filter for a display device, wherein the color filter layer is formed on a surface of either the barrier layer or the overcoat layer. The color filter for a display device according to claim 1,
The color filter for a display device, wherein the barrier layer is formed by a sputtering method. The color filter for a display device according to claim 1,
A color filter for a display device, wherein the plastic film has a linear expansion coefficient at 30 ° C. to 150 ° C. of 0 ppm / ° C. to 40 ppm / ° C. The color filter for a display device according to claim 1,
A color filter for a display device, wherein the plastic film has a glass transition temperature of 200 ° C. or higher. The color filter for a display device according to claim 1,
A color filter for a display device, wherein the plastic film has a total light transmittance of 80% or more. The color filter for a display device according to claim 1,
The color filter for a display device, wherein the barrier layer is an inorganic thin film. In the color filter for display devices according to claim 4,
The color filter for a display device, wherein the overcoat layer is a photocurable resin or a thermosetting resin.   A color filter member including the color filter for a display device according to any one of claims 1 to 13, wherein a transparent conductive film and a column spacer are provided on the surface of the color filter layer continuously imposed on the plastic film, or A color filter member comprising a transparent electrode, a protective film, and a column spacer. The color filter member according to claim 14,
A color filter member characterized in that a dimensional change when immersed in water at 23 ° C. for 30 minutes is 50 ppm or less in an arbitrary direction. In the method for manufacturing a color filter for a display device having a color filter layer formed by heat treatment on a plastic film,
A first step of forming barrier layers on both sides of the plastic film so that the thickness of each barrier layer is in a range of 30 nm to 200 nm;
And a second step of forming the color filter layer. A method for manufacturing a color filter for a display device. In the manufacturing method of the color filter for display devices according to claim 16,
In the first step, the barrier layer is formed by a sputtering method. A method for manufacturing a color filter for a display device. In the manufacturing method of the color filter for display apparatuses of Claim 17,
In the first step,
Forming a first barrier layer on one side of the plastic film in a sputtering apparatus;
Forming an overcoat layer on the surface of the first barrier layer;
A method for producing a color filter for a display device, comprising: forming a second barrier layer on the surface opposite to the surface on which the overcoat layer and the first barrier layer of the plastic film are formed by the sputtering apparatus. In the manufacturing method of the color filter for display devices of Claim 18,
In the first step, the surface of the first barrier layer is subjected to corona treatment after the first barrier layer is formed and before the overcoat layer is formed. In the manufacturing method of the color filter for display devices according to claim 16,
In the first step, when the thickness of each of the barrier layers is r1 and r2, the display device is formed so that r1 / r2 is in a range of 0.5 to 2.0. For producing color filters for use in a car In the manufacturing method of the color filter for display devices according to claim 16,
In the first step,
The barrier layer is continuously formed by roll-to-roll using a roll film forming apparatus including at least a roll unwinding device, a film forming device, and a roll winding device on both surfaces of a plastic film made into a long roll. A method for producing a color filter for a display device. In the manufacturing method of the color filter for display devices according to claim 16,
In the second step,
Using a transfer material in which a layer of colored ionizing radiation curable resin is formed on a transfer base plastic, the colored ionizing radiation curable resin layer of the transfer material is placed on the plastic film with the layer facing the plastic film. A process of heat-pressing the transfer material;
After exposure to the colored ionizing radiation curable resin layer left after peeling the transfer base plastic from the pressure-transferred transfer material through a photomask, or after exposure to the colored ionizing radiation curable resin layer And a continuous process of developing and forming a colored pattern after peeling off the transfer base plastic,
The color filter layer is formed by a roll-to-roll process by repeating each of the above steps for each hue using a transfer material on which a colored ionizing radiation curable resin layer having a different hue is formed. A method for producing a color filter for a display device. In the manufacturing method of the color filter for display devices according to claim 16,
In the second step,
A step of laminating a protective film after directly forming a colored ionizing radiation curable resin layer on the plastic film;
After exposure to the colored ionizing radiation curable resin layer remaining after peeling off the protective film through a photomask, or after exposure to the colored ionizing radiation curable resin layer, development is performed. And a continuous process of forming a colored pattern,
A method for producing a color filter for a display device, wherein the color filter layer is formed by a roll-to-roll process by repeating the steps described above for layers of colored ionizing radiation curable resins having different hues. In the manufacturing method of the color filter for display devices according to claim 16,
In the second step,
A layer of colored ionizing radiation curable resin is directly applied and formed on the plastic film, and the colored ionizing radiation curable resin layer is exposed through a photomask and developed to form a colored pattern. A color filter for a display device, wherein the color filter layer is formed by a roll-to-roll process by repeating the continuous steps for a layer of colored ionizing radiation curable resin having different hues. Manufacturing method. In the manufacturing method of the color filter for display devices according to claim 16,
In the second step,
According to the kind of colored ionizing radiation curable resin, each colored ionizing radiation curable resin layer is formed on the plastic film by arbitrarily combining the production methods according to claims 22 to 24, and the color filter layer A method for producing a color filter for a display device. In the manufacturing method of the color filter for display apparatuses in any one of Claims 22-25,
The colored ionizing radiation curable resin is a radiation-sensitive composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A method for producing a color filter for a display device.

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