JP2012132979A - Method for manufacturing color filter, color filter, image display device, and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter, by which a color filter having excellent brightness and a contrast ratio and suppressing occurrence of color irregularity and density irregularity can be manufactured.SOLUTION: The method for manufacturing a color filter comprises discharging ink by an inkjet system onto a substrate where a large number of cells are formed, and the method includes: a first ink imparting step of discharging a first ink into the cells; a step of removing a first liquid medium from the first ink discharged into the cells to form a colored film; a step of cooling the substrate in an environment at a relative humidity of 10% or lower and an ambient temperature of 15°C or higher and 35°C or lower; a step of discharging a second ink containing a curable resin material into the cells where the first ink is discharged; and a step of removing a second liquid medium from the second ink discharged into the cells to form a resin film. The curable resin material contains a polymer X and a polymer Y.

Description

  The present invention relates to a color filter manufacturing method, a color filter, an image display device, and an electronic apparatus.

A color filter is generally used for a liquid crystal display (LCD) or the like that performs color display.
In color filters, pigments are widely used as colorants from the viewpoint of light resistance and the like.
A color filter has conventionally formed a coating film composed of a material (colored portion forming composition) containing a colorant, a photosensitive resin, a functional monomer, a polymerization initiator, etc. on a substrate, and then a photomask. It has been manufactured by using a so-called photolithography method in which a photosensitive process, a developing process, and the like are performed. In such a method, the colors are usually overlapped by repeating the operation of forming a coating film corresponding to each color on almost the entire surface of the substrate, curing only a part thereof, and removing most of the other part. Manufacture color filters so that they do not match. For this reason, the coating film formed in the production of the color filter has only a part remaining as a colored part in the finally obtained color filter, and most of it is removed in the production process. Become. For this reason, not only the manufacturing cost of a color filter rises but it is not preferable also from a viewpoint of resource saving.

On the other hand, in recent years, a method for forming a colored portion of a color filter using an inkjet head (droplet discharge head) has been proposed (see, for example, Patent Document 1). Such a method can reduce the waste of the colored portion forming composition, thereby reducing the burden on the environment and reducing the manufacturing cost.
By the way, as described above, the color filter manufacturing method using the ink jet method is excellent in productivity. However, with a color filter manufactured using an inkjet head, it is difficult to display an image with higher contrast and higher brightness, and streaky irregularities (color irregularities and density irregularities) are likely to occur in the displayed image. There was a problem.

JP 2004-2815 A

  An object of the present invention is to provide a color filter that is manufactured using an inkjet method, has excellent brightness and contrast ratio, and suppresses occurrence of uneven color and uneven density, and efficiently manufactures the color filter. Another object of the present invention is to provide a method for manufacturing a color filter, and to provide an image display device and an electronic apparatus provided with the color filter.

これにより、明度およびコントラスト比に優れ、かつ、色むら、濃度むらの発生が抑制されたカラーフィルターを効率よく製造することができるカラーフィルターの製造方法を提供することができる。
また、製造されるカラーフィルターの耐久性を優れたものとすることができる。
また、着色膜とは別に、樹脂膜を形成することにより、製造されるカラーフィルターの耐溶剤性、当該カラーフィルターを備えた液晶表示装置の液晶層の電圧保持率等を特に優れたものとすることができる。
また、形成すべき着色部の構成材料を２種のインクに分けて含有させることにより、インクの吐出安定性を向上させることができ、インクジェット法による高速描画が可能となるため、全体としての、カラーフィルターの生産性を特に優れたものとすることができる。 Such an object is achieved by the present invention described below.
The method for producing a color filter of the present invention is a method for producing a color filter by discharging ink by an inkjet method onto a substrate provided with a large number of cells,
A first ink application step of discharging a first ink containing a colorant and a first liquid medium in which the colorant is dispersed and / or dissolved into the cell;
A first liquid medium removing step of removing the first liquid medium from the first ink ejected into the cell and forming a colored film;
A cooling step of cooling the substrate on which the colored film is formed in an environment of a relative humidity of 10% or less and an ambient temperature of 15 ° C. or more and 35 ° C. or less;
A second ink that discharges a second ink containing a curable resin material and a second liquid medium that disperses and / or dissolves the curable resin material into the cell in which the first ink has been discharged. An ink application process,
A second liquid medium removing step of removing the second liquid medium from the second ink ejected into the cell and forming a resin film,
The curable resin material includes a monomer component x1 represented by the following formula (11), a monomer component x3 represented by the following formula (13), and a monomer component represented by the following formula (14). a polymer X comprising x4;
And a polymer Y containing a monomer component y1 represented by the following formula (15).

Accordingly, it is possible to provide a method for producing a color filter that can efficiently produce a color filter that is excellent in brightness and contrast ratio and that is free from occurrence of color unevenness and density unevenness.
Moreover, the durability of the manufactured color filter can be made excellent.
Further, by forming a resin film separately from the colored film, the solvent resistance of the manufactured color filter, the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter, and the like are particularly excellent. be able to.
In addition, by containing the constituent material of the colored portion to be formed separately into two types of ink, it is possible to improve the ejection stability of the ink and to enable high-speed drawing by the inkjet method, The productivity of the color filter can be made particularly excellent.

これにより、明度およびコントラスト比に優れ、かつ、色むら、濃度むらの発生が抑制されたカラーフィルターをより効率よく製造することができる。 In the method for producing a color filter of the present invention, the curable resin material has an alkoxysilyl group-containing vinyl monomer component n1 represented by the following formula (21) and a cyclic ether group having 3 to 5 members. It is preferable to include a vinyl monomer component n2 and a copolymer N including a hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymerization chain portion in the side chain.

Thereby, it is possible to more efficiently manufacture a color filter that is excellent in lightness and contrast ratio and in which the occurrence of uneven color and uneven density is suppressed.

In the method for producing a color filter of the present invention, the copolymer N preferably has a weight average molecular weight of 500 or more and 100,000 or less.
As a result, the temporal stability (long-term storage stability) of the second ink and the ejection stability of the second ink can be made particularly excellent, and the productivity of the color filter can be made sufficiently excellent. Furthermore, the flatness of the resin film formed using the second ink can be made more reliable, and the occurrence of color unevenness and the like in the image displayed using the color filter can be more effectively achieved. Can be prevented.

In the method for producing a color filter of the present invention, the content of the vinyl monomer component n1 in the copolymer N is preferably 1 wt% or more and 95 wt% or less.
Thereby, the compatibility fall of the polymer X and the polymer Y can be prevented more effectively.
In the method for producing a color filter of the present invention, the content of the vinyl monomer component n2 in the copolymer N is preferably 1 wt% or more and 95 wt% or less.
Thereby, the solvent resistance of the obtained resin film can be improved more effectively, and the mechanical strength can also be improved.

In the method for producing a color filter of the present invention, the content of the vinyl monomer component n3 in the copolymer N is preferably 0.1 wt% or more and 95 wt% or less.
Thereby, the compatibility of the polymer N with the polymer X and the polymer Y can be made more effective.
In the method for producing a color filter of the present invention, the first liquid medium is diethylene glycol dimethyl ether, 1,3-butylene glycol diacetate, triethylene glycol diethyl ether, bis (2-butoxyethyl) ether, diethylene glycol monobutyl ether acetate. And one or more selected from the group consisting of 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate.
Thereby, the droplet discharge property of the first ink can be made particularly excellent, and the productivity of the color filter can be made particularly excellent. In addition, since the first liquid medium can be suitably removed before application of the second ink, and the formed colored film can be excellent in solvent resistance, the first ink It is possible to more reliably prevent the colorant contained therein from diffusing into the resin film formed by the second ink. As a result, it is possible to more effectively prevent a decrease in brightness and contrast ratio, color unevenness and density unevenness, and a good voltage holding ratio (VHR) of a liquid crystal layer of a liquid crystal display device provided with a color filter. Can be.

  In the method for producing a color filter of the present invention, the second liquid medium is propylene glycol-n-butyl ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate, 3-ethoxypropionic acid. It is preferable to include one or more selected from the group consisting of ethyl, bis (2-butoxyethyl) ether, diethylene glycol monobutyl ether acetate, and 1,3-butylene glycol diacetate.

  Thereby, the droplet discharge property of the second ink can be made particularly excellent, and the productivity of the color filter can be made particularly excellent. Further, it is possible to more reliably prevent the colorant from diffusing into the second ink (resin film) from the colored film formed from the first ink. As a result, it is possible to more effectively prevent a decrease in brightness and contrast ratio, color unevenness and density unevenness, and a good voltage holding ratio (VHR) of a liquid crystal layer of a liquid crystal display device provided with a color filter. Can be.

The color filter of the present invention is manufactured by the method for manufacturing a color filter of the present invention.
Thereby, it is possible to provide a color filter which is manufactured using an ink jet method, has excellent brightness and contrast ratio, and suppresses occurrence of uneven color and uneven density.
Further, the durability of the color filter can be improved.
In addition to the colored film, by having a resin film, the solvent resistance of the color filter, the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter, and the like can be made particularly excellent.

An image display device according to the present invention includes the color filter according to the present invention.
Accordingly, it is possible to provide an image display device that can stably display an image that is excellent in brightness and contrast ratio, and that suppresses the occurrence of color unevenness and density unevenness.
An electronic apparatus according to the present invention includes the image display device according to the present invention.
As a result, it is possible to provide an electronic device that can stably display an image that is excellent in brightness and contrast ratio and in which the occurrence of color unevenness and density unevenness is suppressed.

It is sectional drawing which shows suitable embodiment of the color filter of this invention. It is sectional drawing which shows suitable embodiment of the manufacturing method of the color filter of this invention. It is a perspective view which shows the droplet discharge apparatus used for manufacture of a color filter. It is sectional drawing which shows embodiment of a liquid crystal display device. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Hereinafter, preferred embodiments of the present invention will be described in detail.
"Color filter"
First, prior to the description of the method for manufacturing a color filter of the present invention, an example of a color filter manufactured by the method for manufacturing a color filter of the present invention will be described.
FIG. 1 is a cross-sectional view showing a preferred embodiment of the color filter of the present invention.

  As shown in FIG. 1, the color filter 1 includes a substrate 11 and a colored portion 12 formed using a color filter ink set to be described later. As the colored portion 12, a first colored portion 12A, a second colored portion 12B, and a third colored portion 12C formed using different types of ink are provided. A partition wall 13 is provided between the adjacent colored portions 12. Note that the first colored portion 12A, the second colored portion 12B, and the third colored portion 12C may be formed using the second ink and different types of first ink. In the following description, in addition to the second ink, each colored portion is formed with the first colored portion 12A using red ink and the second colored portion 12B using green ink. A case where the third colored portion 12C is formed using blue ink will be mainly described.

<Board>
The substrate 11 is a plate-like member having optical transparency, and has a function of holding the colored portion 12 and the partition wall 13.
The substrate 11 is preferably made of a substantially transparent material. Thereby, a clearer image can be formed by the light transmitted through the color filter 1.

  The substrate 11 is preferably excellent in heat resistance and mechanical strength. Thereby, for example, deformation due to heat applied during the manufacture of the color filter 1 can be reliably prevented. Examples of the constituent material of the substrate 11 that satisfies such conditions include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer, and hydrogenated products thereof.

<Coloring part>
The colored portion 12 is formed using a color filter ink set as described later.
Each colored portion 12 (first colored portion 12A, second colored portion 12B, and third colored portion 12C) is formed using a color filter ink set as described later. Each colored portion 12 is provided in a cell 14 which is a region surrounded by a partition wall 13 which will be described later.

Each colored portion 12 includes a colored film 121 formed using a first ink, which will be described later, and a resin film 122 formed using a second ink.
This colored part 12 is manufactured by the manufacturing method of the color filter of this invention mentioned later. As a result, the display image of the color filter 1 is excellent in brightness and contrast ratio, and generation of uneven color and uneven density is suppressed. Further, the durability of the color filter 1 can be improved. Further, by having the resin film 122 separately from the colored film 121, the solvent resistance of the color filter 1, the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter, and the like are particularly excellent. Can do. In addition, with the above-described configuration, the thickness of the resin film 122 that hardly affects the color of the display image is adjusted while making the content of the colorant (pigment) in each colored portion suitable. It is possible to make the thickness of the colored portions (12A, 12B, 12C) of each color uniform easily and reliably. For this reason, when such a color filter 1 is used for an image display device as described later, a common electrode provided on the surface of the coloring portion 12 and the partition wall 13 opposite to the surface facing the substrate 11 has Due to the difference in level between the colored portion 12 and the partition wall 13, it is possible to reliably prevent the occurrence of problems such as disconnection.

  By the way, in order to prevent the disconnection of the common electrode as described above, a flattened film made of a transparent resin material is formed between the colored portion and the partition wall and the common electrode to prevent the disconnection of the common electrode. Conceivable. However, when such a color filter is used in an image display device, when light passes through the color filter, a part of the light is easily reflected on the planarization film, and the light that has been repeatedly reflected is reflected by other The colored portion is transmitted. As a result, the light that has been repeatedly reflected is transmitted through other colored portions other than the colored portion to be transmitted, and the resulting image is unclear in shape and color tone. On the other hand, in the present invention, occurrence of such a problem can be reliably prevented.

In addition, the colored film 121 is disposed in a portion in contact with the substrate 11 in the colored portion 12. Thus, by providing the colored film 121 along the substrate 11, the colored film 121 becomes particularly smooth, and the color filter 1 has a particularly suppressed density unevenness and color unevenness at each part. Become.
The first colored portion 12A, the second colored portion 12B, and the third colored portion 12C are of different colors. For example, the first colored portion 12A can be a red filter region (R), the second colored portion 12B can be a green filter region (G), and the third colored portion 12C can be a blue filter region (B). One set of colored portions 12A, 12B, and 12C of different colors constitutes one pixel. In the color filter 1, a predetermined number of colored portions 12 are arranged in the horizontal direction and the vertical direction. For example, when the color filter 1 is a high-definition color filter, 1366 × 768 pixels are arranged, and when the color filter 1 is a full high-definition color filter, 1920 × 1080 pixels are arranged. In the case of a super high vision color filter, 7680 × 4320 pixels are arranged. Note that the color filter 1 may be provided with a spare pixel outside the effective area, for example.

<Partition wall>
A partition wall (bank) 13 is provided between the adjacent colored portions 12. Thereby, it can prevent reliably that the adjacent coloring parts 12 will mix colors, As a result, a clear image can be displayed reliably.
The partition wall 13 may be made of a transparent material, but is preferably made of a light-shielding material. Thereby, an image with excellent contrast can be displayed. The color of the partition wall (light shielding part) 13 is not particularly limited, but is preferably black. Thereby, the contrast of the displayed image can be made particularly excellent.

  The height of the partition wall 13 is not particularly limited, but is preferably substantially the same as the film thickness of the colored portion 12. Thereby, the color mixture between the adjacent coloring parts 12 can be prevented reliably. The specific thickness of the partition wall 13 is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 3.5 μm or less. As a result, color mixing between the adjacent colored portions 12 can be reliably prevented, and the viewing angle characteristics of the image display device and electronic apparatus including the color filter 1 can be improved.

  The partition wall 13 may be made of any material, but for example, is preferably made mainly of a resin material. Thereby, the partition wall 13 can be easily formed as having a desired shape by a method as described later. Moreover, when the partition 13 has a function as a light-shielding part, it may include a light-absorbing material such as carbon black as a constituent material.

《Color filter manufacturing method》
Next, the manufacturing method of the color filter of this invention is demonstrated.
FIG. 2 is a cross-sectional view showing a preferred embodiment of a method for manufacturing a color filter, and FIG. 3 is a perspective view showing a droplet discharge device used for manufacturing the color filter.
In the method for producing a color filter of the present invention, a first ink containing a colorant and a first liquid medium in which the colorant is dispersed and / or dissolved is ejected into a region (cell) surrounded by a partition wall. A first ink applying step, a first liquid medium removing step of removing the first liquid medium from the first ink discharged into the cell to form a colored film, and a colored film being formed. A cooling step for cooling the substrate in an environment with a relative humidity of 10% or less and an ambient temperature of 15 ° C. or more and 35 ° C. or less, and a predetermined monomer component as described later in the cell in which the first ink is discharged. A second ink application step for discharging a second ink including a curable resin material including the second curable resin material and a second liquid medium for dispersing and / or dissolving the curable resin material; The second liquid medium is removed from the second ink to form a resin film. It is characterized in that it has a liquid medium removal step.

  By having such characteristics, it is possible to efficiently manufacture a color filter that is excellent in lightness and contrast ratio and in which the occurrence of color unevenness and density unevenness is suppressed. Moreover, the durability of the manufactured color filter can be made excellent. Further, by forming a resin film separately from the colored film, the solvent resistance of the manufactured color filter, the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter, and the like are particularly excellent. be able to. In addition, by separately ejecting the first ink and the second ink into the cell, it is possible to reliably prevent the viscosity of each ink from being increased and to have excellent ejection stability of each ink. It can be. In addition, when used in an image display device, since the thickness of each colored portion is uniform, even when a common electrode is provided, it is possible to reliably prevent disconnection of the common electrode, and an appropriate and clear display can be obtained. It will be.

  As shown in FIG. 2, the color filter manufacturing method of the present embodiment includes a substrate preparation step (1a) for preparing the substrate 11, a partition formation step (1b, 1c) for forming the partition 13 on the substrate 11, The first ink application step (1d) for applying the first ink 21 to the region (cell) surrounded by the partition wall 13 by the inkjet method, and the first liquid property from the first ink 21 discharged into the cell. A first liquid medium removing step (1e) for removing the medium, a cooling step for cooling the substrate 11 under a predetermined environment, and the second ink 22 being ejected into the cell in which the first ink 21 has been ejected. A second ink applying step (1f) and a second liquid medium removing step (1g) for removing the second liquid medium from the second ink 22 ejected into the cell. .

Hereinafter, each step will be described in detail.
<Board preparation process>
First, the substrate 11 is prepared (1a). The substrate 11 prepared in this step is preferably subjected to a cleaning process. In addition, the substrate 11 prepared in this step has been subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, and the like. Also good.

<Partition forming process>
Next, the radiation-sensitive composition for forming the partition walls of the substrate 11 is applied to almost the entire one surface of the substrate 11 to form the coating film 3 (1b). In addition, after giving a radiation sensitive composition on the board | substrate 11, you may perform a prebaking process as needed.
Then, the partition 13 is formed by performing a post-exposure baking process (PEB) by irradiating with a radiation through a photomask, and further performing a developing process using an alkaline developer (1c).

  Moreover, you may perform a liquid-repellent process with respect to the coating film 3 before image development processing. For example, before the development treatment, a fluororesin may be applied to the coating film 3 by a stamp method or the like, and fluorine is doped on the surface of the coating film 3 (radiation sensitive composition) by plasma polymerization treatment. Also good. By performing such treatment, only the bank surface (upper surface in the drawing, the portion excluding the inner wall surface) is made liquid repellent, contributing to further planarization of the surface of the colored portion 12 formed in a later step. Further, a fluororesin having a light specific gravity may be added to the radiation-sensitive composition so as to be oriented only on the surface.

<First ink application step>
Next, the first ink 21 containing the colorant and the first liquid medium in which the colorant is dispersed and / or dissolved is applied to the cell 14 surrounded by the partition wall 13 by an inkjet method ( 1d).
This step is performed using a plurality of types of first inks 21 corresponding to a plurality of colored films 121 to be formed. At this time, since the partition wall 13 is provided, it is reliably prevented that two or more kinds of the first inks 21 are mixed.

The first ink 21 is discharged using a droplet discharge device as shown in FIG.
As shown in FIG. 3, the droplet discharge device 100 used in this step is supplied with the first ink 21 from the tank 101 that holds the first ink 21, the tube 110, and the tube 110. A discharge scanning unit 102. The ejection scanning unit 102 includes a droplet ejection unit 103 in which a plurality of droplet ejection heads (inkjet heads) are mounted on a carriage, and a first position control device 104 (moving unit) that controls the position of the droplet ejection unit 103. A stage 106 that holds the substrate 11 (hereinafter also simply referred to as “substrate 11”) on which the partition wall 13 is formed in the above-described process, and a second position control device 108 (moving means) that controls the position of the stage 106. The control means 112 is provided. The tank 101 and a plurality of droplet discharge heads in the droplet discharge means 103 are connected by a tube 110, and the first ink 21 is supplied from the tank 101 to each of the plurality of droplet discharge heads by compressed air. The

  The first position control device 104 moves the droplet discharge means 103 along the X-axis direction and the Z-axis direction orthogonal to the X-axis direction in response to a signal from the control means 112. Further, the first position control device 104 also has a function of rotating the droplet discharge means 103 around an axis parallel to the Z axis. In the present embodiment, the Z-axis direction is a direction parallel to the vertical direction (that is, the direction of gravitational acceleration). The second position controller 108 moves the stage 106 along the Y-axis direction orthogonal to both the X-axis direction and the Z-axis direction in response to a signal from the control unit 112. Further, the second position control device 108 also has a function of rotating the stage 106 around an axis parallel to the Z axis.

The stage 106 has a plane parallel to both the X-axis direction and the Y-axis direction. The stage 106 is configured so that the substrate 11 having the cells 14 to which the first ink 21 is to be applied can be fixed or held on the plane.
As described above, the droplet discharge means 103 is moved in the X-axis direction by the first position control device 104. On the other hand, the stage 106 is moved in the Y-axis direction by the second position control device 108. That is, the first position control device 104 and the second position control device 108 change the relative position of the droplet discharge head with respect to the stage 106 (the substrate 11 held on the stage 106 and the droplet discharge means 103 are relatively Moving).

The control unit 112 is configured to receive ejection data representing a relative position where the first ink 21 is to be ejected from the external information processing apparatus.
Using the droplet discharge device 100 as described above, the first ink 21 corresponding to the colored films 121 of the plurality of colors that the color filter 1 has is applied to the cells 14. By using the apparatus as described above, the first ink 21 can be efficiently and selectively applied to the cells 14. Further, as described above, the first ink 21 has excellent ejection stability, and even when droplets are ejected for a long period of time, flight bending and the amount of ejected droplets are small. Problems such as destabilization are extremely unlikely to occur. Therefore, a plurality of types of first inks 21 used to form the colored films 121 of different colors are mixed (mixed) or a plurality of colors that are originally required to have the same color density. Problems such as variations in the color density between the portions 12 can be reliably prevented. In the configuration shown in the figure, the droplet discharge device 100 has only one color for the tank 101 holding the first ink 21, the tube 110, etc., but the color filter 1 has a plurality of these members. It may have a plurality of colors corresponding to the colored portion 12. In manufacturing the color filter 1, a plurality of droplet discharge devices 100 corresponding to the first ink 21 of a plurality of colors may be used.

In addition, as described above, in the method for producing a color filter of the present invention, the constituent material of the colored portion is divided into the first ink and the second ink, so that the first ink and the second ink are contained. The discharge stability can be made excellent. For this reason, when droplets are discharged as described above, it is possible to reliably prevent unintended variations in the droplet amount of the first ink 21 applied to each cell 14.
In the present invention, the droplet discharge head may use an electrostatic actuator as a driving element instead of a piezoelectric element. The droplet discharge head may be configured to use an electrothermal conversion element as a drive element and discharge the first ink 21 using thermal expansion of a material by the electrothermal conversion element.

<First liquid medium removing step>
Next, the first liquid medium is removed from the first ink 21 in the cell 14 (1e). In this way, by removing the first liquid medium from the first ink 21, the fluidity of the first ink 21 can be lost. When the first liquid medium is removed in this step and the colored film 121 is formed, even when the second ink 22 is applied in the subsequent second ink application step, the first ink 21 The constituent material is reliably prevented from diffusing into the applied second ink 22. As a result, the colored portion 12 having a configuration including the colored film 121 and the resin film 122 can be formed, and the effects described above are exhibited. In particular, since the first ink 21 contains a pigment as a colorant, the removal of the first liquid medium causes the pigment particles to agglomerate firmly and reliably prevent diffusion to the second ink. The

The removal of the first liquid medium is usually performed by heating.
When removing the first liquid medium by heating, the heating temperature is, for example, preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 200 ° C. or higher and 280 ° C. or lower. Thereby, in this step, the first liquid medium is surely removed, and the colored film 121 in which the elution of the component into the second ink 22 does not easily occur can be more reliably formed. In addition, it is possible to reliably prevent adverse effects on the substrate 11 and the like.

In this step, the substrate 11 to which the first ink 21 is applied may be in a reduced pressure environment. Thereby, the first liquid medium can be efficiently removed while preventing adverse effects on the substrate 11 and the like.
In this step, energy irradiation such as ultraviolet rays, electron beams, or radiation may be performed.
Moreover, this process may be comprised by two or more processes. That is, the first liquid medium may be removed by the pre-removing step and the main removing step.

<Cooling process>
Next, the substrate 11 on which the colored film 121 is formed is cooled and stored in an environment where the relative humidity is 10% or less and the ambient temperature is 15 ° C. or more and 35 ° C. or less (cooling step).
By performing such a process, it is possible to prevent moisture from being absorbed into the colored film 121.

  By the way, although the coloring part 12 which has the resin film 122 formed using the curable resin containing a monomer component which is mentioned later has the advantage that it is especially excellent in solvent resistance and adhesiveness, a colored film When a large amount of moisture is absorbed by 121, the moisture reacts with the alkoxyl group of the monomer component of the curable resin during the second second liquid medium removing step described later, and the curable resin These components are separated, and there is a problem that the solvent resistance and adhesion are deteriorated.

On the other hand, as in the present invention, after removing the first liquid medium, the colored film 121 is cooled and stored in an environment where the relative humidity is 10% or less and the ambient temperature is 15 ° C. or more and 35 ° C. or less. It is possible to prevent moisture from being absorbed inside, and to prevent the components of the cured resin as described above from separating. As a result, the colored portion 12 to be formed can have excellent solvent resistance and adhesion.
As described above, in the present invention, the substrate 11 is cooled in an environment where the relative humidity is 10% or less and the ambient temperature is 15 ° C. or more and 35 ° C. or less. However, the substrate 11 is 5% or less and the ambient temperature is 20 ° C. It is more preferable to cool in an environment of 30 ° C. or lower. Thereby, it is possible to more effectively prevent moisture from being absorbed into the colored film 121.

<Second ink application step>
Next, the second ink 22 is applied into the cell 14 (1e).
As described above, the first liquid medium is removed from the first ink 21 in the cell 14, and the colored film 121 is formed. For this reason, when the second ink 22 is applied to the cell 14 to which the first ink 21 is applied (the cell 14 on which the colored film 121 is formed), the components of the first ink 21 and the second ink are applied. 22 is prevented from being mixed with each other, and the colored portion 12 having a laminated structure of the colored film 121 and the resin film 122 can be reliably formed. In particular, the second liquid medium containing the second ink 22 has a lower boiling point than the first liquid medium constituting the first ink 21. When the second ink 22 containing such a second liquid medium is applied, the aggregation of the pigment constituting the colored film 121 in the cell 14 is promoted. Therefore, when the second ink 22 is applied In addition, mixing of the components of the first ink 21 and the components of the second ink 22 is surely prevented, and the colored portion 12 that forms the laminated structure of the colored film 121 and the resin film 122 is more reliably formed. Can be formed. Further, as described above, since the first ink 21 includes a part of the constituent components of the colored portion 12, the discharge stability of the droplets of the second ink 22 may be excellent. it can. As a result, since the desired amount of the second ink 22 can be landed reliably at the target position, it is possible to prevent unintentional thickness variations of the colored portions 12 in the final color filter 1. Can do. Moreover, since high-speed drawing by the inkjet method is possible, the productivity of the color filter 1 as a whole can be made particularly excellent.
The application of the second ink 22 into the cell 14 is performed by an ink jet type droplet ejecting apparatus, and the droplet ejecting apparatus 100 as described above is used in the same manner as the first ink 21. It can be carried out.

The second ink 22 is a cell to which the first ink 21 having the smallest solid content among the plurality of first inks 21 among the cells to which the plurality of first inks 21 is to be applied. On the other hand, it is preferable to give the most amount. Thereby, the thickness of the colored part 12 can be adjusted easily and reliably, and a color filter in which the thickness of the colored part 12 is particularly uniform can be manufactured. For this reason, the obtained color filter 1 is one in which uneven density and uneven color of each part are particularly suppressed. Further, when such a color filter 1 is used in an image display device described later, a common electrode provided on the surface of the coloring portion 12 and the partition wall 13 opposite to the surface facing the substrate 11 is colored. The level difference between the portion 12 and the partition wall 13 can reliably prevent problems such as disconnection.
In particular, in the cell 14 to which a plurality of types of first inks 21 are applied, the more the second ink 22 is applied to the cells 14 in which the solid content of the applied first ink 21 is smaller. preferable. Thereby, the thickness of the colored part 12 to be formed can be made particularly uniform.

<Second liquid medium removing step>
Next, the second liquid medium is removed from the second ink 22 in the cell 14 to form the resin film 122, and the colored portion 12 including the colored film 121 and the resin film 122 is obtained (1g). . Thereby, the color filter 1 is obtained.
As described above, since the first ink 21 contains a part of the constituent components of the colored portion 12, the resin film 122 formed using the second ink 22 has a high surface flatness. It becomes. As a result, the manufactured color filter 1 is excellent in the brightness and contrast ratio of the display image, and the occurrence of uneven color and uneven density is suppressed. Further, the surface of the colored film 121 made of a material containing a pigment is covered with the resin film 122, whereby the solvent resistance of the color filter 1 and the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter 1 are obtained. Etc. can be made particularly excellent. Moreover, the color filter 1 in which each coloring part 12 has a uniform thickness can be obtained.

The removal of the second liquid medium can be performed by heating, for example.
When removing the second liquid medium by heating, the temperature of the substrate 11 is, for example, preferably 60 ° C. or higher and 260 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower. Thereby, the second liquid medium can be efficiently removed from the second ink 22. In addition, it is possible to reliably prevent adverse effects on the substrate 11 and the like. Further, the curing reaction of the curable resin material contained in the second ink can be surely advanced, and the reliability and durability of the manufactured color filter 1 can be made particularly excellent.

In this step, the substrate 11 provided with the second ink 22 may be in a reduced pressure environment. Thereby, the first liquid medium can be efficiently removed while preventing adverse effects on the substrate 11 and the like.
In this step, energy irradiation such as ultraviolet rays, electron beams, or radiation may be performed.

<Ink set for color filter>
Next, an ink set (color filter ink set) used in the method for producing a color filter of the present invention will be described.
The color filter ink set used in the method for producing a color filter of the present invention includes a colorant and a first liquid medium in which the colorant is dispersed and / or dissolved, and is used for forming a colored film. And a second ink that forms a resin film by being discharged into the same cell as the first ink, the second ink comprising a curable resin material and the curable resin material A monomer component x1 represented by the following formula (11) and a monomer represented by the following formula (13): a second liquid medium that disperses and / or dissolves A polymer X including a component x3 and a monomer component x4 represented by the following formula (14) and a polymer Y including a monomer component y1 represented by the following formula (15) are included.

  In this way, the colored film is formed using the first ink containing the colorant, and the resin film is formed using the second ink containing the curable resin material as described above. By forming a colored portion having a high level of surface flatness of the colored portion, the brightness and contrast ratio of the display image of the produced color filter are excellent, and color unevenness, Generation of uneven density can be effectively prevented. In addition to the colored film, by having a resin film, the color filter manufactured has particularly excellent solvent resistance and durability, voltage holding ratio of the liquid crystal layer of the liquid crystal display device provided with the color filter, etc. It can be. In general, the ink used for the production of the color filter is completely different from that applied to a printer (for consumer use) and contains a high-boiling liquid as a liquid medium and has a high content of colorant and resin. However, in the ink set for a color filter of the present invention, there are two kinds of constituent materials for the colored portion to be formed. By containing the ink separately, it is possible to improve the ejection stability of the ink and to enable high-speed drawing by the ink jet method, so that the productivity of the color filter as a whole is particularly excellent. Can do.

  The color filter ink set used in the present invention may include at least one type of first ink and at least one type of second ink, but may include a plurality of types of first ink and at least one type of ink. It is preferable that the second ink is provided. Thereby, it can use suitably for manufacture of a color filter with a wide color reproduction range. In addition, the brightness and contrast ratio of the display image as the entire color filter to be manufactured can be made particularly excellent, and the occurrence of uneven color and uneven density can be more effectively prevented. Further, the durability and reliability of the produced color filter as a whole can be made particularly excellent.

In addition, the color filter ink set of the present invention includes a first red ink (red ink), a first green ink (green ink), and a blue first ink which are the three colors constituting the three primary colors of light. 1 ink (blue ink). Thereby, a color filter with a wide color reproduction range can be manufactured easily and efficiently. In the following description, the color filter ink set includes three types of first inks of “red ink (R ink)”, “green ink (G ink)”, and “blue ink (B ink)”. A representative explanation will be given.
In addition, the color filter ink set only needs to include at least one second ink, and may include a plurality of types. However, in the following description, the color filter ink set is the second ink set. A case where one type of ink is provided and the second ink is used for all the cells will be representatively described.

<First ink>
The first ink constituting the color filter ink set includes a colorant, a liquid medium in which the colorant is dispersed and / or dissolved (first liquid medium), and the like. It is used for forming a colored film of a filter. Thereby, the viscosity of the 1st ink and the 2nd ink can be made low, and the discharge property of these inks can be made excellent. That is, since the resin material contained in the first ink containing the colorant is small, an increase in viscosity due to the interaction between the colorant and the resin material can be prevented. In addition, by including a resin material as a constituent material of the colored portion in the second ink described later, the flatness of the surface of the colored film formed by the first ink can be made particularly excellent, The brightness and contrast ratio of the display image of the manufactured color filter can be made more excellent, and the occurrence of uneven color and uneven density can be more effectively prevented.

<Colorant>
The color filter usually has a plurality of different colored portions (generally, three colored portions corresponding to RGB). And each 1st ink which comprises the ink set for color filters contains the coloring agent according to the color tone of the coloring part which should be formed, respectively. As the colorant constituting the first ink, for example, various pigments and various dyes can be used, but the first ink preferably contains a pigment as the colorant. Thereby, the light resistance, heat resistance, etc. of the manufactured color filter can be made particularly excellent. In addition, in a color filter manufactured using a conventional ink jet method, when a pigment is included as a colorant, problems such as a decrease in brightness, contrast ratio, color unevenness, and density unevenness occurred more remarkably. However, in the present invention, even when a pigment is included as a colorant, the occurrence of the above problems can be reliably prevented. That is, when a pigment is used as the colorant, the effect of the present invention is more remarkably exhibited.

(Red ink)
The red ink usually contains a red colorant.
Examples of the colorant contained in the red ink include C.I. I. Pigment Red 2,3,5,17,22,23,38,81, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 52: 1, 53: 1, 57: 1. 63: 1,112,122,144,146,149,166,170,176,177,178,179,185,202,207,209,254,101,102,105,106,108,108: 1 etc. Pigments and C.I. I. Direct Red 2, 4, 9, 23, 26, 28, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Acid Red 35, 42, 51, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 145, 151, 154, 157, 158, 211, 249, 254 257, 261, 263, 266, 289, 299, 301, 305, 319, 336, 337, 361, 396, 397, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Basic red 12,13,14,15,18,22,23,24,25,27,29,35,36,38,39,45,46 etc. are mentioned, 1 type selected from these, or Two or more kinds can be used in combination.

Examples of the colorant constituting the red ink include those described above. I. Pigment red 177, C.I. I. It is preferable to include pigment red 254 and red ink containing at least one of these derivatives. Conventionally, when a colorant (pigment) as described above is included, problems such as a decrease in brightness and contrast ratio, color unevenness, and density unevenness have occurred more prominently. Even when a colorant (pigment) is contained, it is possible to reliably prevent the occurrence of the above problems. That is, when the above colorant (pigment) is used, the effect of the present invention is more remarkably exhibited.
C. I. Pigment Red 177 derivatives, C.I. I. In the case of containing a compound (derivative) represented by the following formula (30) or the following formula (31) as a pigment red 254 derivative, the effects as described above are more remarkably exhibited.

  In addition to the colorant as described above, red ink includes, for example, Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 34, 35, 35: 1, 37. 37: 1, 42, 43, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 157, 166, 168, 175, 180 , 184, 185 and the like. Thereby, the color tone of the colored part formed can be adjusted more suitably. Among these, pigment yellow 138, 139, 150, 184, and 185 are preferable, and pigment yellow 150 is more preferable. Thereby, the effect mentioned above is exhibited more notably.

  The content of the colorant in the red ink is preferably 7.0 wt% or more and 30.0 wt% or less, and more preferably 7.5 wt% or more and 25.0 wt% or more. Thereby, in the color filter manufactured using the ink set for color filters, a higher color density can be ensured and it can be used for clearer image display. Further, in the manufacturing method using the conventional ink jet method, when the content of the colorant in the ink is relatively high as described above, the ejection stability is particularly low, and the ink droplets are ejected. In particular, problems such as flying bends and instability of droplet discharge amount were particularly likely to occur. Also, in the past, particularly when a colored portion is formed by discharging droplets on a large substrate (for example, G5 or more), the occurrence of defective products due to variations in the discharge amount at each site in the surface becomes significant. There is a problem that the productivity of the color filter is remarkably lowered. On the other hand, in the present invention, even when a colorant is contained at a relatively high concentration, the occurrence of the above problems can be surely prevented, and the color at each part of the produced color filter can be prevented. It is possible to reliably prevent unevenness, unevenness of density, etc., and variation in characteristics among individuals, and a color filter can be manufactured with excellent productivity. That is, when the first ink contains a relatively high concentration of the colorant as described above, the effect of the present invention is more remarkably exhibited. In addition, the durability of the manufactured color filter can be made particularly excellent.

(Green ink)
The green ink usually contains a green colorant.
The colorant contained in the green ink is not particularly limited. I. Pigment Green 7,36,15,17,18,19,26,50,58, etc., C.I. I. And dyes such as Acid Green 16.

  Examples of the colorant constituting the green ink include those described above. I. It is preferable to include green ink including pigment green 58. Conventionally, when a colorant (pigment) as described above is included, problems such as a decrease in lightness and contrast ratio, color unevenness, and density unevenness have occurred more prominently. Even when a colorant (pigment) is contained, it is possible to reliably prevent the occurrence of the above problems. That is, when the above colorant (pigment) is used, the effect of the present invention is more remarkably exhibited.

Further, the green ink is C.I. I. When the pigment green 58 is included, it is preferable to further include a sulfonated pigment derivative as a sub-pigment. Thereby, the coloring property of the colored part formed using the green ink as the first ink can be further improved.
Green ink is C.I. I. When the pigment green 58 and the sulfonated pigment derivative are included, the sulfonated pigment derivative preferably contains a compound (derivative) represented by the following formula (32). Thereby, the effects as described above are more remarkably exhibited.

  Green ink is C.I. I. When the pigment green 58 and the pigment derivative (sulfonated pigment derivative) as described above are included, the content of the pigment derivative (sulfonated pigment derivative) is not particularly limited. I. Pigment Green 58 (main pigment): 10 parts by weight or more and 80 parts by weight or less is preferable with respect to 100 parts by weight, and more preferably 30 parts by weight or more and 70 parts by weight or less. Thereby, the contrast and brightness of the display image of the produced color filter 1 can be made particularly excellent.

  In addition to the colorant as described above, the green ink includes, for example, Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 34, 35, 35: 1, 37. 37: 1, 42, 43, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 157, 166, 168, 175, 180 , 184, 185 and the like. Thereby, the color tone of the colored part formed can be adjusted more suitably. Among these, pigment yellow 138, 139, 150, 184, and 185 are preferable, and pigment yellow 150 is more preferable. Thereby, the effect mentioned above is exhibited more notably.

  The content of the colorant in the green ink is preferably 8.0 wt% or more and 25.0 wt% or less, and more preferably 8.5 wt% or more and 18.0 wt% or less. Thereby, in the color filter manufactured using the ink set for color filters, a higher color density can be ensured and it can be used for clearer image display. Further, in the manufacturing method using the conventional ink jet method, when the content of the colorant in the ink is relatively high as described above, the ejection stability is particularly low, and the ink droplets are ejected. In particular, problems such as flying bends and instability of droplet discharge amount were particularly likely to occur. Also, in the past, particularly when a colored portion is formed by discharging droplets on a large substrate (for example, G5 or more), the occurrence of defective products due to variations in the discharge amount at each site in the surface becomes significant. There is a problem that the productivity of the color filter is remarkably lowered. On the other hand, in the present invention, even when a colorant is contained at a relatively high concentration, the occurrence of the above problems can be surely prevented, and the color at each part of the produced color filter can be prevented. It is possible to reliably prevent unevenness, unevenness of density, etc., and variation in characteristics among individuals, and a color filter can be manufactured with excellent productivity. That is, when the first ink contains a relatively high concentration of the colorant as described above, the effect of the present invention is more remarkably exhibited. In addition, the durability of the manufactured color filter can be made particularly excellent.

(Blue ink)
The blue ink usually contains a blue colorant.
Examples of the colorant contained in the blue ink include C.I. I. Pigment blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6, 17: 1,18,27,28,29,35,36,60,80, C. I. Examples thereof include dyes such as Acid Blue 9, 45, 80, 83, 90, and 185, and one or more selected from these can be used in combination.

  Examples of the colorant constituting the blue ink include those described above. I. It is preferable to have a blue ink containing Pigment Blue 15: 6. Conventionally, when a colorant (pigment) as described above is included, problems such as a decrease in lightness and contrast ratio, color unevenness, and density unevenness have occurred more prominently. Even when a colorant (pigment) is contained, it is possible to reliably prevent the occurrence of the above problems. That is, when the above colorant (pigment) is used, the effect of the present invention is more remarkably exhibited.

Also, the blue ink is C.I. I. In the case of including Pigment Blue 15: 6, C.I. I. Pigment Violet 23 is preferably included. Thereby, the coloring property of the colored part formed using the blue ink as the first ink can be further improved.
The content of the colorant in the blue ink is preferably 6.0 wt% or more and 20.0 wt% or less, and more preferably 6.5 wt% or more and 15.0 wt% or less. As a result, it is possible to ensure a sufficient color density in the manufactured color filter while improving the blue ink discharge performance from the droplet discharge head (inkjet head) for manufacturing the color filter. The reproduction range can be widened. Moreover, in the manufactured color filter, the uniformity of color density between colored portions of different colors can be made particularly excellent. Moreover, the durability of the manufactured color filter can be made excellent.

<First liquid medium>
The first liquid medium (first liquid medium) has a function of dispersing and / or dissolving the colorant as described above. That is, the first liquid medium functions as a dispersion medium and / or a solvent. In general, most of the first liquid medium is removed in the process of manufacturing the color filter.

  As the liquid constituting the first liquid medium, for example, ester compounds, ether compounds, hydroxy ketones, carbonic acid diesters, cyclic amide compounds and the like can be used. Among them, [1] polyhydric alcohols (for example, ethylene glycol) , Propylene glycol, butylene glycol, glycerin, etc.) condensates (polyhydric alcohol ethers), polyhydric alcohols or alkyl ethers of polyhydric alcohol ethers (eg, methyl ether, ethyl ether, butyl ether, hexyl ether, etc.) Ester (eg, formate, acetate, propionate, etc.), acetates, [2] ester of polyvalent carboxylic acid (eg, succinic acid, glutaric acid, etc.) (eg, methyl ester, etc.), [3] at least in the molecule One hydroxyl group and Ether compounds having one carboxyl group even without (hydroxy acid), esters and the like, (4) polyhydric alcohol and carbonic acid diester having a chemical structure as obtained in the reaction with phosgene is preferred.

  Among them, the first liquid medium is diethylene glycol dimethyl ether, 1,3-butylene glycol diacetate, triethylene glycol diethyl ether, bis (2-butoxyethyl) ether, diethylene glycol monobutyl ether acetate, and 2- (2-methoxy It is preferable that it includes one or more selected from -1-methylethoxy) -1-methylethyl acetate. Thereby, the droplet discharge property of the first ink can be made particularly excellent, and the productivity of the color filter can be made particularly excellent. In addition, since the first liquid medium can be suitably removed before application of the second ink, and the formed colored film can be excellent in solvent resistance, the first ink It is possible to more reliably prevent the colorant contained therein from diffusing into the resin film formed by the second ink. As a result, it is possible to more effectively prevent a decrease in brightness and contrast ratio, color unevenness and density unevenness, and a good voltage holding ratio (VHR) of a liquid crystal layer of a liquid crystal display device provided with a color filter. Can be.

  Further, the content of the first liquid medium in the first ink is preferably 60 wt% or more and 91 wt% or less, and more preferably 65 wt% or more and 90 wt% or less. When the content of the first liquid medium is a value within the above range, the discharge property of the first ink from the droplet discharge head can be made particularly excellent. In addition, the thickness of the colored film of the produced color filter can be made uniform, color unevenness and density unevenness in each part can be more effectively suppressed, and uniformity of characteristics among individuals Can be made particularly excellent. Moreover, in the manufactured color filter, a sufficient color density can be ensured and the color reproduction range can be widened.

<Polymer M>
The first ink is represented by a monomer component m1 represented by the following formula (1), a monomer component m2 having a carboxyl group or an acid anhydride group, and the following formula (3). The polymer M containing the monomer component m3 may be included.

By including such a polymer M, the adhesion of the colored film to the substrate can be made particularly excellent, and the durability of the produced color filter can be made particularly excellent. In addition, the long-term storability (first ink life) of the first ink is extremely excellent, and it is possible to effectively prevent the occurrence of problems such as deterioration in quality due to the mass production of the first ink. In addition, since the frequency of replacement of the first ink can be reduced when the color filter is manufactured, the productivity of the color filter and the reliability of the manufactured color filter can be improved.
In addition, the polymer M may consist essentially of a single compound, or may be a mixture of a plurality of types of compounds.

(Monomer component m1)
The polymer M contains a monomer component m1 represented by the above formula (1), that is, a compound having a blocked isocyanate group (hereinafter also referred to as “block isocyanate group”) as a monomer component. It will be. The polymer M constituting the first ink may include a plurality of monomer components m1 represented by the general formula (1) in the molecule.

In the monomer component m1 represented by the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ represents a residue of an isocyanate group blocking agent R ³ H.
Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ² include a linear or branched divalent saturated aliphatic hydrocarbon group (alkylene group). A divalent saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms such as ethylene, trimethylene and propylene groups is preferred.

Examples of the isocyanate group blocking agent R ³ H include oxime blocking agents such as formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclohexanone oxime, diacetyl monooxime, and benzophenone oxime. A pyrazole block agent such as 3,5-dimethylpyrazole; an alcohol block agent such as methanol and ethanol; a phenol block agent such as phenol and cresol; a mercaptan block agent such as butyl mercaptan; acetanilide, ε-caprolactam, γ -Acid amide blocking agents such as butyrolactam; active methylene blocking agents such as dimethyl malonate and methyl acetoacetate; imides such as succinimide and maleic imide Lock agent; urea blocking agents; N- phenylcarbamate type blocking agents of phenyl carbamate, and the like; diphenylamine, amine blocking agents such as aniline, ethylene imine, etc. imine blocking agents such as polyethyleneimine.
As an isocyanate group blocking agent, an oxime blocking agent and a pyrazole blocking agent are preferable, and those represented by the following formula (5) are more preferable.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁶ and R ⁷ in the formula (5) include linear or branched alkyl groups, and the number of carbon atoms such as methyl, ethyl, and propyl groups. 1 or more and 4 or less linear or branched alkyl group is preferable. Examples of the ring in which R ⁶ and R ⁷ are bonded to each other together with the adjacent carbon atom include a cycloalkane having about 3 to 12 members (preferably 5 or 6 members) such as a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. A ring etc. are mentioned.

  Specific examples of the monomer component m1 represented by the formula (1) include 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylideneamino). (Oxycarbonylaminoethyl) methacrylate) (represented by the following formula (6)), 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl methacrylate (represented by the following formula (7)) ) And the like.

  The content of the monomer component m1 in the polymer M (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is 1 wt% or more and 99 wt% or less (for example, 10 wt% or more and 95 wt% or less). It is preferably 20 wt% or more and 90 wt% or less, more preferably 25 wt% or more and 88 wt% or less. In addition, when the polymer M contains a plurality of types of monomer components m1, it is preferable that the sum of the contents of the plurality of types of monomer components m1 satisfies the above-described conditions. Further, when the polymer M is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is used as the content value of the monomer component m1. can do. Moreover, when the polymer M is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component m1 at the content described above.

(Monomer component m2)
The polymer M contains a monomer component m2 having a carboxyl group or an acid anhydride group as a monomer component. The polymer M constituting the first ink may include a plurality of types of monomer components m2 in the molecule.
By including such a monomer component m2 as a monomer component in the polymer M, it is possible to improve the wetting and spreading of the first ink on the substrate, and the mixing of bubbles and the like A colored film that is reliably prevented and has excellent adhesion to the substrate can be suitably formed. Further, by containing the monomer component m2 as the monomer component, the long-term storage stability of the first ink can be made particularly excellent.

  Examples of the monomer component m2 include unsaturated carboxylic acids or acid anhydrides thereof. Specific examples of the monomer component m2 include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and acid anhydrides thereof (maleic anhydride, itaconic anhydride). Acid) and the like, and among them, acrylic acid and methacrylic acid (represented by the following formula (2)) are particularly preferable.

  The content of the monomer component m2 in the polymer M (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 0.5 wt% or more and 98 wt% or less (for example, 2.5 wt% or more). 70 wt% or less), preferably 3 wt% or more and 50 wt% or less, more preferably 5 wt% or more and 40 wt% or less. When the content of the monomer component m2 in the polymer M is a value within the above range, the above-described monomer component m1 and the monomer component m3 described in detail later are not impaired, and the above-described functions are not impaired. The effect as described above can be expressed more remarkably. On the other hand, when the content of the monomer component m2 in the polymer M is less than the lower limit, the effect of including the monomer component m2 may not be sufficiently exhibited. On the other hand, when the content of the monomer component m2 in the polymer M exceeds the upper limit, the content of the monomer components m1, m3, etc. may be relatively decreased, and these functions may not be sufficiently exhibited. There is sex. In addition, when the polymer M contains a plurality of types of monomer components m2, it is preferable that the sum of the contents of the plurality of types of monomer components m2 satisfies the above-described conditions. Further, when the polymer M is a mixture of plural kinds of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is adopted as the content value of the monomer component m2. can do. Moreover, when the polymer M is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component m2 with the content as described above.

(Monomer component m3)
The polymer M contains the monomer component m3 ((meth) acrylic acid ester) represented by the above formula (3) as a monomer component. The polymer M constituting the first ink may contain a plurality of monomer components m3 represented by the general formula (3) in the molecule.

  By including such a monomer component m3 as a monomer component in the polymer M, the flatness of the colored film formed using the first ink can be made high. Further, by containing the monomer component m3 as a monomer component in the polymer M, the discharge stability of the first ink can be improved. Further, by containing the monomer component m3 as a monomer component in the polymer M, the storage stability (long-term storage property) of the first ink can be made excellent.

Examples of the hydrocarbon group having 16 to 25 carbon atoms in R ⁵ include alkyl groups such as hexadecyl (cetyl), heptadecyl, octadecyl (stearyl), nonadecyl, icosyl and docosyl (behenyl) groups; 10-cyclohexyldecyl, 12 A group in which an alicyclic hydrocarbon group such as cyclohexyldodecyl, 14-cyclohexyltetradecyl, 16-cyclohexylhexadecyl and the like are bonded to an alkyl group; 10-phenyldecyl, 12-phenyldodecyl, 14-phenyltetradecyl, 16 -Aralkyl groups, such as a phenyl hexadecyl group, etc. are mentioned.

Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 16 to 25 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); Aryloxy group such as phenoxy group; alicyclic hydrocarbon group-substituted oxy group such as cyclohexyloxy group and dicyclopentanyloxy group; and 1 to 15 carbon atoms such as aralkyloxy group such as benzyloxy group (preferably, And a hydrocarbon group-substituted oxy group having 1 to 12 carbon atoms.
Specific examples of the monomer component m3 include cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

As described above, the number of carbon atoms of the hydrocarbon group (which may have a hydrocarbon group-substituted oxy group) contained in the monomer component m3 constituting the polymer M (hereinafter also referred to as the carbon number of R ⁵ ). Is 16 or more and 25 or less, particularly preferably 16 or more and 22 or less, and more preferably 16 or more and 20 or less. Thereby, the effect mentioned above is exhibited more notably. On the other hand, when the carbon number of R ⁵ is less than the lower limit value or exceeds the upper limit value, the excellent effects as described above cannot be obtained. Thus, the polymer M has one big feature in that it includes a monomer component (monomer component m3) having a group (R ⁵ ) having a predetermined number of carbon atoms.

  The content of the monomer component m3 in the polymer M (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 0.5 wt% or more and 98 wt% or less (for example, 2.5 wt% or more). 70 wt% or less), preferably 3 wt% or more and 50 wt% or less, more preferably 5 wt% or more and 40 wt% or less. When the content of the monomer component m3 in the polymer M is a value within the above range, the above-described effects are more prominent without inhibiting the functions of the monomer components m1, m2, and the like. Can be expressed. On the other hand, when the content of the monomer component m3 in the polymer M is less than the lower limit, the effect of including the monomer component m3 may not be sufficiently exhibited. On the other hand, if the content of the monomer component m3 in the polymer M exceeds the upper limit, the content of the monomer components m1, m2, etc. may be relatively decreased, and these functions may not be sufficiently exhibited. There is sex. In addition, when the polymer M contains a plurality of types of monomer components m3, it is preferable that the sum of the content ratios of the plurality of types of monomer components m3 satisfies the above conditions. Further, when the polymer M is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component m3. can do. Moreover, when the polymer M is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component m3 at the above-described content.

Polymer ratio of the monomer component m1 in _{M (C m1 [wt%]} ) and the monomer ratio of the components _{m2 (C m2 [wt%]} ) , it is preferable to satisfy the following relationship. That is, C _m1 / C _m2 is preferably 2/98 or more and 98/2 or less, more preferably 20/80 or more and 95/5 or less, and 40/60 or more and 95/5 or less. Further preferred.
Further, the ratio of monomer component m1 in polymer M ( _Cm1 [wt%]) and the ratio of monomer component m3 ( _Cm3 [wt%]) preferably satisfy the following relationship. . That is, C _m1 / C _m3 is preferably 2/98 or more and 98/2 or less, more preferably 20/80 or more and 95/5 or less, and 40/60 or more and 95/5 or less. Further preferred.
Examples of the polymer M include those represented by the following formula (8).

  Moreover, the polymer M may contain components other than the monomer components m1, m2, and m3 described above. Thereby, for example, the effects derived from the chemical structures of other monomer components can be obtained while exhibiting the above-described characteristics. Examples of such components include monomer component m4, monomer component m5, monomer component m6, monomer component m7 and the like as described below.

(Monomer component m4)
The polymer M may contain the monomer component m4 ((meth) acrylic acid ester) represented by the following formula (4) as a monomer component.

Since the polymer M contains the monomer component m4, the solubility of the polymer M in the first ink even when the first liquid medium constituting the first ink is highly hydrophilic. And the transparency of the colored film formed using the first ink can be made excellent.
In the monomer component m4, R ⁹ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a hydrocarbon group-substituted oxy group, and the hydrocarbon group has 1 to 12 carbon atoms. It is preferable that: Examples of the hydrocarbon group represented by R ⁹ include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl group; Alicyclic hydrocarbon groups such as cyclohexyl, dicyclopentanyl and isobornyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl groups; groups in which two or more of these are bonded, etc. Is mentioned.

  Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 1 to 15 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); Aryloxy group such as phenoxy group; alicyclic hydrocarbon group-substituted oxy group such as cyclohexyloxy group and dicyclopentanyloxy group; and 1 to 15 carbon atoms such as aralkyloxy group such as benzyloxy group (preferably, And a hydrocarbon group-substituted oxy group having 1 to 12 carbon atoms.

  Specific examples of the monomer component m4 include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, di Examples include cyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, and the like.

As described above, the carbon number of the hydrocarbon group (which may have a hydrocarbon group-substituted oxy group) included in the monomer component m4 (hereinafter also referred to as the carbon number of R ⁹ ) is 1 or more and 15 or less. However, it is particularly preferably 1 or more and 8 or less, and more preferably 1 or more and 4 or less. Thereby, the effect mentioned above is exhibited more notably.
Examples of the polymer M including the monomer component m4 as described above include those represented by the following formula (9).

(Monomer component m5)
The polymer M may contain the monomer component m5 which is an aromatic vinyl compound as a monomer component.
When the polymer M contains the monomer component m5, the discharge stability of the first ink can be made particularly excellent. Further, the colored film formed using the first ink is particularly excellent in adhesion to the substrate, and problems such as cracks are not particularly likely to occur.
Specific examples of the monomer component m5 include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, and the like.

(Monomer component m6)
The polymer M may include a monomer component m6 that is a hydroxyl group-containing compound as a monomer component.
Specific examples of the monomer component m6 include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy. Polyhydric alcohol and acrylic acid such as hexyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc. Or a compound obtained by ring-opening polymerization of ε-caprolactone to a monoesterified product of methacrylic acid, a monoesterified product of the above polyhydric alcohol and acrylic acid or methacrylic acid, ethylene oxide, or propylene oxide. Ring-opening polymerized hydroxyl containing compounds, and the like to.

(Monomer component m7)
The polymer M may contain the monomer component m7 which is a vinyl compound having a 3- to 5-membered cyclic ether group as a monomer component.
The monomer component m7 (a vinyl compound having a 3- to 5-membered cyclic ether group) includes an oxirane ring (epoxy group) -containing polymerizable unsaturated compound, an oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound, and an oxolane ring. (Oxolanyl group) -containing polymerizable unsaturated compounds are included.

By including the monomer component m7 in the polymer M, it is possible to further improve the solvent resistance of the colored film formed using the first ink, the adhesion to the substrate, and the like.
Examples of the oxirane ring (epoxy group) -containing polymerizable unsaturated compound include oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, and 2-oxy Polymerizable unsaturated compounds containing an oxirane ring (monocyclic) such as ranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, etc. ((Meth) acrylic acid ester derivatives and the like); 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, Epoxy group-containing alicyclic rings such as 3,4-epoxycyclohexane rings such as-(3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate and 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds containing the formula carbocycle ((meth) acrylic acid ester derivatives and the like); 5,6-epoxy- such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate Polymerizable unsaturated compounds containing a 2-bicyclo [2.2.1] heptane ring (such as (meth) acrylic acid ester derivatives); epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5. 2.1.0 ^2,6] decan-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2, ] Decan-8-yl (meth) acrylate or mixtures thereof,], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decan-9-yloxy) ethyl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate, or these Mixture], 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane ring such as epoxidized dicyclopentenyloxybutyl (meth) acrylate, epoxidized dicyclopentenyloxyhexyl (meth) acrylate, etc. Examples thereof include polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives). As another oxirane ring (epoxy group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, an aromatic vinyl compound containing an epoxy group, or the like can also be used. Examples of the aromatic vinyl compound containing an epoxy group include styrene derivatives such as 4-vinylbenzylglycidyl ether, 4-vinylbenzyloxirane, 4-vinylphenethyloxirane.

Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3- Methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl -3-Oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meta ) Acrylate, 3-[(3-Methyl-3-oxetanyl) methyloxy] propyl Pill (meth) acrylate, 3 - and [(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, vinyl ether compounds containing oxetanyl group, allyl ether compounds containing oxetanyl group.
Examples of the oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound include tetrahydrofurfuryl (meth) acrylate, vinyl ether compounds containing an oxolanyl group, and allyl ether compounds containing an oxolanyl group.

When the polymer M includes the monomer component m7 as described above, a 3- to 5-membered cyclic ether group (oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxolanyl group)) is Acts as a curable group. The 3- to 5-membered cyclic ether group mainly contributes to improvement of chemical resistance (solvent resistance, alkali resistance, etc.).
When the polymer M contains at least one monomer component selected from the group consisting of the monomer components m4, m5, m6 and m7 in addition to the monomer components m1, m2 and m3, The total content of the monomer components m4, m5, m6 and m7 in the polymer M is preferably 60 wt% or less, more preferably 50 wt% or less, and further preferably 40 wt% or less. preferable. Thereby, the effect by including the monomer components m4, m5, m6, and m7 is exhibited while the effect by including the monomer components m1, m2, and m3 described above is sufficiently exhibited.

The weight average molecular weight of the polymer M is preferably 500 or more and 100,000 or less, more preferably 1000 or more and 40000 or less, and further preferably 2000 or more and 30000 or less. As a result, the contrast ratio and brightness of the color filter manufactured using the color filter ink set can be made particularly excellent, and the durability of the color filter can be made particularly excellent. Further, the storage stability (long-term stability) of the first ink, the ejection stability, the solvent resistance of the formed colored film, and the like can be made excellent.
Further, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer M is preferably 1 or more and 3 or less.

When the first ink contains the polymer M, the content of the polymer M in the first ink is preferably 0.1 wt% or more and 5.5 wt% or less, and 0.2 wt% or more and 4. More preferably, it is 5 wt% or less. Thereby, the effect by including the polymer M can be more effectively exhibited while fully exhibiting the functions of other components.
Further, the first ink may include a polymer component other than the polymer M (hereinafter referred to as “other polymer component”). When the other polymer component is included, the other polymer component contained in the first ink is preferably 3.0 wt% or less, and more preferably 2.0 wt% or less. Thereby, the effect of this invention can be exhibited reliably.

<Dispersant>
The dispersant is a component that contributes to improving the dispersibility of the pigment particles. By including the dispersant in the first ink, it is possible to improve the storage stability of the first ink and the discharge stability of the droplets of the first ink.
In particular, the first ink preferably contains an acid value dispersant having a predetermined acid value and an amine value dispersant having a predetermined amine value as a dispersant. As a result, the effect of the acid value dispersant that exhibits the viscosity reduction effect that lowers the viscosity of the ink is compatible with the effect of the amine value dispersant that stabilizes the viscosity of the ink, and the dispersion of the pigment in the first ink is achieved. The stability can be made particularly excellent, and the discharge stability of the first ink droplet can be made particularly excellent. Further, the coexistence of the acid value dispersant and the amine value dispersant in the first ink improves the dispersion stability of the pigment in the first ink and the ejection stability of the droplets of the first ink. Although it is excellent, after removing the first liquid medium from the first ink to form a colored film, the colored film can have particularly excellent solvent resistance. This constituent material is difficult to elute into the second ink, and the flatness of the surface of the colored film formed using the first ink can be made particularly excellent. As a result, the contrast of an image displayed using the obtained color filter can be made particularly excellent.

[Acid value dispersant]
As described above, the acid value dispersant has a predetermined acid value (excluding zero).
The acid value (acid value when converted to solid content) of the acid value dispersant is not particularly limited, but is preferably 5 KOHmg / g or more and 370 KOHmg / g or less, and preferably 20 KOHmg / g or more and 270 KOHmg / g or less. More preferably, it is 30 KOHmg / g or more and 135 KOHmg / g or less. When the acid value of the acid value dispersant is within the above range, the synergistic effect due to the combined use with the amine value dispersant is more remarkably exhibited. The acid value of the dispersant can be determined by a method based on DIN EN ISO 2114, for example.
Note that the acid value dispersant does not have a predetermined amine value, that is, the amine value is zero.

  Specific examples of the acid value dispersant include Dispersic P104, Dispersic P104S, Dispersic 220S, Dispersic 110, Dispersic 111, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 2095 (above, BYK Chemie) EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, EFKA 7554 (manufactured by Ciba Specialty Co., Ltd.); (Above, manufactured by Lubrizol), Hinoact KF-1000 (Kawaken Fine Chemi) Le Co., Ltd.). In addition, it cannot be overemphasized that the acid value dispersing agent applied to this invention is not limited to what was illustrated.

[Amine value dispersant]
As described above, the amine value dispersant has a predetermined amine value (excluding zero).
The amine value (amine value when converted to solid content) of the amine value dispersant is not particularly limited, but is preferably 5 KOH mg / g or more and 200 KOH mg / g or less, and preferably 25 KOH mg / g or more and 170 KOH mg / g or less. More preferably, it is 30 KOHmg / g or more and 130 KOHmg / g or less. When the amine value of the amine value dispersant is within the above range, the synergistic effect due to the combined use with the acid value dispersant is more remarkably exhibited. The amine value of the dispersant can be determined by a method based on DIN 16945, for example.
The amine value dispersant does not have a predetermined acid value, that is, the acid value is zero.

  Specific examples of the amine value dispersant include Dispersic 102, Dispersic 160, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 164, Dispersic 166, Dispersic 167, Dispersic 168, Dispersic 2150, Dispersic LPN6919, Dispersic 9075, Dispersic 9077 (above, manufactured by BYK Chemie); EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4080, EFKA 4080 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4 03, EFKA 4800 (above, manufactured by Ciba Specialty); Addisper PB711 (above, manufactured by Ajinomoto Fine-Techno); Anti-Terra-205 (produced by Big Chemie), KF-1525, Hinoact 1300M, Hinoact T9050, Hinoact T6000, Hinoact T7000, Hinoact T8000, Hinoact T8000E (manufactured by Kawaken Fine Chemical Co., Ltd.) and the like. In addition, it cannot be overemphasized that the amine number dispersing agent applied to this invention is not limited to what was illustrated.

When the content of the acid value dispersant in the first ink is C _A [wt%] and the content of the amine value dispersant in the first ink is C _B [wt%], 0.1 ≦ C _It is preferable to satisfy the relationship of _A 1 / C _B ≦ 1, and it is more preferable to satisfy the relationship of 0.15 ≦ C _A / C _B ≦ 0.5. By satisfying such a relationship, the synergistic effect by using the acid value dispersant and the amine value dispersant in combination is more remarkably exhibited.

The acid value of the acid value dispersant is AV [KOH mg / g], the amine value of the amine value dispersant is BV [KOH mg / g], the content of the acid value dispersant is C _A [wt%], the amine When the content of the valent dispersant is C _B [wt%], it is preferable to satisfy the relationship of 0.01 ≦ (AV × C _A ) / (BV × C _B ) ≦ 1.9, 0.10 More preferably, the relationship of ≦ (AV × C _A ) / (BV × C _B ) ≦ 0.95 is satisfied. By satisfying such a relationship, the synergistic effect by using the acid value dispersant and the amine value dispersant in combination is more remarkably exhibited.

[Other dispersants]
The first ink may contain a dispersant other than an acid value dispersant and an amine value dispersant. That is, the first ink may contain a dispersant having both an acid value and an amine value of zero.
Specific examples of such a dispersant include Dispersic 101, Dispersic 103, Dispersic 106, Dispersic 108, Dispersic 109, Dispersic 112, Dispersic 116, Dispersic 140, Dispersic 142, Disperse. Big 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2050, Dispersic 2070 (above, manufactured by BYK Chemie); EFKA 4008, EFKA 4009, EFKA 4010 , EFKA 4406, EFKA 4408, EFKA 4015 (above, manufactured by Ciba Specialty); Solsperse 90 0, Sol Sparse 13000, Sol Sparse 20000, Sol Sparse 21000, Sol Sparse 24000, Sol Sparse 26000, Sol Sparse 27000, Sol Sparse 28000, Sol Sparse 32000, Sol Sparse 32500, Sol Sparse 32550, Sol Sparse 33500, Sol Sparse 35100, Sol Sparse 35200, Sol Sparse 38500, Sol Sparse 200000, Sol Sparse 200000 As mentioned above, manufactured by Lubrizol); Ajisper PA111, Azisper PB821, Azisper PB822, Azisper PB824 (Ajinomoto Fine Techno Co., Ltd.); Disparon 1850, Disparon 1860, Disparon 2150, Disparon 7004, Disparon DA-100, Disparon A-234, Disparon DA-325, Disparon DA-375, Disparon DA-705, Disparon DA-725, Disparon PW-36 (manufactured by Enomoto Kasei Co., Ltd.); and FLOREN DOPA-14, FLOREN DOPA-15B, FLOREN DOPA-17, Floren DOPA-22, Floren DOPA-44, Floren TG-710, Floren D-90 (manufactured by Kyoei Chemical Co., Ltd.), etc. Can be used. However, when such a dispersant (other dispersant) is included, the content ratio (the sum of the contents when plural kinds of “other dispersants” are included) is the content ratio of the acid value dispersant, and The content is preferably less than the content of the amine value dispersant. Thereby, the effect by using an acid value dispersing agent and an amine value dispersing agent together is more reliably exhibited.
The content of the dispersant in the first ink is not particularly limited, but is preferably 0.5 wt% or more and 10.2 wt% or less, more preferably 0.6 wt% or more and 8.0 wt% or less. .

<Other ingredients>
Although the 1st ink should just contain a coloring agent and a 1st liquid medium, it may contain further components (other components) other than the above.
Examples of such components include various crosslinking agents, thermal acid generators, photoacid generators, various polymerization initiators, acid crosslinking agents, surfactants, sensitizers, light stabilizers, various dispersants, and light emitting materials. , Leveling agents, antioxidants, ultraviolet absorbers, adhesion improvers, various polymerization accelerators, various light stabilizers, ceramics such as glass, zirconia, alumina, titanium oxide, adhesion promoters, ultraviolet absorbers, aggregation prevention An agent or the like can be used.

A leveling agent smoothes the surface of the 1st ink provided in the cell by reducing the surface tension of the 1st ink, and flattens a colored film. For this reason, when the first ink has the leveling agent, the surface of the first ink in the cell can be made flat. For this reason, the colored film to be formed is flat.
Examples of the leveling agent include acrylic leveling agents, vinyl ether leveling agents, silicone leveling agents, fluorine-silicon leveling agents, and acetylene glycol leveling agents. Among such leveling agents, acrylic leveling agents, vinyl ether leveling agents, and acetylene glycol leveling agents are preferably used. In particular, it is preferable to use one or more selected from Surfinol DF-58, LHP-95, LHP-90, and LF1970 in combination. Thereby, the surface of the formed colored film is further flattened, and the obtained color filter has particularly small color unevenness and density unevenness at each part.

The antioxidant can prevent deterioration of the first ink due to oxidation or the like, and can prevent deterioration of the colorant or the like due to heat or light in the colored film formed by the first ink.
Examples of the antioxidant include various phosphorus-based antioxidants, various sulfur-based antioxidants, various hindered phenol-based antioxidants, various antioxidants such as various hindered amine-based antioxidants, and the like. Among these, it is preferable to use at least one of a hindered amine antioxidant and a hindered phenol antioxidant, more preferably a hindered phenol antioxidant, and even more preferably TINUVIN152. Such an antioxidant suitably prevents deterioration of the first ink and the colored film and does not easily affect the optical characteristics such as color, brightness, and contrast ratio in the formed colored film. is there.

  The viscosity of the first ink at 25 ° C. (viscosity measured using a vibration viscometer) is not particularly limited, but is preferably 4 mPa · s or more and 12 mPa · s or less, preferably 5 mPa · s or more and 11 mPa · s. The following is more preferable. When the viscosity of the first ink is within the above range, clogging in the droplet discharge head is performed while the variation in the appropriate amount of the first ink discharged is particularly small in droplet discharge by the inkjet method. Occurrence and the like can be prevented more reliably. In addition, the measurement of the viscosity of the first ink (the same applies to the second ink described later) can be performed using, for example, a vibration viscometer, and can be performed in particular according to JIS Z8809.

<< second ink >>
Next, the second ink constituting the color filter ink set will be described.
The second ink includes a monomer component x1 represented by the above formula (11), a monomer component x3 represented by the above formula (13), and a monomer component x4 represented by the following formula (14). A curable resin material containing a polymer X containing a monomer component y1 represented by the following formula (15), and a second material that disperses and / or dissolves the curable resin material. And a liquid medium. By using such a second ink, a resin film composed of a resin material can be formed on the surface of the colored film formed using the first ink described above, and the surface of the colored portion (The surface of the resin film) can be made particularly excellent in flatness, the display image of the produced color filter is excellent in brightness and contrast ratio, and the occurrence of uneven color and uneven density is suppressed. can do. Moreover, the durability of the manufactured color filter can be made excellent. Further, by forming a resin film separately from the colored film, the solvent resistance of the manufactured color filter, the voltage holding ratio of the liquid crystal layer of the liquid crystal display device including the color filter, and the like are particularly excellent. be able to. In addition, by containing the constituent material of the colored portion to be formed separately into two types of ink, it is possible to improve the ejection stability of the ink and to enable high-speed drawing by the inkjet method, The productivity of the color filter can be made particularly excellent.

  The effect as described above is that the content of the colorant in the resin film formed by the second ink is lower than the content of the colorant in the color film formed by the first ink. In particular, it is more prominent by using a material that does not substantially contain a colorant as the second ink, and that it does not substantially contain a colorant in the resin film. Is done.

<Curable resin material>
The second ink includes a curable resin material (binder resin).
The curable resin material contained in the second ink contains a polymer X and a polymer Y as described below.
[Polymer X]
Polymer X includes monomer component x1 represented by formula (11), monomer component x3 represented by formula (13), and monomer component x4 represented by formula (14). Is included. Examples of the polymer X include those represented by the following formula (17).

  By including such a polymer X in the second ink, the flatness of the surface of the colored portion to be formed can be made particularly high. As a result, it is possible to more reliably prevent the occurrence of color unevenness, density unevenness, contrast, brightness reduction, and the like at each part of the color filter manufactured using the color filter ink set. Further, as a whole of the curable resin material constituting the second ink, the characteristic that the curing reaction is not allowed to proceed substantially at a predetermined temperature or less, and the curing reaction can be efficiently proceeded at a temperature higher than that (hereinafter, referred to as the following). It is also possible to make the color portion formed using the color filter ink set particularly excellent in solvent resistance, etc. The durability and reliability of the filter can be made particularly excellent. In addition, the voltage holding ratio (VHR) of the liquid crystal layer of the liquid crystal display device including the color filter can be improved. Further, by including the polymer X, the affinity and compatibility of each polymer component in the second ink (particularly the affinity and compatibility with the polymer Y described later) are sufficiently excellent. Therefore, while fully exhibiting the features of the polymer X, the discharge stability of the second ink is excellent, and the transparency of the resin film formed using the second ink is high. be able to.

  In addition, the polymer X may consist essentially of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer X is a mixture of a plurality of types of compounds, each compound contains monomer components x1, x3, and x4.

(Monomer component x1)
The polymer X contains the monomer component x1 represented by the formula (11) as a monomer component.
By containing such a monomer component x1 as a monomer component, an unintentional reaction (polymerization reaction) of the curable resin material during storage of the second ink or ejection of droplets can be reliably prevented. However, in the curing treatment performed in a heating environment, the curing reaction (polymerization reaction) of the curable resin material can be more suitably advanced. That is, by containing the monomer component x1, the switching characteristics of the curing reaction for the curable resin material can be made particularly excellent. In addition, by including the monomer component x1 as the monomer component, for example, the long-term storage stability and ejection stability of the second ink can be improved. Moreover, the hardness etc. of the resin film (colored part) formed can be made excellent by containing the monomer component x1 as a monomer component.

  The content of the monomer component x1 in the polymer X (a value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 30 wt% or more and 90 wt% or less, and 40 wt% or more. More preferably, it is 80 wt% or less. When the content of the monomer component x1 in the polymer X is a value within the above range, the above-described effects can be achieved without inhibiting the functions of the monomer components x2, x3, and x4 described in detail later. It can be expressed more significantly. On the other hand, if the content of the monomer component x1 in the polymer X is less than the lower limit value, the effect of including the monomer component x1 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x1 in the polymer X exceeds the upper limit, the content of the monomer components x2, x3, and x4 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. Further, the reaction rate of the polymer X at a high temperature decreases, and it becomes difficult to produce a color filter with sufficiently excellent productivity. In addition, when the polymer X is a mixture of plural kinds of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is adopted as the content value of the monomer component x1. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x1 at the content as described above.

(Monomer component x2)
The polymer X may contain the monomer component x2 represented by the following formula (12) as a monomer component.

By storing such a monomer component x2 as a monomer component (in particular, together with the monomer component x1 described above and the monomer component x3 described in detail later), the second ink is stored. The curing reaction (polymerization reaction) of the curable resin material is performed in a curing process in a heated environment while reliably preventing unintentional reaction (polymerization reaction) of the curable resin material during discharge or droplet discharge. It is possible to proceed more suitably. In particular, in the curing treatment under a heating environment, the rising of the polymerization reaction of the curable resin material can be improved, and the polymerization reaction can be continuously advanced. Moreover, by including the monomer component x2 as the monomer component, the hardness of the formed resin film (colored portion) can be made particularly excellent.
Examples of the polymer X containing the monomer component x2 as a monomer component include those represented by the following formula (19).

  The content of the monomer component x2 in the polymer X (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is preferably 5 wt% or more and 60 wt% or less, preferably 10 wt% or more. More preferably, it is 50 wt% or less. When the content of the monomer component x2 in the polymer X is a value within the above range, without inhibiting the functions of the monomer component x1 and the monomer components x3 and x4 described in detail later, The effects as described above can be expressed more remarkably. On the other hand, when the content of the monomer component x2 in the polymer X is less than the lower limit, the effect of including the monomer component x2 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x2 in the polymer X exceeds the upper limit, the content of the monomer components x1, x3, and x4 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. In addition, the reactivity of the polymer X at a relatively low temperature increases, and the storage stability of the second ink tends to decrease. In addition, when the polymer X is a mixture of a plurality of kinds of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component x2. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x2 at the above-described content.

(Monomer component x3)
The polymer X contains the monomer component x3 represented by the above formula (13) as a monomer component.
When the polymer X contains the monomer component x3 as the monomer component, the colored portion (resin film) to be formed can have particularly excellent chemical resistance, solvent resistance, and the like. Thereby, even if it is a case where post-processing, such as chemical | medical agent application | coating and washing | cleaning, is performed after a hardening process, generation | occurrence | production of the bad influence by these can be prevented reliably.

In addition, the monomer component x3 has a sufficiently low reactivity at a relatively low temperature (for example, 100 ° C. or lower) in the polymer X, similarly to the monomer component x1 described above. In a heating environment such as the heat treatment applied in step 1, it exhibits sufficient reactivity. For this reason, in the curing process performed in a heating environment while reliably preventing unintentional reaction (polymerization reaction) of the curable resin material at the time of storing the second ink or discharging the droplets, the curable resin The curing reaction (polymerization reaction) of the material can be suitably advanced.
Further, by including the monomer component x3 as the monomer component, for example, the long-term storage stability and ejection stability of the second ink can be made particularly excellent.

  The content of the monomer component x3 in the polymer X (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is preferably 2 wt% or more and 20 wt% or less, preferably 3 wt% or more. More preferably, it is 15 wt% or less. When the content of the monomer component x3 in the polymer X is a value within the above range, without inhibiting the functions of the monomer components x1 and x2 described above and the monomer component x4 described in detail later, The effects as described above can be expressed more remarkably. On the other hand, when the content of the monomer component x3 in the polymer X is less than the lower limit, the effect of including the monomer component x3 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x3 in the polymer X exceeds the upper limit, the content of the monomer components x1, x2, and x4 is relatively decreased, and these functions are not sufficiently exhibited. there is a possibility. In addition, the resin film formed using the second ink becomes too hard, and there is a tendency that followability with respect to deformation of the substrate or the like accompanying a temperature change is lowered. In addition, when the polymer X is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is adopted as the content value of the monomer component x3. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x3 with the content as described above.

(Monomer component x4)
The polymer X contains the monomer component x4 represented by the formula (14) as a monomer component.
By containing such a monomer component x4 as a monomer component, when forming the colored portion (resin film), when removing the second liquid medium from the second ink, the solid content concentration Along with the increase, the thixotropic property and viscosity of the second ink are increased, and it is possible to more reliably prevent the occurrence of unintended irregularities on the surface of the formed colored portion (resin film).

Moreover, the monomer component x4 has a hydroxyl group at the terminal. By having such a structure, the reactivity in a heating environment such as a curing process can be further enhanced while the reactivity at a relatively low temperature (for example, 100 ° C. or less) is sufficiently low. Accordingly, in the curing process performed in a heating environment, the curable resin is reliably prevented from unintentional reaction (polymerization reaction) of the curable resin material during storage of the second ink or droplet discharge. The curing reaction (polymerization reaction) of the material can proceed more suitably.
In addition, by including the monomer component x4 as the monomer component, for example, the long-term storage stability and ejection stability of the second ink can be made particularly excellent.

  The content of the monomer component x4 in the polymer X (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is preferably 2 wt% or more and 20 wt% or less, preferably 3 wt% or more. More preferably, it is 15 wt% or less. When the content of the monomer component x4 in the polymer X is a value within the above range, the above-described effects are more remarkable without inhibiting the functions of the monomer components x1, x2, and x3. Can be expressed. On the other hand, when the content of the monomer component x4 in the polymer X is less than the lower limit, the effect due to the inclusion of the monomer component x4 may not be sufficiently exhibited. On the other hand, when the content of the monomer component x4 in the polymer X exceeds the upper limit, the content of the monomer components x1, x2, and x3 is relatively lowered, and these functions are not sufficiently exhibited. there is a possibility. Moreover, the tendency for the hardness of the resin film (colored part) formed using the second ink to decrease appears. In addition, when the polymer X is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) of these compounds is used as the content value of the monomer component x4. can do. Moreover, when the polymer X is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component x4 with the content as described above.

The polymer X may include a monomer component (other monomer component) other than the monomer components x1, x2, x3, and x4 described above. Thereby, for example, the effects derived from the chemical structures of other monomer components can be obtained while exhibiting the above-described characteristics.
When the polymer X contains other monomer components (monomer components other than the monomer components x1, x2, x3, x4), the content of other monomer components in the polymer X ( When a plurality of other monomer components are included, the sum of these contents) is preferably 15 wt% or less, and more preferably 10 wt% or less.

The weight average molecular weight of the polymer X is preferably 1000 or more and 50000 or less, more preferably 1200 or more and 10,000 or less, and further preferably 1500 or more and 5000 or less. As a result, the temporal stability (long-term storage stability) of the second ink and the ejection stability of the second ink can be made particularly excellent, and the productivity of the color filter can be made sufficiently excellent. Furthermore, the flatness of the colored portion (resin film) formed using the second ink can be made more reliable, and color unevenness or the like in the image displayed using the color filter can be generated. It can prevent more effectively.
Further, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer X is preferably 1 or more and 3 or less.

[Polymer Y]
The polymer Y contains the monomer component y1 represented by the above formula (15). Examples of the polymer Y include those represented by the following formula (18).

By including such a polymer Y, while making the ejection stability of the second ink excellent, it is possible to particularly improve the adhesion to the partition walls of the resin film, the solvent resistance, The durability and reliability of the manufactured color filter can be made particularly excellent. In addition, the voltage holding ratio (VHR) of the liquid crystal layer of the liquid crystal display device including the color filter can be improved.
The polymer Y may be substantially composed of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer Y is a mixture of a plurality of types of compounds, each compound contains the monomer component y1.

(Monomer component y1)
The polymer Y contains the monomer component y1 represented by the formula (15) as a monomer component.
By containing such a monomer component y1 as the monomer component, the adhesion of the formed resin film to the partition walls and the like can be made particularly excellent. As a result, the durability of the color filter can be made particularly excellent.

  The content of the monomer component y1 in the polymer Y (value obtained by conversion in terms of the weight of the monomer used for polymer synthesis) is preferably 30 wt% or more and 90 wt% or less, and 40 wt% or more. More preferably, it is 80 wt% or less. When the content of the monomer component y1 in the polymer Y is a value within the above range, for example, when the polymer Y includes the monomer component y2 described in detail later as the monomer component, the unit The effects as described above can be expressed more significantly without inhibiting the function of the monomer component y2. On the other hand, when the content of the monomer component y1 in the polymer Y is less than the lower limit value, the effect of including the monomer component y1 may not be sufficiently exhibited. On the other hand, when the content of the monomer component y1 in the polymer Y exceeds the upper limit, for example, when the polymer Y includes the monomer component y2 described in detail later as the monomer component, Accordingly, the content of the monomer component y2 may be reduced, and the function of the monomer component y2 may not be sufficiently exhibited. Further, when the colored liquid (resin film) is formed, when the second liquid medium is removed from the second ink, the tendency of the viscosity of the second ink to increase as the solid content concentration increases, Involuntary unevenness is likely to occur on the surface of the colored portion (resin film) to be formed. In addition, when the polymer Y is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component y1. can do. Moreover, when the polymer Y is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component y1 at the content as described above.

(Monomer component y2)
The polymer Y may contain the monomer component y2 represented by the following formula (16) as a monomer component.

  By containing such a monomer component y2 as a monomer component (particularly, together with the monomer component y1 described above), curability at the time of storing the second ink, discharging a droplet, or the like. In the curing treatment performed in a heated environment, the curing reaction (polymerization reaction) of the curable resin material can be suitably advanced while preventing the unintentional reaction (polymerization reaction) of the resin material more reliably. In particular, in the curing treatment under a heating environment, the rising of the polymerization reaction of the curable resin material can be improved, and the polymerization reaction can be continuously advanced. Moreover, the hardness etc. of the resin film (colored part) formed can be made excellent by containing the monomer component y2 as a monomer component.

Further, when the polymer Y contains the monomer component y2, the affinity and compatibility with the polymer X described above can be sufficiently improved. As a result, even when the second ink contains the polymer X together with the polymer Y, the discharge stability of the second ink can be made excellent, and the second ink can be used. The formed resin film is excellent in transparency (a reduction in light transmittance due to the opacity of the curable resin material is prevented), particularly excellent in adhesion to the partition walls and the like, and is less prone to problems such as cracks. On the other hand, if the monomer component y2 is not included as a monomer component, when the polymer X is included, it becomes difficult to sufficiently improve the affinity and compatibility with the polymer X. The second ink is inferior in ejection stability, and the produced color filter is liable to have uneven color and has sufficiently excellent contrast, durability and reliability. It can be difficult.
An example of the polymer Y containing the monomer component y2 as a monomer component is represented by the following formula (20).

  The content of the monomer component y2 in the polymer Y (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 10 wt% or more and 70 wt% or less, and more preferably 20 wt% or more. More preferably, it is 60 wt% or less. When the content of the monomer component y2 in the polymer Y is a value within the above range, the above-described effects can be expressed more significantly without inhibiting the function of the monomer component y1 described above. Can do. On the other hand, when the content of the monomer component y2 in the polymer Y is less than the lower limit value, the effect of including the monomer component y2 may not be sufficiently exhibited. On the other hand, when the content of the monomer component y2 in the polymer Y exceeds the upper limit, the content of the monomer component y1 is relatively lowered, and the function of the monomer component y1 is not sufficiently exhibited. there is a possibility. In addition, the reactivity of the polymer Y at a relatively low temperature increases, and the storage stability of the second ink tends to decrease. In addition, when the polymer Y is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the monomer component y2. can do. Moreover, when the polymer Y is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the monomer component y2 with the content as described above.

In addition, the polymer Y may contain monomer components (other monomer components) other than the monomer components y1 and y2 described above. Thereby, for example, the effects derived from the chemical structures of other monomer components can be obtained while exhibiting the above-described characteristics.
When the polymer Y contains other monomer components (monomer components other than the monomer components y1 and y2), the content of other monomer components in the polymer Y (multiple types of other components) In the case where the monomer component is included, the sum of these contents) is preferably 15 wt% or less, and more preferably 10 wt% or less.

The weight average molecular weight of the polymer Y is preferably 1000 or more and 50000 or less, more preferably 1200 or more and 10,000 or less, and further preferably 1500 or more and 5000 or less. As a result, the temporal stability (long-term storage stability) of the second ink and the ejection stability of the second ink can be made particularly excellent, and the productivity of the color filter can be made sufficiently excellent. Furthermore, the flatness of the resin film formed using the second ink can be made more reliable, and the occurrence of color unevenness and the like in the image displayed using the color filter can be more effectively achieved. Can be prevented.
Moreover, it is preferable that the dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the polymer Y is 1 or more and 3 or less.

[Copolymer N]
The curable resin includes an alkoxysilyl group-containing vinyl monomer component n1 represented by the following formula (21), a vinyl monomer component n2 having a cyclic ether group of 3 to 5 members, and a side chain. A copolymer N containing a hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymerization chain portion may be contained.

This copolymer N has a high affinity with the polymer X and the polymer Y described above. For this reason, the compatibility of the said polymer X and the said polymer Y can be made excellent by including such a copolymer N. FIG. As a result, the effects as described above due to the inclusion of each of the polymer X and the polymer Y can be made more remarkable.
By the way, in the polymer Y, the alkoxyl group in the molecule may be modified by moisture absorbed in the colored film, moisture in the air, etc., and the compatibility with the polymer X may be reduced. . Thus, when compatibility of the polymer X and the polymer Y falls, each will isolate | separate in a resin film, and the effect which planarizes each coloring part of the polymer X and the polymer Y will be impaired. There's a problem. However, even if the polymer Y is modified as described above due to the effect of preventing moisture absorption into the colored film by having the cooling step as described above, and the copolymer N being included, Due to the synergistic effect with the effect of preventing the compatibility between the polymer X and the polymer Y from being lowered, the flatness of the formed colored portion can be made higher.
In addition, by including the copolymer N, the adhesion of the resin film to the partition walls, the solvent resistance and the heat resistance can be made particularly excellent, and the transparency of the resin film is made higher. Can do.

(Vinyl monomer component n1)
The copolymer N contains the alkoxysilyl group-containing vinyl monomer component n1 represented by the above formula (21) as a monomer component.
By including such an alkoxysilyl group-containing vinyl monomer component n1 as a monomer component, the copolymer N has higher affinity for the polymer X and the polymer Y. As a result, it is possible to prevent a decrease in the compatibility between the polymer X and the polymer Y.

  Examples of the alkyl group having 1 to 7 carbon atoms in R1 of the above formula (21) include straight chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl group, etc. Examples thereof include a branched alkyl group. Among these, a methyl group and an ethyl group are preferable. R1 is particularly preferably a hydrogen atom or a methyl group.

  Examples of the divalent hydrocarbon group in A in the above formula (21) include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, Examples thereof include an arylene group such as a phenylene group, a cycloalkylene group such as a cyclohexylene group, and a group in which two or more of these are bonded. Among these, a linear or branched alkylene group having 1 to 6 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, and propylene groups is more preferable. preferable.

  Examples of the alkyl group having 1 to 6 carbon atoms in R2, R3, and R4 in the above formula (21) include straight chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, and hexyl groups. Or a branched alkyl group. Among these, linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl groups are preferable.

Examples of the aryl group in R2 and R3 of the above formula (21) include phenyl and naphthyl groups.
Examples of the alkoxyl group having 1 to 6 carbon atoms in R2 and R3 of the above formula (21) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, pentoxy, hexyloxy groups and the like. A linear or branched alkoxyl group is mentioned.

Representative examples of the alkoxysilyl group-containing vinyl monomer n1 represented by the above formula (21) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- (Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- ( (Meth) acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxybutylphenyldimethoxysilane And alkoxysilyl group-containing polymerizable unsaturated compounds such as γ- (meth) acryloyloxybutylphenyldiethoxysilane, and the like. Among these, one kind or two or more kinds can be used in combination.
The content of the vinyl monomer component n1 in the copolymer N is preferably 1 wt% or more and 95 wt% or less, more preferably 10 wt% or more and 90 wt% or less, and 20 wt% or more and 85 wt% or less. Is more preferable. Thereby, the effect by including the vinyl monomer component n1 as a monomer component can be exhibited more efficiently.

(Vinyl monomer component n2)
The copolymer N contains a vinyl monomer component n2 having a cyclic ether group of 3 to 5 members as a monomer component.
By including such a vinyl monomer component n2 as a monomer component, the resulting resin film is improved in solvent resistance and excellent in mechanical strength.

In the copolymer N, the vinyl monomer component n2 having a cyclic ether group of 3 to 5 members includes an oxirane ring (epoxy group) -containing polymerizable unsaturated compound and an oxetane ring (oxetanyl group) -containing polymerizable compound. Saturated compounds and polymerizable unsaturated compounds containing an oxolane ring (oxolanyl group) are included.
Examples of the oxirane ring (epoxy group) -containing polymerizable unsaturated compound include oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, and 2-oxy Polymerizable unsaturated compounds containing an oxirane ring (monocyclic) such as ranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, etc. ((Meth) acrylic acid ester derivatives and the like); 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, Epoxy group-containing alicyclic rings such as 3,4-epoxycyclohexane rings such as-(3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate and 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds containing the formula carbocycle ((meth) acrylic acid ester derivatives and the like); 5,6-epoxy- such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate Polymerizable unsaturated compounds containing a 2-bicyclo [2.2.1] heptane ring (such as (meth) acrylic acid ester derivatives); epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5. 2.1.0 ^2,6] decan-9-yl (meth) acrylate; 3,4-epoxytricyclo [5.2.1.0 ^2, ] Decan-8-yl (meth) acrylate], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^2,6] decane-9 Yloxy) ethyl (meth) acrylate; 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate], epoxidized dicyclopentenyloxybutyl Polymerizable unsaturated compounds containing 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring such as (meth) acrylate and epoxidized dicyclopentenyloxyhexyl (meth) acrylate ((meth) Acrylic ester derivatives and the like). As another oxirane ring (epoxy group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, or the like can also be used.

  Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, ( 3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3 -Ethyl-3-oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (Meth) acrylate, 3-[(3-methyl-3-oxetanyl) methyloxy ] Propyl (meth) acrylate, 3 - [and (3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, vinyl ether compounds containing oxetanyl group, allyl ether compounds containing oxetanyl group.

Examples of the oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound include tetrahydrofurfuryl (meth) acrylate, vinyl ether compounds containing an oxolanyl group, and allyl ether compounds containing an oxolanyl group.
Among the above, the vinyl monomer component n1 is preferably an oxirane ring (epoxy group) -containing polymerizable unsaturated compound, and the epoxy group is formed on an alicyclic carbocycle (monocyclic or polycyclic). More preferred is a vinyl monomer containing an alicyclic epoxy group.

  The content of the vinyl monomer component n2 in the copolymer N is preferably 1 wt% or more and 95 wt% or less, more preferably 5 wt% or more and 80 wt% or less, and 12 wt% or more and 70 wt% or less. Is more preferable. Thereby, the effect by including the vinyl monomer component n2 as a monomer component can be exhibited more efficiently.

(Vinyl monomer component n3)
The copolymer N contains a hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymerization chain portion in the side chain as a monomer component.
By including such a monomer component n3, the compatibility of the polymer N with the polymer X and the polymer Y can be further improved. Further, the viscosity of the second ink can be made suitable, and the ejection stability of the second ink can be made excellent.

  Examples of the hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymerization chain portion in the side chain include monoesterified products of polyhydric alcohol and acrylic acid or methacrylic acid [for example, 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc.] and a compound obtained by ring-opening polymerization of ε-caprolactone (6-hexanolide addition polymer, degree of polymerization of ε-caprolactone is about 1 to 6).

As a representative example of the hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymerization chain portion in the side chain, a 6-hexanolide addition polymer of 2-hydroxyethyl (meth) acrylate (degree of polymerization of 1 to 6) And the like) (Placcel FA series, Plaxel FM series, etc., manufactured by Daicel Chemical Industries, Ltd.).
In the copolymer N, the vinyl monomer component n1, the vinyl monomer component n2, and the vinyl monomer component n3 may each be one type or may be two or more types.

The content of the vinyl monomer component n3 in the copolymer N is preferably 0.1 wt% or more and 95 wt% or less, more preferably 0.2 wt% or more and 50 wt% or less, and 0.2 wt%. It is preferably 30 wt% or less. Thereby, the effect by including the vinyl monomer component n3 as a monomer component can be exhibited more efficiently.
The total content of the vinyl monomer n1, the vinyl monomer n2, and the vinyl monomer n3 in the copolymer N is preferably 40 wt% or more and 100 wt% or less, and is 50 wt% or more and 100 wt% or less. More preferably, it is 60 wt% or more and 100 wt% or less, more preferably 80 wt% or more and 100 wt% or less.

Moreover, as a monomer component which comprises the copolymer N, components other than the said vinyl monomer component may be contained.
Examples of the monomer component other than the vinyl monomer component include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, and (meth) acrylic acid aralkyl. Examples thereof include esters, aromatic vinyl compounds, hydroxyl group-containing monomers [(meth) acrylic acid hydroxyalkyl esters], carboxyl group or acid anhydride group-containing monomers.

The weight average molecular weight of the copolymer N is preferably 500 or more and 100,000 or less, more preferably 1000 or more and 40000 or less, and further preferably 2000 or more and 30000 or less. As a result, the temporal stability (long-term storage stability) of the second ink and the ejection stability of the second ink can be made particularly excellent, and the productivity of the color filter can be made sufficiently excellent. Furthermore, the flatness of the resin film formed using the second ink can be made more reliable, and the occurrence of color unevenness and the like in the image displayed using the color filter can be more effectively achieved. Can be prevented.
Moreover, it is preferable that the dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer N is about 1-3.

  The content of the curable resin material described above in the second ink is preferably 2.0 wt% or more and 30.0 wt% or less, and more preferably 3.0 wt% or more and 28.0 wt% or less. As a result, the surface of the formed resin film has a higher flatness while suppressing the increase in the viscosity of the second ink, and the discharge property of the second ink from the droplet discharge head is particularly excellent. It can be. Further, the thickness of the formed resin film can be easily adjusted.

Further, the curable resin material constituting the second ink may include a polymer other than those described above. For example, the second ink may include the polymer M described as the constituent component of the first ink described above. Thereby, the flatness of the surface of the colored part (resin film) can be made higher, and the contrast, brightness, etc. of the display image of the produced color filter can be made particularly excellent.
Further, the second ink may include various thermoplastic resins in addition to the curable resin material.

<Second liquid medium>
The second liquid medium (second liquid medium) has a function of dispersing and / or dissolving the polymer M as described above. That is, the second liquid medium functions as a dispersion medium and / or a solvent. Usually, most of the second liquid medium is removed in the process of manufacturing the color filter.
Although it does not specifically limit as a liquid which comprises a 2nd liquid medium, For example, what was mentioned by the 1st liquid mentioned above can be used.

  Among the above, the second liquid medium is propylene glycol-n-butyl ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate, ethyl 3-ethoxypropionate, bis (2-butoxy). It is preferable to include one or more selected from ethyl) ether, diethylene glycol monobutyl ether acetate, and 1,3-butylene glycol diacetate. Thereby, the droplet discharge property of the second ink can be made particularly excellent, and the productivity of the color filter can be made particularly excellent. Further, it is possible to more reliably prevent the colorant from diffusing into the second ink (resin film) from the colored film formed from the first ink. As a result, it is possible to more effectively prevent a decrease in brightness and contrast ratio, color unevenness and density unevenness, and a good voltage holding ratio (VHR) of a liquid crystal layer of a liquid crystal display device provided with a color filter. Can be.

  The content ratio of the second liquid medium in the second ink is preferably 40 wt% or more and 99 wt% or less, and more preferably 60 wt% or more and 95 wt% or less. When the content of the second liquid medium is a value within the above range, the discharge property of the second ink from the droplet discharge head is particularly excellent, and the thickness of the colored portion of the color filter to be manufactured Can be made more uniform. For this reason, the obtained color filter is one in which density unevenness and color unevenness in each part are particularly effectively suppressed, and when used in an image display device, a particularly clear image can be displayed. .

  The viscosity at 25 ° C. of the second liquid medium is not particularly limited, but is preferably 1.0 mPa · s or more and 4.0 mPa · s or less, and is 1.5 mPa · s or more and 3.5 mPa · s or less. Is more preferable. When the viscosity of the second liquid medium at 25 ° C. is a value within the above range, the discharge property of the second ink from the droplet discharge head is particularly excellent, and the coloring portion of the produced color filter The thickness uniformity can be made higher. For this reason, the obtained color filter is one in which density unevenness and color unevenness in each part are particularly effectively suppressed, and when used in an image display device, a particularly clear image can be displayed. .

  Further, the viscosity at 25 ° C. of the second ink constituting the color filter ink set is preferably 2.0 mPa · s or more and 9.0 mPa · s or less, and preferably 3.0 mPa · s or more and 7. It is more preferably 0 mPa · s or less. This makes it possible to more reliably prevent clogging and the like in the droplet discharge head while making the variation in the droplet amount of the second ink to be discharged particularly small in the droplet discharge by the inkjet method as will be described later. can do. As a result, the obtained color filter can further improve the uniformity of each colored portion, and can display a particularly clear image when used in an image display device.

  Further, the second ink may contain components other than those described above. Examples of such components include the components exemplified in the other components as the constituent components of the first ink. For example, the second ink may contain a colorant, but preferably does not contain the colorant. When the second ink contains a colorant, the content of the colorant contained in the second ink is preferably 0.5 wt% or less, and more preferably 0.2 wt% or less. .

<Image display device>
Next, a preferred embodiment of a liquid crystal display device that is an image display device (electro-optical device) having the color filter 1 will be described.
FIG. 4 is a cross-sectional view showing a preferred embodiment of the liquid crystal display device. As shown in the figure, the liquid crystal display device 60 includes a color filter 1, a substrate (opposite substrate) 66 disposed on the side of the color filter 1 on which the colored portion 12 is provided, a color filter 1 and a substrate 66. And a polarizing plate 67 provided on the side opposite to the surface of the substrate 11 of the color filter 1 facing the liquid crystal layer 62 (lower side in FIG. 4). And a polarizing plate 68 provided on the side of the substrate 66 opposite to the surface facing the liquid crystal layer 62 (upper side in FIG. 4). A common electrode 61 is provided on the surface of the color filter 1 on which the colored portion 12 and the partition wall 13 are provided (the surface opposite to the surface of the colored portion 12 and the partition wall 13 facing the substrate 11). On the surface of the (opposite substrate) 66 facing the liquid crystal layer 62 and the color filter 1, pixel electrodes 65 are arranged in a matrix at positions corresponding to the colored portions 12 of the color filter 1. Further, an alignment film 64 is provided between the common electrode 61 and the liquid crystal layer 62, and an alignment film 63 is provided between the substrate 66 (pixel electrode 65) and the liquid crystal layer 62.

The substrate 66 is a substrate having optical transparency with respect to visible light, and is, for example, a glass substrate.
The common electrode 61 and the pixel electrode 65 are made of a material having optical transparency to visible light, and are made of, for example, ITO.
Thus, in the liquid crystal display device 60 provided with the color filter 1, each coloring part 12 which comprises the color filter 1 has a uniform thickness. In the liquid crystal display device 60 provided with such a color filter 1, the height difference (step) between the colored portions 12 and the partition walls 13 is uniform throughout the color filter 1. Therefore, the common electrode 61 is difficult to be disconnected, and the liquid crystal display device 60 can perform image display reliably and appropriately. Further, even when heat or an external impact is applied to the liquid crystal display device 60, it is possible to reliably prevent problems such as disconnection of the common electrode 61 disposed on the liquid crystal layer 62 side of the color filter 1. Therefore, the durability of the liquid crystal display device 60 is excellent. Further, the color filter 1 of the liquid crystal display device 60 does not have a flattening film that covers the entire surface of the substrate 11 on the partition wall 13, and therefore can irradiate light only on a target colored portion with certainty. It becomes. As a result, the liquid crystal display device can widen the color reproduction range, and can appropriately display an image with a clear shape, color tone, and the like.

  Although omitted in the drawing, a plurality of switching elements (for example, TFTs: thin film transistors) are provided so as to correspond to the respective pixel electrodes 65. For each pixel electrode 65 corresponding to each coloring portion 12, by controlling the voltage application state between the common electrode 61, in the region corresponding to each coloring portion 12 (each pixel electrode 65), Light transmittance can be controlled.

In the liquid crystal display device 60, light emitted from a backlight (not shown) enters from the polarizing plate 68 side (upper side in FIG. 4). And the light which permeate | transmitted the liquid crystal layer 62 and entered into each coloring part 12 (12A, 12B, 12C) of the color filter 1 is polarized as light of the color corresponding to each coloring part 12 (12A, 12B, 12C). The light is emitted from the plate 67 (lower side in FIG. 4).
Since the liquid crystal display device 60 includes the color filter 1 manufactured by using the color filter ink set and method of the present invention as described above, the occurrence of color unevenness, density unevenness, etc. is prevented, and brightness and An image having an excellent contrast ratio can be stably displayed over a long period of time.

"Electronics"
An image display device (electro-optical device) 1000 such as a liquid crystal display device having the color filter 1 as described above can be used for display portions of various electronic devices.
FIG. 5 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 having a keyboard 1102 and a display unit 1106. The display unit 1106 is supported by the main body 1104 via a hinge structure so as to be rotatable. Yes.
In the personal computer 1100, the display unit 1106 includes an image display device 1000.

FIG. 6 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 is provided with an image display device 1000 in a display unit, together with a plurality of operation buttons 1202, an earpiece 1204, and a mouthpiece 1206.
FIG. 7 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.

Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an image sensor such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.
On the back of the case (body) 1302 in the digital still camera 1300, an image display device 1000 is provided in the display unit, and is configured to display based on an imaging signal from the CCD, and a finder that displays a subject as an electronic image. Function as.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

The electronic apparatus of the present invention includes, for example, a television (for example, a liquid crystal television), a video camera, a viewfinder type, a monitor in addition to the above-described personal computer (mobile personal computer), mobile phone, and digital still camera. Direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV monitor , Electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographic display devices, ultrasonic diagnostic devices, endoscopy) Mirror display device), Group detector, various measuring instruments, gages (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors such, can be applied to the projection type display device such as a projector. In particular, televisions have a remarkable tendency to increase the size of the display unit in recent years. However, in an electronic device having such a large display unit (for example, a display unit having a diagonal length of 80 cm or more), uneven color and uneven density are present. Although it tends to be conspicuous, the application of the present invention can surely prevent the occurrence of such a problem. That is, when applied to an electronic device having a large display unit as described above, the effects of the present invention are more remarkably exhibited.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

  For example, in the above-described embodiment, after the first ink corresponding to the colored portion of each color is applied to the cell, the first liquid medium is removed from the first ink in the cell at a time. That is, although the first liquid medium removing step is described as being performed only once, the first ink applying step and the first liquid medium removing step are repeatedly performed corresponding to each color. May be.

For example, the first ink application step and the second ink application step may each be performed a plurality of times.
In addition, each unit constituting the color filter, the image display device, and the electronic device can be replaced with an arbitrary one that exhibits the same function, or another configuration can be added.
In the above-described embodiment, the case where the color filter ink set includes the three types (three colors) of the first ink and the one type of second ink corresponding to the three primary colors of light has been mainly described. The numbers and types (colors) of the first ink and the second ink constituting the color filter ink set are not limited to those described above. For example, the color filter ink set of the present invention may include four or more types of first ink.

  In the above-described embodiment, the color filter ink set is described as including only one type of second ink, but may include a plurality of types of second ink. For example, the color filter ink set may include a plurality of types of second inks corresponding to the plurality of types of first inks, respectively, and the composition may be different for each second ink. In particular, by adjusting the content of the curable resin material for each second ink, the amount of the curable resin material to be applied to each second ink while making the discharge amounts of the plurality of second inks all the same Can be different. This makes it easier to set the discharge conditions during droplet discharge.

Next, specific examples of the present invention will be described.
[1] Synthesis of polymer (Synthesis Example 1)
In a reaction vessel (flask) equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, 100 parts by weight of diethylene glycol monobutyl ether acetate as a solvent (solvent) was added and heated to 80 ° C. Subsequently, 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylideneaminooxycarbonylaminoethyl) as the monomer component m1 was placed in the flask. ) Methacrylate): 60 parts by weight, methacrylic acid as monomer component m2: 20 parts by weight, stearyl methacrylate as monomer component m3: 20 parts by weight in diethylene glycol monobutyl ether acetate: 30 parts by weight It dropped in the flask over 4 hours using the dripping pump. On the other hand, a solution prepared by dissolving 5 parts by weight of azobisdimethylvaleronitrile as a radical initiator (polymerization initiator) in 90 parts by weight of diethylene glycol monobutyl ether acetate was added to the flask for 4 hours using another dropping pump. It was dripped in. After completion of the dropping of the polymerization initiator, the temperature is maintained (aged) at the same temperature for 4 hours, and then cooled to room temperature, and the monomer component m1, m2, m3 is represented by the above formula (8) A polymer M1 as a combined M was obtained.

(Synthesis Examples 2 to 8)
The same operation as in Synthesis Example 1 except that the solvent (solvent) used in the synthesis of the polymer, the types of monomer components, the ratio of each component were adjusted, and the composition of the polymer was changed as shown in Table 1. Went. As a result, seven types of polymers M (polymers M2 to M8) were obtained.
(Synthesis Example 9)
In a reaction vessel (flask) equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, 314 parts by weight of diethylene glycol monobutyl ether acetate as a solvent (solvent) was added and heated to 90 ° C. Subsequently, 2,2′-azobis (isobutyronitrile) (AIBN) as a radical initiator: 20 parts by weight and diethylene glycol monobutyl ether acetate (solvent): 30 parts by weight were added to the flask. The monomer component (compound) represented by the formula (11) x1: 180 parts by weight, the monomer component (compound) x2 represented by the formula (12): 90 parts by weight, the formula (13) Monomer component (compound) x3: 15 parts by weight, monomer component (compound) x4: 15 parts by weight represented by the above formula (14), 2,2'-azobis (isobutyronitrile) ) (AIBN): A solution prepared by dissolving 50 parts by weight of diethylene glycol monobutyl ether acetate: 200 parts by weight was added dropwise using a dropping pump over 5 hours, and further aged for 4 hours. Then, it cooled to room temperature and obtained the polymer X1 as the polymer X represented by the said Formula (19) including the monomer components x1, x2, x3, x4.

(Synthesis Examples 10 to 16)
The same operation as in Synthesis Example 9 was performed except that the type of solvent (solvent) used in the synthesis of the polymer and the ratio of each component were adjusted and the composition of the polymer was changed as shown in Table 1. As a result, seven types of polymers X (polymers X2 to X8) were obtained.
(Synthesis Example 17)
In a reaction vessel (flask) equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, 314 parts by weight of diethylene glycol monobutyl ether acetate as a solvent (solvent) was added and heated to 90 ° C. Subsequently, 2,2′-azobis (isobutyronitrile) (AIBN) as a radical initiator: 20 parts by weight and diethylene glycol monobutyl ether acetate (solvent): 30 parts by weight were added to the flask. , Monomer component (compound) y1: 200 parts by weight represented by formula (15), monomer component (compound) y2 represented by formula (16): 100 parts by weight, 2,2′- A solution prepared by dissolving 50 parts by weight of azobis (isobutyronitrile) (AIBN) in 200 parts by weight of diethylene glycol monobutyl ether acetate was added dropwise over 5 hours using a dropping pump, and further aged for 4 hours. Then, it cooled to room temperature and obtained the polymer Y1 as the polymer Y containing the monomer components y1 and y2 and represented by the said Formula (20).

(Synthesis Examples 18 and 19)
The same operation as in Synthesis Example 17 was performed except that the type of solvent (solvent) used in the synthesis of the polymer and the ratio of each component were adjusted and the composition of the polymer was changed as shown in Table 1. As a result, two types of polymers Y (polymers Y2 and Y3) were obtained.
(Synthesis Example 20)
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer is flowed with a suitable amount of nitrogen to form a nitrogen atmosphere. Diethylene glycol monobutyl ether acetate as a solvent (solvent): 100 parts by weight is added and heated to 80 ° C. with stirring. did. Next, in the flask, γ-methacryloxypropyltrimethoxysilane (trade name “SZ6030”, manufactured by Toray Dow Corning Co., Ltd.) as vinyl monomer component n1: 70 parts by weight, as vinyl monomer component n2 Glycidyl methacrylate (GMA): 25 parts by weight, 6-hexanolide addition polymer of 2-hydroxyethyl acrylate as vinyl monomer component n3 (average polymerization degree 3) (trade name “Placcel FA-3”, Daicel Chemical (Manufactured by Kogyo Co., Ltd.): A solution prepared by dissolving 5 parts by weight in 30 parts by weight of diethylene glycol monobutyl ether acetate was added dropwise over about 4 hours using a dropping pump. On the other hand, a solution prepared by dissolving 5 parts by weight of a polymerization initiator [2,2′-azobis (2,4-dimethylvaleronitrile)] in 90 parts by weight of diethylene glycol monobutyl ether acetate was added over about 4 hours using another dropping pump. And dropped into the flask. After completion of the dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer N1 as a copolymer N. The produced copolymer N1 had a weight average molecular weight Mw of 9000 and a dispersity of 1.80.

(Synthesis Example 21)
As the vinyl monomer component n1, γ-methacryloxypropyltrimethoxysilane (trade name “SZ6030”, manufactured by Toray Dow Corning Co., Ltd.): 70 parts by weight, as the vinyl monomer component n2, glycidyl methacrylate (GMA) : 25 parts by weight, as vinyl monomer component n3, 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate (average polymerization degree 3) (trade name “Placcel FM-3”, manufactured by Daicel Chemical Industries, Ltd.): 5 Except having used the weight part, operation similar to the said synthesis example 20 was performed, and the copolymer N2 was obtained. The produced copolymer N2 had a weight average molecular weight Mw of 9300 and a dispersity of 1.86.

(Synthesis Example 22)
As the vinyl monomer component n1, γ-methacryloxypropyltrimethoxysilane (trade name “SZ6030”, manufactured by Toray Dow Corning Co., Ltd.): 50 parts by weight, as the vinyl monomer component n2, glycidyl methacrylate (GMA) 49 parts by weight, as vinyl monomer component n3, 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average polymerization degree 3) (trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd.): 1 weight A copolymer N3 was obtained by carrying out the same operations as in Synthesis Example 20 except that the above components were used. The produced copolymer N3 had a weight average molecular weight Mw of 8,900 and a dispersity of 1.82.

(Synthesis Example 23)
As vinyl monomer component n1, γ-methacryloxypropyltrimethoxysilane (trade name “SZ6030”, manufactured by Toray Dow Corning Co., Ltd.): 70 parts by weight, as vinyl monomer component n2, 3,4-methacrylic acid 3,4- Epoxycyclohexylmethyl (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.): 25 parts by weight, 6-hexanolide addition polymer of 2-hydroxyethyl acrylate as vinyl monomer component n3 (average polymerization degree 3) (Trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd.): A copolymer N4 was obtained in the same manner as in Synthesis Example 20 except that 5 parts by weight were used. The produced copolymer N4 had a weight average molecular weight Mw of 9000 and a dispersity of 1.80.

Table 1 collectively shows the ratio of each monomer component constituting each polymer synthesized in Synthesis Examples 1 to 19 and the weight average molecular weight Mw of each polymer. In the table, methacrylic acid 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl (= 2- (1-methylpropylideneaminooxycarbonylaminoethyl) methacrylate) is represented by “m1a” and methacrylic acid. 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl is denoted by “m1b”, 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl acrylate is denoted by “m1c”, Methacrylic acid is indicated by “m2a”, acrylic acid is indicated by “m2b”, stearyl methacrylate is indicated by “m3a”, behenyl methacrylate is indicated by “m3b”, palmityl acrylate is indicated by “m3c”, and lignoceryl methacrylate is indicated. Indicated as “m3d”, methyl methacrylate as “m4a”, acrylic Ethyl is indicated by “m4b”, pentyl acrylate is indicated by “m4c”, styrene is indicated by “m5”, 2-hydroxyethyl methacrylate is indicated by “m6”, and 3,4-epoxytricyclo [5.2. A mixture of 1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate was designated “m7”. The polymers synthesized as described above all had a dispersity (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1 or more and 3 or less.

[2] Preparation of color filter ink set (ink set 1)
In the following manner, a color filter ink set composed of three types of first ink and one type of second ink was prepared.
<Preparation of first ink set>
Dispersic 166 as a dispersant, polymer M1, and diethylene glycol monobutyl ether acetate functioning as a solvent (component of the first liquid medium in the first ink) that dissolves polymer M1 The polymer M solution in which the polymer M1 was dissolved in a solvent was obtained by stirring the mixture for 10 minutes with a disper mill (polymer M solution preparation step). At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm.

Next, as described below, a pigment is added to the polymer M solution obtained in the polymer M solution preparation step, and inorganic beads are added in multiple stages using a stirrer (bead mill) to perform fine dispersion treatment. A fine dispersion step was performed.
First, a pigment was added to the obtained polymer M solution and stirred for 10 minutes. At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm. Examples of the pigment include C.I. I. Pigment Green 58 powder, a sulfonated pigment derivative (sub-pigment) powder having a chemical structure represented by the following formula (34), and C.I. I. A mixture with Pigment Yellow 150 was used. At this time, the mixture was diluted with diethylene glycol monobutyl ether acetate so that the pigment content in the mixture of the polymer M solution and the pigment was 16 wt%.

Next, inorganic beads having an average particle size of 0.8 mm (first inorganic beads, manufactured by Zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) are added and stirred at room temperature for 30 minutes. First-stage distributed processing (first processing) was performed. At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm.
Next, the inorganic beads (first inorganic beads) are removed by filtration using a filter (“PALL HDCII Membrane Filter”, manufactured by PALL), and then inorganic beads having a mean particle diameter of 0.1 mm (second Inorganic beads, made of zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) were added, and the mixture was further stirred for 30 minutes to perform the second stage dispersion treatment (second treatment). At this time, the rotation speed of the stirring blade of the bead mill (stirrer) was set to 2000 rpm. At this time, the pigment dispersion was diluted with diethylene glycol monobutyl ether acetate so that the pigment content in the obtained pigment dispersion was 13 wt%.
Thereafter, the inorganic beads (second inorganic beads) were removed by filtration using a filter (“PALL HDCII Membrane Filter” (trade name), manufactured by PALL) to obtain a pigment dispersion.

Next, as a liquid medium for dilution (first liquid medium), diethylene glycol monobutyl ether acetate and diethylene glycol mononormal butyl ether were added and mixed (dilution step). This step was performed by putting each of the above materials into a stirrer (uniaxial mixer) having an internal capacity of 400 cc and stirring for 10 minutes with a disper mill. At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm. As a result, a target green first ink (G ink) was obtained.
In addition, the first red ink (R ink) and the first blue ink (B ink) are the same as the first green ink except that the type of pigment and the amount of each component used are changed. Was prepared.

<Preparation of second ink>
A second ink was obtained by mixing the polymer X1, the polymer Y1, the polymer N1, and diethylene glycol monobutyl ether acetate as the second liquid medium.
By combining the second ink thus obtained and the first ink set, an ink set for a color filter composed of four types of inks was obtained.

(Ink set 2 to 10)
The color set is the same as the ink set 1 except that the types and amounts of materials used for preparing the first ink and the second ink constituting the color filter ink set are shown in Tables 2 and 3. A filter ink set was prepared.
(Ink set 11)
By mixing Dispersic 111 and Dispersic 166 as dispersants, polymer M7, pigment, polymer X8, and 1,3-butylene glycol diacetate and diethylene glycol mononormal butyl ether as liquid media A green ink (G ink) was prepared. Further, a red ink (R ink) and a blue ink (B ink) were prepared in the same manner as the green ink (G ink) except that the type of pigment and the amount of each component used were changed. An ink set for color filters made of various inks was obtained.

  Tables 2 and 3 collectively show the types and contents of the constituent components of each ink constituting each of the above-described ink filters. In the table, C.I. I. Pigment Green 58 is changed to “PG58”, C.I. I. Pigment Green 36 is “PG36”, a powder composed of a pigment derivative represented by the above formula (34) (one sulfo group in the molecule) is “SPD1”, and a pigment derivative represented by the following formula (35) (SPD2), a powder composed of (two sulfo groups in the molecule), C.I. I. Pigment Red 177 is “PR177”, C.I. I. Pigment Red 254 is "PR254", C.I. I. Pigment Red 177 and a pigment derivative represented by the formula (30) were mixed with “PR177D”, C.I. I. A mixture of Pigment Red 254 and a pigment derivative represented by Formula (31) is “PR254D”, C.I. I. Pigment Blue 15: 6 is changed to “PB15: 6”, C.I. I. Pigment Yellow 150 is changed to “PY150”, C.I. I. Pigment Violet 23 is “PV23”, Dispersic 111 is “DA1”, Dispersic 2095 is “DA2”, Dispersic P104 is “DA3”, Dispersic 166 is “DA4”, Dispersic 9075 is “DA5”, Dispersic 2001 is “DA6”, diethylene glycol monobutyl ether acetate is “S1”, 1,3-butylene glycol diacetate is “S2”, and 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate is “S3”. Bis (2-butoxyethyl) ether is "S4", ethyl octoate is "S5", diethylene glycol mononormal butyl ether is "S6", triethylene glycol mononormal butyl ether is "S7", 3-ethoxypropoxy It showed the phosphate ethyl with "S8".

  In addition, C.I. I. The content of the pigment derivative represented by the formula (30) in the mixture of Pigment Red 177 and the pigment derivative represented by the formula (30) was 0.1 wt% or more and 10 wt% or less. In addition, C.I. I. The content of the pigment derivative represented by the formula (31) in the mixture of Pigment Red 254 and the pigment derivative represented by the formula (31) was 0.1 wt% or more and 10 wt% or less. Further, the viscosity at 25 ° C. of the first ink constituting the color filter ink set measured in accordance with JIS Z8809 using a vibration viscometer is 5 mPa · s or more and 11 mPa · s or less. The value was within the range. In addition, the viscosity at 25 ° C. of each of the second inks constituting each color filter ink set measured in accordance with JIS Z8809 using a vibration viscometer is 1.5 mPa · s or more and 3 The value was within a range of not more than 5 mPa · s.

［３］液滴吐出の安定性評価（吐出安定性評価）
前記各カラーフィルター用インクセットを構成する各インクについて、下記に示すような試験による評価を行った。

[3] Stability evaluation of droplet discharge (Evaluation of discharge stability)
Each ink constituting each color filter ink set was evaluated by the following test.

[3.1] Evaluation of accuracy of landing position Prepare a droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber) and the ink set for each color filter, and set the frequency of the piezoelectric element to 5 kHz. With the drive waveform optimized, each ink was continuously ejected with 1200000 droplets (1200000 droplets) from each nozzle of the droplet ejection head. For the 1200000 droplets ejected from the designated nozzle near the center of the droplet ejection head, the average value of the deviation amount d from the center aiming position of the center position of each landed droplet is obtained, and the following five steps Evaluation was performed according to the criteria of It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amount d is less than 0.05 μm.
B: The average value of the shift amounts d is 0.05 μm or more and less than 0.10 μm.
C: The average value of the shift amounts d is 0.10 μm or more and less than 0.13 μm.
D: The average value of the shift amount d is 0.13 μm or more and less than 0.16 μm.
E: The average value of the shift amounts d is 0.16 μm or more.

[3.2] Stability evaluation of droplet discharge amount Prepare a droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber) and the ink set for each color filter, and set the frequency of the piezoelectric element. With the drive waveform optimized at 5 kHz, 1500000 droplets (1500000 droplets) were continuously discharged from each nozzle of the droplet discharge head for each ink. For the two specified nozzles on the left and right ends of the droplet discharge head, the total weight of the discharged droplets is obtained, and the absolute value ΔW [ng] of the difference between the average discharge amounts of the droplets discharged from the two nozzles is calculated. Asked. A ratio (ΔW / W _T ) of ΔW with respect to the target discharge amount W _T [ng] of the droplet was obtained and evaluated according to the following five-stage criteria. As the value of [Delta] W / W _T is small, it can be said that the greater the stability of the droplet discharge amount.

A: The value of ΔW / _{W T} is less than 0.050.
B: The value of ΔW / _{W T} is less than 0.050 than 0.250.
C: The value of ΔW / _{W T} is less than 0.250 than 0.550.
D: The value of ΔW / _{W T} is less than 0.550 than 0.780.
E: The value of ΔW / _{W T} is 0.780 or more.

[3.3] Evaluation of intermittent printing performance A droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber) and the ink set for each color filter are prepared, and the frequency of the piezoelectric element is set to 5 kHz. With the drive waveform optimized, for each ink, 10000 (10000 drops) droplets were continuously discharged from each nozzle of the droplet discharge head, and then the droplet discharge was interrupted for 300 seconds ( First sequence). Thereafter, similarly, the operation of continuously discharging the droplets and interrupting the discharge of the droplets were repeated. For the specified nozzle near the center of the droplet discharge head, the average weight W ₁ [ng] of the droplets discharged in the first sequence and the average weight W ₁₀₀ [ng] of the droplets discharged in the 100th sequence And asked. Then, the ratio (| W ₁ −W ₁₀₀ | / W _T ) of the absolute value of the difference between W ₁ and W ₁₀₀ to the target discharge amount W _T [ng] of the droplet is obtained, and the following five criteria are used. ,evaluated. | _W 1 _-W 100 | as the value of / _{W T} is small, it can be said to be excellent in intermittent printing performance (stability of the droplet discharge quantity).

_A: | _{W 1 -W} 100 | value of / _{W T} is less than 0.045.
_B: | _{W 1 -W} 100 | value of / _{W T} is less than 0.045 than 0.120.
_C: | _{W 1 -W} 100 | value of / _{W T} is less than 0.120 than 0.430.
_D: | _{W 1 -W} 100 | value of / _{W T} is less than 0.430 than 0.670.
_E: | _{W 1 -W} 100 | value of / _{W T} is 0.670 or more.

[3.4] Continuous Discharge Test Using a droplet discharge device as shown in FIG. 3 installed in a chamber (thermal chamber) and the ink set for each color filter in an environment of 25 ° C. and 40% RH, By operating the droplet discharge device continuously for 400 hours, each ink constituting the color filter ink set was discharged.
The nozzle clogging rate ([(number of clogged nozzles) / (total number of nozzles)] × 100) obtained after continuous operation is found and the nozzles are clogged. With respect to the above, it was examined whether or not clogging can be eliminated by a cleaning member made of a plastic material. The results were evaluated according to the following five-step criteria.

A: No nozzle clogging occurs.
B: The occurrence rate of nozzle clogging is less than 0.4% (excluding zero), and clogging can be eliminated by cleaning.
C: The occurrence rate of nozzle clogging is 0.4% or more and less than 0.8%, and clogging can be eliminated by cleaning.
D: The occurrence rate of nozzle clogging is 0.8% to less than 1.1%, and clogging can be eliminated by cleaning.
E: The occurrence rate of nozzle clogging is 1.1% or more, or clogging cannot be eliminated by cleaning.
In addition, said evaluation was performed on the same conditions about each Example and the comparative example.

[4] Ink storage stability evaluation (long-term stability evaluation)
[4.1] Evaluation of storage stability of ink containing pigment (long-term stability evaluation)
Of the inks constituting each of the color filter ink sets, the ink containing the pigment (the first ink in each example and the ink in Comparative Example 1) was left in an environment of 50 ° C. for 80 days and then visually observed. Was observed and evaluated according to the following five-stage criteria.

A: No change from before heating is observed.
B: Almost no aggregation or sedimentation of pigment particles is observed.
C: Slight aggregation / precipitation of pigment particles is observed.
D: Aggregation / sedimentation of pigment particles is clearly observed.
E: Aggregation / sedimentation of pigment particles is noticeable.

[4.2] Storage stability evaluation of the second ink (long-term stability evaluation)
The second ink constituting each color filter ink set was subjected to gel permeation chromatography (GPC) immediately after preparation (before heating) and after standing in an environment of 55 ° C. for 80 days ( Mw and Mn after heating were determined and evaluated according to the following five-step criteria.

A: Change rate of Mw / Mn before and after heating is less than 5%.
B: Change rate of Mw / Mn before and after heating is 5% or more and less than 10%.
C: Mw / Mn change rate before and after heating is 10% or more and less than 15%.
D: Change rate of Mw / Mn before and after heating is 15% or more and less than 20%.
E: Change rate of Mw / Mn before and after heating is 20% or more.
The above results are shown in Tables 4 and 5.

[5] Production of color filter (Example 1)
8000 color filters were manufactured through the following steps [5.1] to [5.7].
[5.1] Substrate preparation process First, a soda glass substrate (G5 size: 1100 × 1300 mm) having a silica (SiO ₂ ) film that prevents elution of sodium ions on both sides is prepared and subjected to a cleaning treatment. did.
Next, the radiation-sensitive composition for forming partition walls containing carbon black was applied to the entire surface of one of the cleaned substrates to form a coating film.
Next, prebaking was performed under the conditions of heating temperature: 110 ° C. and heating time: 120 seconds.

[5.2] Partition Formation Step After that, radiation is applied through a photomask to perform post-exposure baking (PEB), and then CF ₄ and He gas are used at 1: 9 (volume ratio). Pre-bake treatment and post-exposure bake treatment were performed under conditions of an atmospheric pressure plasma polymerization apparatus in which a mixed gas was introduced, an output of 800 W, a distance from the plasma generator to the table: 0.5 mm, and a treatment table speed: 10 m / s. Only the surface of the coated film was doped with fluorine. Thereafter, development processing using an alkali developer was performed, and further, post-baking processing was performed to form partition walls. PEB was performed under the conditions of heating temperature: 110 ° C., heating time: 120 seconds, and radiation irradiation intensity: 150 mJ / cm ² . The development process was performed by, for example, a vibration dipping method. The development processing time was 60 seconds. Moreover, the post-baking process was performed on the conditions of heating temperature: 140 degreeC and heating time: 10 minutes. The formed partition wall had a thickness of 2.0 μm.

[5.3] First Ink Application Step Next, using a droplet discharge device as shown in FIG. 3, the first ink was discharged into a cell as a region surrounded by a partition wall. At this time, the first inks of the three colors were used so that the first inks of the respective colors were not mixed. Further, the first ink was discharged after the frequency of the piezo element of the droplet discharge device was set to 5 kHz and the drive waveform was optimized.

[5.4] First Liquid Medium Removal Step Thereafter, the first liquid medium is removed by performing a heat treatment at 230 ° C. for 60 minutes on a hot plate to remove three colors (red (R) , Green (G), blue (B)) colored films were formed.
[5.5] Cooling Step The substrate on which the colored film was formed was cooled for 30 minutes in an environment where the relative humidity was 10% or less and the ambient temperature was 25 ° C. or less.

[5.6] Second Ink Application Step Next, a second ink was ejected into a cell from which the first ink was ejected, using a droplet ejection device as shown in FIG. At this time, in each cell, the second ink was applied in such an amount that the average thickness of the formed colored portion (laminated body of the colored portion and the resin film) was 2.0 μm. The second ink was ejected after the frequency of the piezoelectric element of the droplet ejection device was set to 5 kHz and the drive waveform was optimized.
[5.7] Second liquid medium removing step After that, a heat treatment is performed on a hot plate at 100 ° C. for 60 minutes, and further, a heat treatment is performed in an oven at 200 ° C. for 15 minutes. Three colored portions composed of a film and a resin film were formed.

[5.8] Washing Step Thereafter, washing with N-methyl-2-pyrrolidone and γ-butyrolactone was performed, and a color filter as shown in FIG. 1 was obtained.
Further, in the same manner as described above, by using only one type of ink containing a colorant and coloring portions of the same color are formed in all cells, coloring is performed by using the same method as described above. A green monochromatic color filter having only a green colored portion as a part, a red monochromatic color filter having only a red colored portion as a colored portion, and a blue single color filter having only a blue colored portion as a colored portion were produced.

(Examples 2 to 10)
A color filter was produced in the same manner as in Example 1 except that the ink set shown in Table 6 was used and the relative humidity, ambient temperature, and cooling time in the cooling step were set to the conditions shown in Table 6.
(Comparative Examples 1 and 2)
A color filter was produced in the same manner as in Example 1 except that the ink set shown in Table 6 was used and the relative humidity, ambient temperature, and cooling time in the cooling step were set to the conditions shown in Table 6.

In Comparative Example 2, the amount of ink (ink containing the polymer M, the polymer X, and the polymer Y as the pigment and the resin material) in the above-mentioned [5.3] first ink application step is set. The thickness of the colored portion formed by the solid content in the ink is changed to 2.0 μm, and [5.6] the second ink application step and [5.7] the second liquid. 8000 color filters were manufactured in the same manner as in the above example except that the conductive medium removing step was omitted.
The production conditions for each example and each comparative example are shown in Table 6.

[6] Evaluation of color filter The following evaluation was performed using each color filter obtained as described above.
[6.1] Flatness of colored portion Among the color filters of the respective Examples and Comparative Examples, a color filter manufactured for the 4000th sheet was prepared.
About these color filters, the difference (DELTA) D of the maximum height and the minimum height of a coloring part was calculated | required using the stylus type roughness meter (the Tencor company make, P-15), and it evaluated in accordance with the following five steps | standards. .

A: ΔD is less than 0.14 μm.
B: ΔD is 0.14 μm or more and less than 0.26 μm.
C: ΔD is 0.26 μm or more and less than 0.40 μm.
D: ΔD is 0.40 μm or more and less than 0.50 μm.
E: ΔD is 0.50 μm or more.

[6.2] Evaluation of contrast ratio For each of the above Examples and Comparative Examples, the three types of single color filters (green single color filter, red single color filter, blue single color filter) produced as described above were used. Contrast ratio (CR) was calculated | required using the contrast tester (Kisaka Electric Co., Ltd. make, CT-1), and it evaluated as follows.
For the red single color filter, the CR when x = 0.651 was evaluated according to the following five-step criteria.

A: CR is 3000 or more.
B: CR is 2500 or more and less than 3000.
C: CR is 2100 or more and less than 2500.
D: CR is 1800 or more and less than 2100.
E: CR is less than 1800.

For the green color filter, the CR when y = 0.600 was evaluated according to the following four criteria.
A: CR is 3900 or more.
B: CR is 3600 or more and less than 3900.
C: CR is 3300 or more and less than 3600.
D: CR is 2900 or more and less than 3300.
E: CR is less than 2900.

For the blue single color filter, the CR when y = 0.141 was evaluated according to the following four criteria.
A: CR is 3200 or more.
B: CR is 2800 or more and less than 3200.
C: CR is 2500 or more and less than 2800.
D: CR is 2300 or more and less than 2500.
E: CR is less than 2300.

[6.3] Lightness Evaluation A liquid crystal display device as shown in FIG. 4 is used under the same conditions by using the color filter manufactured for the 8000th sheet among the color filters of the respective examples and comparative examples. Manufactured. These liquid crystal display devices were evaluated as shown below. For the liquid crystal display device, each color is displayed in a single color, and tristimulus values are obtained by the xyY colorimetric method using a chromaticity meter (manufactured by Minolta, CM-3700d, using C light source as the light source) as follows. Evaluation was performed.

That is, for the single color display of red, the Y value when x = 0.651 was evaluated according to the following five-step criteria.
A: Brightness Y is 21.0 or more.
B: Lightness Y is 20.5 or more and less than 21.0.
C: Brightness Y is 19.9 or more and less than 20.5.
D: Lightness Y is 18.0 or more and less than 19.9.
E: Lightness Y is less than 18.0.

In addition, for the monochrome display of green, the Y value when y = 0.600 was evaluated according to the following five-stage criteria.
A: Brightness Y is 57.0 or more.
B: The brightness Y is 55.3 or more and less than 57.0.
C: Brightness Y is 53.3 or more and less than 55.3.
D: Brightness Y is 51.0 or more and less than 53.3.
E: Lightness Y is less than 51.0.

For the blue single color display, the Y value when y = 0.141 was evaluated according to the following five-step criteria.
A: Brightness Y is 11.8 or more.
B: The brightness Y is 11.5 or more and less than 11.8.
C: Brightness Y is 10.8 or more and less than 11.5.
D: The brightness Y is 10.0 or more and less than 10.8.
E: Lightness Y is less than 10.0.

[6.4] Color unevenness and density unevenness About the liquid crystal display device of each of the above examples and comparative examples manufactured in [6.3], red single color display, green single color display, blue single color display in a dark room Then, visual observation was performed in a state where white single color display was performed, and the occurrence of color unevenness and density unevenness at each part was evaluated according to the following five-stage criteria.

A: Color unevenness and density unevenness are not recognized at all.
B: Color unevenness and density unevenness are hardly recognized.
C: Color unevenness and density unevenness are slightly recognized.
D: Color unevenness and density unevenness are clearly recognized.
E: Color unevenness and density unevenness are noticeable.

[6.5] Voltage holding ratio of liquid crystal layer The liquid crystal display devices of the respective examples and comparative examples manufactured in the above [6.3] are prepared, and a voltage of 5 V is applied to the liquid crystal layer for 60 microseconds. The voltage holding ratio (VHR) 16.5 milliseconds after the application was canceled after applying at a span of 16.5 milliseconds, the voltage holding ratio measuring system for liquid crystal (product name “MZ1800” manufactured by Micronics) And evaluated according to the following four-stage criteria.
A: VHR is 98% or more.
B: VHR is 96% or more and less than 98%.
C: VHR is 91% or more and less than 96%.
D: VHR is less than 91%.

[6.6] Characteristic difference between individuals Prepare color filters manufactured on the 1st to 20th sheets and the 7980 to 7999th sheets among the color filters of the respective examples and comparative examples, In a dark room, red single color display, green single color display, blue single color display, and white single color display were performed, and colorimetry was performed using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). From the results, for each of the examples and comparative examples, the color difference (in the Lab display system) that is the largest among the color filters manufactured in the 1st to 20th sheets and 7980 to 7999th sheets (total 40 color filters), respectively. Color difference ΔE) was determined and evaluated according to the following five-step criteria.

A: Color difference (ΔE) is less than 1.5.
B: Color difference (ΔE) is 1.5 or more and less than 2.7.
C: Color difference (ΔE) is 2.7 or more and less than 3.6.
D: Color difference (ΔE) is 3.6 or more and less than 4.6.
E: Color difference (ΔE) is 4.6 or more.

[6.7] Heat cycle test Among the color filters of the respective examples and comparative examples, the color filters manufactured in the 5021st to 5030th sheets were used, and the liquid crystal display as shown in FIG. 4 under the same conditions. The device was manufactured.
Using these liquid crystal display devices, light leakage (white spots, bright spots) occurs when visual observation is performed in a dark room with red single color display, green single color display, and blue single color display. Confirmed that there is no.

Next, the color filter was removed from the liquid crystal display device.
Each removed color filter is placed in a 20 ° C. environment for 1.5 hours, then in a 55 ° C. environment for 2.5 hours, then in a 20 ° C. environment for 1.5 hours, and then at −20 ° C. It was left in the environment for 2.5 hours. Thereafter, the environmental temperature was returned again to 20 ° C., which was set as one cycle (8 hours), and this cycle was repeated 50 times in total (400 hours in total).

Thereafter, using these color filters, a liquid crystal display device as shown in FIG. 4 was assembled again.
Using these liquid crystal display devices, visual observation is performed in a dark room with red single color display, green single color display, and blue single color display, and the occurrence of light leakage (white spots, bright spots) is observed. The evaluation was made according to the following 6-step criteria.

A: There is no color filter in which light leakage (white spots, bright spots) occurs.
B: Light leakage (white spots, bright spots) is observed in one or two color filters.
C: Light leakage (white spots, bright spots) is observed in 3 to 4 color filters.
D: Light leakage (white spots, bright spots) is observed in 5 to 7 color filters.
E: Light leakage (white spots, bright spots) is observed in 8 to 9 color filters.
F: Light leakage (white spots, bright spots) is observed in 10 color filters.

[6.8] Evaluation of solvent resistance Liquid crystal as shown in FIG. 4 under the same conditions using the color filters manufactured in the 4001st to 4005th sheets among the color filters of the respective examples and comparative examples. A display device was manufactured. About these liquid crystal display devices, red monochromatic display, green monochromatic display, and blue monochromatic display were performed, and colorimetry was performed using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.).

Next, the color filter was removed from the liquid crystal display device.
Each removed color filter was immersed in a solvent at 50 ° C. for 60 minutes, and then a liquid crystal display device as shown in FIG. 4 was assembled again.
About these liquid crystal display devices, red monochromatic display, green monochromatic display, and blue monochromatic display were performed, and colorimetry was performed using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.).

From these results, the color difference before and after immersion of the color filter in the solvent (color difference ΔE in the Lab display system) was determined for each of the examples and comparative examples, and evaluated according to the following three criteria.
A: Color difference (ΔE) is less than 3.0.
B: Color difference (ΔE) is 3.0 or more and less than 3.5.
C: Color difference (ΔE) is 3.5 or more.

As the solvent, γ-butyrolactone (γ-BL), isopropyl alcohol (IPA), N-methyl-2-pyrrolidone (NMP), 0.5N hydrochloric acid (HCl), 0.5N aqueous sodium hydroxide solution (NaOH) are used. It was.
These results are shown in Tables 7 and 8. In the table, for the ejection stability evaluation and long-term stability evaluation of the ink, the evaluation result for R ink in the “R” column, the evaluation result for G ink in the “G” column, and the “B” column Shows the evaluation result for B ink, the evaluation result for the second ink in the "second" column, and the evaluation of the red colored portion or red display in the "R" column for the color filter evaluation. As a result, the evaluation result about a green coloring part or green display was shown in the column of "G", and the evaluation result about a blue coloring part or blue display was shown to the column of "B".

As is clear from Tables 7 and 8, excellent results were obtained in the present invention, whereas satisfactory results were not obtained in the comparative example.
Further, when a commercially available liquid crystal television was disassembled and the liquid crystal display device part was replaced with one manufactured as described above, and the same evaluation as described above was performed, the same result as above was obtained.

  DESCRIPTION OF SYMBOLS 1 ... Color filter 11 ... Board | substrate 12 ... Coloring part 12A ... 1st coloring part 12B ... 2nd coloring part 12C ... 3rd coloring part 13 ... Partition 14 ... Cell 21 ... 1st ink 22 ... 2nd ink DESCRIPTION OF SYMBOLS 121 ... Colored film 122 ... Resin film 3 ... Coating film 60 ... Liquid crystal display device 61 ... Common electrode 62 ... Liquid crystal layer 63, 64 ... Orientation film 65 ... Pixel electrode 66 ... Substrate (counter substrate) 67, 68 ... Polarizing plate 100 ... Droplet discharge device 101 ... Tank 102 ... Discharge scanning unit 103 ... Droplet discharge means 104 ... First position control device (moving means) 106 ... Stage 108 ... Second position control device (moving means) 110 ... Tube 112 ... Control means DESCRIPTION OF SYMBOLS 1000 ... Image display apparatus 1100 ... Personal computer 1102 ... Keyboard 1104 ... Main-body part 1106 ... Display unit 12 DESCRIPTION OF SYMBOLS 0 ... Mobile telephone 1202 ... Operation button 1204 ... Earpiece 1206 ... Mouthpiece 1300 ... Digital still camera 1302 ... Case (body) 1304 ... Light receiving unit 1306 ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... Data communication Input / output terminal 1430 ... TV monitor 1440 ... Personal computer

Claims (11)

A method for producing a color filter by ejecting ink by an inkjet method on a substrate provided with a large number of cells,
A first ink application step of discharging a first ink containing a colorant and a first liquid medium in which the colorant is dispersed and / or dissolved into the cell;
A first liquid medium removing step of removing the first liquid medium from the first ink ejected into the cell and forming a colored film;
A cooling step of cooling the substrate on which the colored film is formed in an environment of a relative humidity of 10% or less and an ambient temperature of 15 ° C. or more and 35 ° C. or less;
A second ink that discharges a second ink containing a curable resin material and a second liquid medium that disperses and / or dissolves the curable resin material into the cell in which the first ink has been discharged. An ink application process,
A second liquid medium removing step of removing the second liquid medium from the second ink ejected into the cell and forming a resin film,
The curable resin material includes a monomer component x1 represented by the following formula (11), a monomer component x3 represented by the following formula (13), and a monomer component represented by the following formula (14). a polymer X comprising x4;
And a polymer Y containing a monomer component y1 represented by the following formula (15).

The curable resin material includes an alkoxysilyl group-containing vinyl monomer component n1 represented by the following formula (21), a vinyl monomer component n2 having a cyclic ether group of 3 to 5 members, and side chains. And a copolymer N containing a hydroxyl group-containing vinyl monomer component n3 having an ε-caprolactone ring-opening polymer chain portion.

  The method for producing a color filter according to claim 2, wherein the copolymer N has a weight average molecular weight of 500 or more and 100,000 or less.   The method for producing a color filter according to claim 2 or 3, wherein the content of the vinyl monomer component n1 in the copolymer N is 1 wt% or more and 95 wt% or less.   5. The method for producing a color filter according to claim 2, wherein the content of the vinyl monomer component n <b> 2 in the copolymer N is 1 wt% or more and 95 wt% or less.   The method for producing a color filter according to any one of claims 2 to 5, wherein a content of the vinyl monomer component n3 in the copolymer N is 0.1 wt% or more and 95 wt% or less.   The first liquid medium is diethylene glycol dimethyl ether, 1,3-butylene glycol diacetate, triethylene glycol diethyl ether, bis (2-butoxyethyl) ether, diethylene glycol monobutyl ether acetate, and 2- (2-methoxy- The method for producing a color filter according to any one of claims 1 to 6, comprising one or more selected from the group consisting of (1-methylethoxy) -1-methylethyl acetate.   The second liquid medium is propylene glycol-n-butyl ether, 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate, ethyl 3-ethoxypropionate, bis (2-butoxyethyl) ether The method for producing a color filter according to any one of claims 1 to 7, comprising one or more selected from the group consisting of styrene, diethylene glycol monobutyl ether acetate, and 1,3-butylene glycol diacetate.   A color filter manufactured by the method for manufacturing a color filter according to claim 1.   An image display device comprising the color filter according to claim 9.   An electronic apparatus comprising the image display device according to claim 10.

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