JP5239143B2 - Manufacturing method of color filter and manufacturing method of liquid crystal display device - Google Patents

Description

  The present invention relates to a method for producing a color filter using an ink-jet ink for a color filter used to form a cured layer having a predetermined pattern such as a pixel portion, and a method for producing a liquid crystal display device using the color filter. About.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having high specific gravity.
In general, as shown in FIG. 4, the color liquid crystal display device (101) is provided with a gap portion 33 of about 1 to 10 μm with a color filter 31 and an electrode substrate 32 such as a TFT substrate facing each other. The liquid crystal compound L is filled and the periphery thereof is sealed with a sealing material 34. The color filter 31 has a black matrix layer 36 formed in a predetermined pattern on the transparent substrate 35 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), and blue (B) three primary colors) arranged in a predetermined order, a protective film 38, and a transparent electrode film 39 are stacked in this order from the side close to the transparent substrate. Have taken. An alignment film 40 is provided on the inner surface side of the color filter 1 and the electrode substrate 32 facing the color filter 1. Further, a spacer is provided in the gap 33 in order to maintain a constant and uniform cell gap between the color filter 31 and the electrode substrate 32. As the spacer, pearls 41 having a constant particle diameter are dispersed, or columnar spacers 42 having a height corresponding to the cell gap as shown in FIG. It is formed in a region overlapping with the formed position. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

  In such a color filter, it is usually provided with coloring patterns of three primary colors of red (R), green (G), and blue (B), and electrodes corresponding to the respective pixels of R, G, and B are turned on, By turning it off, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed.

As a conventional method for producing a color filter, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.
Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.
Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.
However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem of high cost, and the yield decreases because the same process is repeated. There is a problem of doing.

As a method of manufacturing a color filter that solves these problems, a method of forming a colored layer (pixel portion) by spraying ink on the surface of a substrate by an inkjet method has been proposed (Patent Document 1). A method using such an ink jet method is effective in that a color filter having a large area can be produced with high productivity, and has attracted attention as a method capable of producing a color filter at a low cost.
In order to form pixels by spraying ink in accordance with an accurate pattern by an inkjet method, straightness and stability when ejected from an inkjet head are required. However, for example, if the ink evaporation rate is too fast, the viscosity of the ink rapidly increases at the nozzle tip of the ink jet head, causing ink droplets to fly, or clogging if they are ejected intermittently after a while. Wake up and can not re-discharge. A pigment is often used as a colorant for a color filter. However, if the pigment dispersibility of the color filter ink is poor, clogging occurs at the nozzle portion of the inkjet head due to aggregation of pigment particles. Therefore, when a pigment is used as the colorant, the pigment dispersibility also affects the ink ejection performance.

JP 2000-187111 A

  When newly replacing an inkjet ink in an inkjet ink supply system, it is difficult to completely remove the ink in the system even after sufficient cleaning. There were cases where clogging occurred and discharge from all the holes onto the substrate could not be performed, or there were cases where it was impossible to re-discharge from the holes that were initially discharged over time. In addition, agglomerates in the ink may be sprayed on the substrate, which may cause poor quality of the color filter.

  In addition, when a pixel is formed by spraying colored ink onto a substrate by an ink jet method, the ink lands on the substrate in a fluid state, so that the ink scatters at the time of landing, resulting in a mixture of different types of inks. Slightly occurs. When a slight color mixture occurred, the pigments sometimes aggregated black and produced protrusions. When the height of the protrusion is large and larger than the cell gap, there arises a problem that the product cannot be obtained unless the protrusion is cut away. On the other hand, even if a slight color mixture occurs, if the protrusions are not large, the color mixture itself hardly affects the color performance of the color filter, so that this is not a problem as a product. Such a problem of ink scattering has become more important due to the recent increase in color filter screen accompanying the increase in screen size of displays.

The present invention has been accomplished in view of the above-mentioned actual situation, and the first object thereof is to suppress the generation of protrusions or the height of protrusions even when ink is scattered and color mixing occurs on the substrate in the ink jet system. An object of the present invention is to provide a method for manufacturing a color filter that can be used.
A second object of the present invention is to provide a method for producing a color filter in which clogging of an ink jet head is reduced after newly replacing the ink jet ink in an ink jet ink supply system.
A third object of the present invention is to provide a method of manufacturing a liquid crystal display device with reduced display defects using a method of manufacturing a color filter that achieves the above object.

In order to achieve the first object, a pigment, a pigment dispersant, a binder component containing one or more selected from a thermosetting binder component and a photocurable binder component, and two or more types of solvents containing a solvent A color filter manufacturing method comprising a colored layer forming step of forming a colored layer by selectively attaching an inkjet ink for a color filter to a predetermined region on a substrate for a color filter by an inkjet method, wherein each of the color filters There is provided a method for producing a color filter, comprising an ink preparation step of controlling the zeta potential of the inkjet ink for use with the same sign.
According to the first aspect of the present invention, the ink preparation step of controlling the zeta potential of each of the two or more types of color filter inkjet inks used for forming the color filter to the same sign can be achieved. Even when the ink scatters upon landing and a slight color mixing occurs between different types of inks, the generation of protrusions or the height of the protrusions can be suppressed. Therefore, the present invention can eliminate the step of polishing the protruding portion due to the cell gap, and is a manufacturing method with high productivity.

In order to achieve the second object, the second aspect of the present invention is a binder component comprising at least one selected from a pigment, a pigment dispersant, a thermosetting binder component, and a photocurable binder component, And a color layer forming step of forming a colored layer by selectively adhering two or more kinds of color filter ink-jet inks containing a solvent to a predetermined region on the color filter substrate by an ink-jet method. A method for producing a color filter, comprising: an ink preparation step for controlling zeta potentials of ink before and after replacement to the same sign when replacing the inkjet ink in the inkjet ink supply system. A manufacturing method is provided.
According to the second aspect of the present invention, when the ink jet ink is replaced in the ink jet ink supply system, the ink preparation step of controlling the zeta potential of the ink before and after the replacement to the same sign is provided. Even if it is difficult to completely remove the pre-replacement ink that was present in the system, clogging of the inkjet head after the replacement of the inkjet ink is reduced, and aggregates in the ink are reduced. It becomes possible to suppress the quality defect of the color filter caused by being sprayed on the substrate.

In the present invention, it is preferable to control the zeta potential of each of the color filter inkjet inks to be negative. Further, it is preferable to control the zeta potential of the ink before and after replacement to be negative. When each zeta potential is controlled to be negative, it becomes possible to further suppress aggregation of pigments. Even if ink is scattered and color mixing occurs on the substrate in the ink jet system, the occurrence of protrusions or protrusions is prevented. The height can be further suppressed, or clogging of the inkjet head is further reduced after the inkjet ink is newly replaced in the inkjet ink supply system.

In the above-described present invention, the two or more kinds of pigment dispersant contained in the ink-jet ink, each independently, I one or more der selected from the group consisting of polyethyleneimine derivatives and polyallylamine derivative, the polyethylene imine The derivative is selected from a polyethyleneimine group, 6-hydroxyhexanoic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, and 4-hydroxydecanoic acid The polyallylamine derivative has a poly (carbonylalkyleneoxy) chain derived from polymerization of at least one hydroxycarboxylic acid, and the polyallylamine derivative is a polyallylamine derivative represented by the following general formula (I): preferred nitrous Rukoto There. Moreover, it is preferable that the pigment dispersant contained in the ink before and after replacement is independently at least one selected from the group consisting of a polyethyleneimine derivative and a polyallylamine derivative. In such a case, it is possible to further suppress aggregation of pigments, and even if ink is scattered and color mixing occurs on the substrate in the inkjet method, the generation of protrusions or the height of protrusions can be further suppressed. The clogging of the ink jet head is further reduced after the ink jet ink is newly replaced in the ink jet ink supply system.

  (Wherein X and Y are each independently hydrogen, a polymerization initiator residue, or a chain transfer catalyst residue; ¹  Represents a free amino group, a group represented by the following general formula (II) or (III), and n represents an integer of 2 to 1,000. However, n R ¹ Among them, at least one represents a group represented by the general formula (III). )

（式中、Ｒ ^２ は遊離のカルボン酸を有するポリエステル、遊離のカルボン酸を有するポリアミド、または遊離のカルボン酸を有するポリエステルアミドのいずれかからカルボキシル基を除いた残基を表す。）
上記本発明においては、前記着色層形成工程の前に、基板表面の所定領域の表面を親液化する親液化工程を更に含み、前記インク層形成領域に、前記２種類以上のカラーフィルター用インクジェットインク、或いは、前記交換後のインクを、インクジェット方式によって選択的に付着させてインク層を形成することが好ましい。この場合には、インク層形成領域にインクを付着させた後、インクの濡れ広がり性が向上し、色抜けや膜厚ムラをより効果的に防止することにより、より良好な画素を形成でき、表示不良が低減されたカラーフィルターを得ることが可能だからである。
また、本発明に係る液晶表示装置の製造方法は、上記本発明に係るカラーフィルターの製造方法を用いてカラーフィルターを製造する工程と、当該製造されたカラーフィルターと液晶駆動側基板を対向させて組み立てる工程を有する。

(In the formula, R ² represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.)
In the present invention, before the colored layer forming step, a lyophilic step of lyophilicizing the surface of a predetermined region of the substrate surface is further included, and the ink layer forming region includes the two or more types of inkjet inks for color filters. Alternatively, it is preferable that the ink layer is formed by selectively attaching the replaced ink by an ink jet method. In this case, after attaching the ink to the ink layer formation region, the wettability of the ink is improved, and more effective pixels can be formed by more effectively preventing color loss and film thickness unevenness, This is because it is possible to obtain a color filter with reduced display defects.
The method for manufacturing a liquid crystal display device according to the present invention includes a step of manufacturing a color filter using the method for manufacturing a color filter according to the present invention, and the manufactured color filter and the liquid crystal driving side substrate are opposed to each other. It has the process of assembling.

According to the method for producing a color filter of the present invention, even if ink is scattered in the ink jet system and color mixing occurs on the substrate, a good pixel or the like in which the generation of protrusions or the height of the protrusions is suppressed is formed. Thus, a color filter with reduced display defects can be manufactured.
In addition, according to the method for producing a color filter of the present invention, clogging of the inkjet head after replacement of the inkjet ink is reduced, and it is suppressed that aggregates in the ink are sprayed on the substrate, Good pixels and the like can be formed, and a color filter with reduced display defects can be manufactured.
In addition, according to the method for manufacturing a liquid crystal display device according to the present invention, since a color filter having better performance with reduced display defects is used, a high-quality liquid crystal display device can be obtained.

  The present invention relates to a color filter manufacturing method and a liquid crystal display device manufacturing method. Hereinafter, a method for manufacturing a color filter and a method for manufacturing a liquid crystal display device will be described in detail.

A. Method for producing color filter A first aspect of the method for producing a color filter according to the present invention is a method in which two or more types of inkjet inks for a color filter containing a pigment, a pigment dispersant, a binder component, and a solvent are applied to a predetermined region on a substrate. In addition, a method for producing a color filter including a colored layer forming step of forming a colored layer by selectively adhering by an ink jet method, wherein the zeta potentials of all the two or more types of ink are controlled to the same sign. It has the process.
According to the first aspect of the present invention, the ink is dispersed at the time of landing by having the ink preparation step of controlling the zeta potentials of all of the two or more types of inks used for forming the color filter to the same sign. Thus, even when a slight color mixing between different types of ink occurs, the generation of protrusions or the height of the protrusions can be suppressed.

The first aspect of the method for producing a color filter of the present invention includes an ink preparation step in which zeta potentials of all of two or more types of inks used for forming a color filter are controlled to have the same sign. The reason why it is possible to suppress the generation of protrusions or the height of protrusions even when a slight color mixing between different types of inks occurs upon landing is considered to be due to the following reasons. .
In other words, when a slight color mixing occurs between different types of inks in the past, severe protrusions are caused by aggregation when charged components such as pigments and pigment dispersants present in different types of ink are mixed. it is conceivable that.
Here, in general, the pigment contained in the ink-jet ink is dispersed by the action of a pigment dispersant, a pigment dispersion aid, etc., and the dispersion centered on the pigment is charged positively or negatively. is there. Then, when the dispersions present in different types of ink are mixed, if one is positively charged and the other is negatively charged, it is considered that the dispersion is attracted positively and negatively to cause significant aggregation of the dispersion. On the other hand, according to the method for producing a color filter of the present invention, two or more types are used because the zeta potentials of all the two or more types of ink used to form the color filter are controlled to the same plus or minus sign. Even if these inks are mixed, it is possible to suppress significant aggregation of the dispersion that is caused by attracting with plus and minus.
For this reason, in the present invention, it is possible to suppress the generation of protrusions or the height of the protrusions even when ink is scattered upon landing and a slight color mixture of different types of inks occurs. Therefore, the present invention can eliminate the step of polishing the protruding portion due to the cell gap, and is a manufacturing method with high productivity.

The second aspect of the method for producing a color filter of the present invention is a method for selectively applying an inkjet ink for a color filter containing a pigment, a pigment dispersant, a binder component, and a solvent to a predetermined region on a substrate by an inkjet method. A color filter manufacturing method including a colored layer forming step of forming a colored layer by adhering to the ink, wherein when the inkjet ink is replaced in the inkjet ink supply system, the zeta potentials of the ink before and after the replacement are mutually It has the ink preparation process controlled to the same code | symbol.
According to the second aspect of the present invention, when the ink jet ink is replaced in the ink jet ink supply system, the ink preparation step of controlling the zeta potential of the ink before and after the replacement to the same sign is provided. Even if it is difficult to completely remove the pre-replacement ink that was present in the system, as described above, the two components of the two types of ink before and after replacement charged with different signs Can be prevented from significantly agglomerating and increasing the viscosity over time, so that clogging of the ink jet head after ink jet ink replacement is reduced, and the color filter by which the aggregate in the ink is sprayed on the substrate It becomes possible to suppress quality defects.

1. Ink Preparation Step Hereinafter, the ink preparation step in the present invention will be described.
(1) First Aspect In the first aspect, two or more types of colored ink layers are prepared by selectively adhering to a predetermined region on a substrate by an inkjet method using two or more types of inkjet inks for color filters. The zeta potentials of all the two or more types of ink-jet inks are controlled to the same sign.

  As an aspect in which two or more types of color ink layers are formed by using two or more types of color filter inkjet inks and selectively adhering to a predetermined region on the substrate by an inkjet method, specifically, for example, R (Red), G (green), and the mode which forms B (blue) pixel are mentioned.

  Here, the zeta potential (electrokinetic potential) is the potential difference between the solid stationary phase and the liquid when relative motion occurs between the liquid and the solid. In the ink for a color filter, pigment or pigment dispersion It is considered as one index representing the state in which the agent or the like is dispersed in the solvent. The zeta potential in the present invention is determined by electrophoresis. Electrophoresis is a phenomenon in which fine particles with surface charges move when an electric field is applied to the liquid. By measuring the movement speed of the fine particles, the zeta potential of the fine particles is proportional to the movement speed. Can do. In the present invention, the zeta potential of the inkjet ink was measured with a laser zeta electrometer (for example, Zetasizer Nano ZS manufactured by Malvern) based on this principle.

  If the zeta potential of all two or more types of inkjet inks used to form a colored ink layer on one substrate matches with a plus or minus sign, even if two or more types of ink are mixed, plus and minus Therefore, it is possible to suppress aggregation of the dispersion centered on the pigment and increase in the viscosity of the ink. In particular, when the zeta potential of all the ink-jet inks is negative, it becomes possible to further suppress the aggregation of the dispersions, and even if color mixing occurs on the substrate due to ink scattering in the ink-jet method, the protrusions Or the height of the protrusions can be further suppressed.

Further, among them, the zeta potential of all the ink-jet inks is preferably −5 mV to −150 mV, and more preferably −40 mV to −130 mV.
In the above two or more types of ink, the difference in zeta potential between the two types of ink for forming a colored ink layer in a predetermined region adjacent to the substrate is preferably 0 mV to 100 mV, and more preferably 0 mV to It is preferably 60 mV.

In order to control the zeta potential of each inkjet ink, it is necessary to select a component that contributes to charging used in each inkjet ink in consideration of the zeta potential. Typical examples of components that contribute to charging in inkjet inks for color filters include pigment dispersants and pigment dispersion aids that have a function of enhancing the action of pigment dispersants.
The inkjet ink for a color filter used in the present invention contains a pigment, a pigment dispersant, a binder component, and a solvent, and may contain other compounds as necessary.

Hereinafter, each component of such ink will be described in order.
(Pigment)
The pigment as the colorant may be selected from any organic colorant and inorganic colorant according to the color required by the pixel (pixel part) R, G, B, etc. and the black matrix layer. it can. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of organic pigments include compounds classified as Pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically those with a Color Index (CI) number. Can be mentioned.
Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

Moreover, in the inkjet ink used for this invention, it is preferable that the dispersion average particle diameter of a pigment is 100 nm or less. In such a case, the pigment dispersibility and the pigment dispersion temporal stability are good, and the ejection stability when ink is used becomes good. In addition, brightness and contrast are improved when the inkjet ink is applied to a color filter after preparation. Here, the dispersion average particle diameter of the pigment was measured at 23 ° C. by a dynamic light scattering method (Doppler scattered light analysis) with a particle size distribution meter (for example, MICROTRAC UPA manufactured by Nikkiso Co., Ltd.) and a measurement time of 360 seconds. The average particle diameter here is a 50% average particle diameter, that is, a volume-based median diameter.
In the case of forming pixels, the pigment is usually blended in a proportion of 1 to 60% by weight, preferably 15 to 40% by weight, based on the total solid content of the inkjet ink. If the amount of the pigment is too small, the transmission density when the ink-jet ink is applied to a predetermined film thickness (usually 0.5 to 2.5 μm) may not be sufficient. Moreover, when there are too many pigments, the characteristics as a coating film such as adhesion to the substrate when the ink-jet ink is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness may be insufficient. There is.

(Pigment dispersant)
The pigment dispersant is blended in the ink to favorably disperse the pigment. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. The pigment dispersant is appropriately selected and used in consideration of the dispersibility of the pigment to be used and the point where the zeta potential of the ink is matched to the desired same sign.

  Among the surfactants, a polymer surfactant having a molecular weight of 1000 or more is preferable. Examples of the polymer surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. Polyoxyethylene alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes.

In the inkjet ink according to the present invention, among the polymeric surfactants, one or more selected from the group consisting of a polyethyleneimine derivative and a polyallylamine derivative is preferable.
Here, the polyethyleneimine derivative is selected from 6-hydroxyhexanoic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid and 4-hydroxydecanoic acid. A plurality of poly (carbonylalkyleneoxy) chains, each containing a plurality of repeating units derivable from at least one other hydroxycarboxylic acid, and derived from 6-hydroxyhexanoic acid A dispersant comprising a polyethyleneimine group in which the weight ratio of units to units derivable from other hydroxycarboxylic acid (s) is in the range of 90:10 to 10:90, or salts thereof. .
Preferably, the weight ratio of units derivable from 6-hydroxyhexanoic acid to units derivable from other hydroxycarboxylic acid (s) is in the range of 20:80 to 80:20, in particular It is in the range of 20:80 to 50:50.

The polyethyleneimine (hereinafter referred to as “PEI”) group may be branched or straight chain and typically has a weight of at least 500, preferably at least 1,000, in particular at least 10,000. It has an average molecular weight. The average molecular weight is preferably less than 600,000, more preferably less than 200,000, in particular less than 50,000.
The poly (carbonylalkyleneoxy) chain (hereinafter referred to as “PCAO chain” in the present specification) is a polyester chain that can be derived by polymerization of the hydroxycarboxylic acid (or the corresponding lactone if appropriate). The chain blocks a plurality of carbonylalkyleneoxy (hereinafter referred to as “CAO”) repeat units that may be derived from 6-hydroxyhexanoic acid and at least one of the other hydroxycarboxylic acids described above. Or it is a copolyester chain included in random arrangement. PCAO chains typically contain, on average, 2 to 100, preferably 3 to 40, more preferably 4 to 15 of the above-mentioned CAO groups, and a chain-stopping terminal group, For example, it may have an oxy terminus such as an optionally substituted alkylcarbonyl, in particular an alkylcarbonyl group containing 12 or more carbon atoms.

The PCAO chain may be attached to the PEI group by a covalent amide and / or ionic salt bond formed between the PEI group and the hydroxycarboxylic acid of the PCAO chain. The acid will be referred to as PCAO acid hereinafter. Such an amide bond may be formed by reaction of a terminal carboxylate group of PCAO acid with a primary or secondary amino group in PEI, while a salt bond is formed with a terminal carboxylate group of PCAO acid. It forms between the positively charged nitrogen atoms of the substituted ammonium groups in PEI.
The weight ratio of PCAO chain to PEI groups is typically 2: 1 to 30: 1, preferably 3: 1 to 20: 1, more preferably 8: 1 to 20: 1, and especially 10: 1. To 15: 1.

Polyethyleneimine derivatives are in the form of polyamines in which the nitrogen atom in the PEI group that is not bound to the PCAO chain is present as a free amino group, or a pair in which the nitrogen atom can be derived from organic and / or inorganic acids. It may be in the form of a salt which exists as a substituted ammonium group associated with an ion, or an intermediate form containing a free amino group and a substituted ammonium group.
Polyethyleneimine derivatives can be prepared by reacting PEI with PCAO acid (s) or precursors thereof.

  The polyallylamine derivative used as a pigment dispersant is a dispersion of a pigment by modifying the amino group of the polyallylamine side chain with polyester, polyamide, or a co-condensate of polyester and polyamide (polyesteramide). It is a polyallylamine derivative represented by the following general formula (I), which has a wide compatibility range with respect to the resin to be used and has excellent pigment dispersibility.

（式中、ＸおよびＹは、それぞれ独立に水素、重合開始剤残基又は連鎖移動触媒残基のいずれかを、Ｒ¹ は遊離のアミノ基、下記一般式（ＩＩ）又は（ＩＩＩ）で示される基を、ｎは２〜１，０００の整数を表す。但しｎ個のＲ^１中、少なくとも１個は一般式（ＩＩＩ）で示される基を表す。）

(Wherein X and Y are each independently hydrogen, a polymerization initiator residue or a chain transfer catalyst residue, R ¹ is a free amino group, represented by the following general formula (II) or (III) Wherein n represents an integer of 2 to 1,000, provided that at least one of n R ¹ represents a group represented by the general formula (III).

（式中、Ｒ^２ は遊離のカルボン酸を有するポリエステル、遊離のカルボン酸を有するポリアミド、または遊離のカルボン酸を有するポリエステルアミドのいずれかからカルボキシル基を除いた残基を表す。）

(In the formula, R ² represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.)

The polyallylamine derivative used in the present invention is, for example, one or more compounds selected from three compounds of polyallylamine and a polyester having a free carboxyl group, polyamide, or a cocondensate of ester and amide (polyesteramide). Obtained by reacting with a compound.
More specifically, the polyallylamine derivative is, for example, a polyallylamine having a polymerization degree of 2 to 1,000 and a polyester having a free carboxyl group and represented by the following general formula (IV) or (V): One of the polyamides represented by the general formula (VI) or (VII) can be prepared as a raw material alone or in combination of two or more.

（式中Ｒ³ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてａは２〜１００の整数を示す。）

(In the formula, R ³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and a represents an integer of 2 to 100.)

（式中Ｒ⁴ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆Ｈ₄ またはＣＨ＝ＣＨを、Ｒ⁵ は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、ポリアルキレングリコールから２つの水酸基を除いた残基を、そしてｂは２〜１００の整数を示す。また、前記鎖中にエーテル結合を有することもある。）

Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁵ is a linear or branched alkylene having 2 to 20 carbon atoms. A group, a residue obtained by removing two hydroxyl groups from polyalkylene glycol, and b represents an integer of 2 to 100. The chain may also have an ether bond.)

（式中Ｒ⁶ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｃは２〜１００の整数を示す。）

(In the formula, R ⁶ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and c represents an integer of 2 to 100.)

（式中Ｒ⁴ は、炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基、Ｃ₆ Ｈ₄ またはＣＨ＝ＣＨを、Ｒ⁷ は炭素原子数２〜２０の直鎖状もしくは分岐のアルキレン基を、そしてｄは２〜１００の整数を示す。）

(Wherein R ⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, C ₆ H ₄ or CH═CH, and R ⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms. A group, and d represents an integer of 2 to 100.)

  The polyallylamine derivative used in the present invention is a polyester in which the repeating components of general formula (IV) and general formula (V) are randomly polymerized on polyallylamine, and the repeating components of general formula (VI) and general formula (VII). Can be produced by reacting a polyamide polymerized randomly with a polyester amide in which the repeating components of general formulas (IV) and / or (V) and general formulas (VI) and / or (VII) are randomly polymerized. Can do. This polyallylamine derivative is, for example, a polyallylamine having a polymerization degree of 2 to 1,000, a polyester having a free carboxyl group, represented by the following general formula (IV) or (V), and the following general formula (VI) or One kind of polyamide represented by (VII) can be prepared as a raw material alone or in combination of two or more kinds.

The polyallylamine derivative used in the present invention is preferably a residue obtained by removing a carboxyl group from a polyester in which R ² has a free carboxylic acid. The polyester preferably has a number average molecular weight in the range of 500 to 20,000.
In the formula (I), the ratio of the polyallylamine of the general formula (III) to the amino group in n R ¹ is preferably 60 to 95%.

  As a commercial product of the polyallylamine derivative, Azisper Pb821 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and as a commercial product of the polyethyleneimine derivative, Solsperse 33500 (manufactured by Nippon Lubrizol Co., Ltd.) can be used.

  Moreover, as a commercial item of the pigment dispersant used for this invention, Disperbyk-110,116,130,140,160,161,162,163,164,165,166,169,170,171,174,180, 182, 183, 184, 185, 2000, 2001, 2020, 2050, 2070, 2090, 2091, 2095, 2096, 2150, etc. (above, manufactured by BYKchemie); EFKA-4008, 4009, 4010, 4047, 4050, 4055, 4080, 4400, 4401, 4402, 4403, 4406, 4500, 4510, 4520, 4530, 4540, 4550, 4560, 4702, 4747, 5010, 5044, 5054, 5055, 5063, 5064, 5065, 5066, 071, 5207, 5244, 5744, etc. (above, manufactured by Efka CHEMICALS); 31845, 32000, 32500, 32550, 32600, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, etc. (above, manufactured by Nihon Lubrizol); Disparon # 2150, # 1210, KS-860, KS- 873N, # 7004, # 1830, # 1850, # 1860, DA-400, DA703-50, DA-705, DA- 725 etc. (above, manufactured by Enomoto Kasei Co., Ltd.); Ajisper Pb822, Pb824, Pb827, etc. (manufactured by Ajinomoto Fine Techno Co., Ltd.).

  In the inkjet ink of the present invention, the content of the pigment dispersant is appropriately adjusted for adjusting the pigment dispersibility and the zeta potential, and is not particularly limited. However, from the viewpoint of pigment dispersibility and pigment dispersion stability over time, 100 wt. It is preferable that it is 5-100 weight part with respect to a part, More preferably, it is 10-80 weight part.

(Binder component)
The ink-jet ink used in the present invention contains a binder component in order to impart film formability and adhesion to the coated surface. In the present invention, the binder component is a component contained in the ink and is contained in order to adhere and fix the pixel at a predetermined position, and is usually a mixture. The ink-jet ink used in the present invention forms an ink layer (coating film) pattern on a substrate by an ink-jet method in order to impart sufficient strength, durability, and adhesion to the coating film, and then the ink layer A binder component that can be cured by a polymerization reaction is used. If it is a binder component which has such a function, the curable binder component applicable to the ink for a color filter use can be used. For example, a polymerization-curable binder component such as a photocurable binder component that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder component that can be polymerized and cured by heating. Can be used.

  As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. An epoxy group is preferably used as the thermosetting functional group. Moreover, you may use further the polymer which has no polymerization reactivity in itself.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

  As an epoxy compound, in order to impart solvent resistance and heat resistance to the cured film, to increase the crosslink density of the polymer with a relatively high molecular weight and the cured film, or to improve the inkjet ejection performance by lowering the viscosity In addition, it is preferable to use a compound having a relatively low molecular weight in combination. As the thermosetting binder component, specifically, binder components as described in paragraph numbers 0132 to 0160 of JP-A-2006-106503 can be used.

(2) Photo-curable binder component For the binder component containing a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, the purpose is to provide film formability and adhesion to the coated surface. It is preferable to include a polymer having a relatively high molecular weight. Here, the relatively high molecular weight means that the molecular weight is higher than that of so-called monomers and oligomers, and the weight average molecular weight can be 5,000 or more. As a polymer having a relatively high molecular weight, any of a polymer having no polymerization reactivity per se and a polymer having a polymerization reactivity per se may be used, and two or more types may be used in combination. May be. And a polymer having a relatively high molecular weight as a main component, if necessary, a polyfunctional monomer or oligomer having two or more photopolymerizable functional groups, a monofunctional monomer or oligomer having one photopolymerizable functional group, A photopolymerization initiator activated by light, a sensitizer, and the like are blended to constitute a photocurable binder component.

When a polymer with no polymerization reactivity is used as a polymer having a relatively high molecular weight, the binder component is a polyfunctional monomer or oligomer having two or more photopolymerizable functional groups. Blend ingredients. In this case, in the binder component, the polyfunctional polymerizable component is polymerized spontaneously by light irradiation or polymerized by the action of other components such as a photopolymerization initiator activated by light irradiation. A network structure is formed in the coating film, and components such as resins and pigments having no polymerization reactivity are encapsulated in the network structure and cured. Specific examples of the photocurable binder component include binder components described in JP-A 2006-106503, paragraphs 0066 to 0128.
Further, in order to impart sufficient adhesion, strength, and hardness to the cured ink layer, the total proportion of the binder component in the total solid content of the ink including the pigment and other components is set to 50 to 75% by weight. Is preferred.

(solvent)
The solvent used in the inkjet ink in the production method of the present invention has a boiling point of 180 ° C. to 260 ° C. as a first solvent, preferably 210 ° C. to 260 ° C. A solvent component having a pressure of 0.5 mmHg or less, preferably 0.1 mmHg or less is contained in an amount of 60 to 95% by weight based on the total amount of the solvent. It is preferable to contain 5-40 weight% with respect to the whole quantity.

  A solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less has an appropriate drying property and evaporation property. Therefore, an inkjet ink containing such a solvent component as a first solvent at a high blending ratio does not dry rapidly when performing either intermittent ejection or continuous ejection, and therefore has an abrupt viscosity at the nozzle tip of the inkjet head. It is difficult to raise and clog, hardly wet the orifice surface, and has excellent discharge direction and discharge amount stability. Therefore, by using such an ink and ejecting it according to a predetermined pattern on the substrate surface by an ink jet method, a colored hardened layer such as a pixel portion or a light shielding portion can be formed accurately and uniformly.

  Furthermore, in the inkjet ink used in the present invention, the drying speed can be optimized by combining an appropriate amount of a solvent component having a boiling point of 130 ° C. or higher and lower than 180 ° C. as the second solvent in addition to the specific first solvent. it can. Although it does not dry rapidly at the nozzle tip of the ink jet head, the solute can be prevented from flowing because the drying speed is moderately high when the ink layer is dried. Therefore, after being ejected onto the substrate, it can be sufficiently leveled by being familiar with the surface of the substrate and then properly dried in a relatively short time by a suitable drying means. Therefore, when such an ink-jet ink is used, a pattern with high uniformity in film thickness in which a thick film portion hardly occurs at the end portion and surface unevenness is reduced can be obtained and dried efficiently.

  The solvent component used as the first solvent may be one type or a mixed solvent of two or more types as long as the solvent has the above boiling point and vapor pressure. The first solvent having the above boiling point and vapor pressure is preferably used in a proportion of 60 to 95% by weight based on the total amount of the solvent. When the proportion of the first solvent is 60% by weight or more of the total amount of the solvent, it is possible to obtain the drying property and the evaporation property suitable for the ink jet system, and the ink jet intermittent discharge stability is improved. The proportion of the first solvent is preferably 70 to 95% by weight of the total amount of solvent, 75 to 95% by weight of the total amount of solvent, and further 80 to 92% by weight of the total amount of solvent. The ink-jet ink used in the present invention may further contain a small amount of a solvent component other than the first solvent and the second solvent, if necessary. This is because the ink of the present invention uses a pigment as a colorant, and therefore it may be necessary to use a dispersion solvent that easily disperses the pigment in order to prepare a pigment dispersion.

  The surface tension of the first solvent at 23 ° C. is preferably 28 mN / m or more from the viewpoint of reducing the outflow of ink to the sparse ink portion during patterning. In addition, when a 1st solvent is a 2 or more types of mixed solvent, it is preferable to have the said surface tension as the whole mixed solvent. Here, the surface tension at 23 ° C. in the present invention can be measured by a surface tension meter (Wilhelmy method) (for example, an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.).

  By forming a wettability variable layer on the substrate surface and exposing it, an ink-philic region is formed on a portion of the substrate where the ink layer is to be formed, and the ink of the present invention is selectively applied to the ink-philic region by the ink jet method. When adhering, the standard solution shown in the wettability test specified in JIS K6768 is used as the first solvent, and the contact angle (θ) after 30 seconds is measured after contacting the droplet, and the Zisman plot is used. A test in which the contact angle with respect to the surface of a test piece having a critical surface tension of 30 mN / m determined by the graph of 25 ° or more, preferably 30 ° or more, and the critical surface tension determined by the same measurement method is 70 mN / m. You may select and use what the contact angle with respect to the surface of a piece shows 10 degrees or less. When the first solvent is a mixed solvent of two or more types, it is preferable that the contact angle as a whole of the mixed solvent is present.

  When an ink is prepared using a solvent that exhibits the above behavior with respect to wettability, the ink exhibits a large repellent property with respect to the surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After changing the wettability of the wettability variable layer to increase the hydrophilicity, the wettability variable layer shows a great affinity for the surface of the wettability variable layer. Therefore, the difference between the wettability of the ink with respect to the ink-philic region formed by selectively exposing a part of the surface of the wettability variable layer and the wettability of the ink repellent region with respect to the surrounding region can be increased. As a result, the ink sprayed onto the ink-philic area by the ink jet method spreads evenly to every corner of the ink-philic area.

  Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. Examples of test pieces having a critical surface tension of 30 mN / m include, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, and the polymer or surface modifier applied on a smooth glass surface. The above test can be actually performed from among those, and the corresponding one can be selected. Moreover, as a test piece which shows critical surface tension 70mN / m, the said test is actually performed from what apply | coated nylon, the glass surface which hydrophilized, etc., and the applicable thing can be selected.

  The first solvent can be selected from the following solvents: glycol ethers such as ethylene glycol monohexyl ether and diethylene glycol monomethyl ether; ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate and the like. Glycol ether esters; aliphatic carboxylic acids such as acetic acid, 2-ethylhexanoic acid and acetic anhydride or anhydrides thereof; aliphatic or aromatic esters such as ethyl acetate and propyl benzoate; such as diethyl carbonate Dicarboxylic acid diesters; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate; ketocarboxylic acid esters such as ethyl acetoacetate; halogenated carbohydrates such as chloroacetic acid and dichloroacetic acid Acids; alcohols or phenols such as ethanol, isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole; alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol; Glycol oligomers such as diethylene glycol and tripropylene glycol; amino alcohols such as 2-diethylaminoethanol and triethanolamine; alkoxy alcohol esters such as 2-ethoxyethyl acetate; ketones such as acetone and methyl isobutyl ketone Morpholines such as N-ethylmorpholine and phenylmorpholine; aliphatic or aromatic amines such as pentylamine, tripentylamine and aniline;

  Specific examples of solvents that can be used as the first solvent include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, Examples thereof include dimethyl succinate and diethyl succinate. These solvents not only satisfy the requirements of a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less, and the dispersibility and dispersion stability of the pigment are relatively good. -A pigment dispersion can be prepared by mixing with a solvent conventionally used for preparing a pigment dispersion, such as methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA), or without using it as a dispersion solvent. it can.

  Furthermore, as these solvents mentioned as specific examples, the standard solution shown in the wettability test specified in JIS K6768 was used, and the contact angle (θ) after 30 seconds was measured by contacting the droplets. The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the graph of the plot is 25 ° or more, and the contact with the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method. The requirement that the angle is 10 ° or less is also satisfied. Therefore, these solvents are also used in the case where the wettability variable layer is provided on the surface of the substrate for exposure and the ink is selectively adhered using the difference in wettability between the exposed portion and the non-exposed portion. It can be suitably used as a solvent.

In addition, by combining the first solvent with a solvent component having a boiling point of 130 ° C. or higher and lower than 180 ° C. as a second solvent in an amount of about 5 to 40% by weight of the total amount of the solvent, the nozzle tip of the inkjet head does not dry rapidly. It is possible to suppress the flow of the solute during layer drying, to appropriately adjust the drying speed, and to form the surface shape of the colored layer more uniformly. The solvent component used as the second solvent may be used alone or in combination of two or more as long as it has the above boiling point.
Among these, the boiling point of each solvent component used for the second solvent is 140 ° C. to 180 ° C., particularly 140 ° C. to 175 ° C. This is preferable because a good coating film with reduced unevenness is easily obtained.

  Moreover, it is preferable that the viscosity at 23 degreeC of said 2nd solvent is 0.5-6 mPa * s. In such a case, by including the second solvent, it is possible to appropriately lower the viscosity of the ink without hindering the effect of the first solvent, and the wettability of the ink itself is improved. As a result, the landed ink droplets are likely to wet and spread to every corner of the entire ink layer formation region. As a result, even when the substrate is diversified, it is possible for the landed ink to spread and spread to the cracks in the black matrix, preventing pixel color loss and brightness reduction, and further reducing display defects. Color filters can be manufactured. There is also a method of landing ink toward the edge of the region in order to adhere the ink to the corner of the region, but this method may cause the ink to flow out from the gap of the black matrix. On the other hand, wetting and spreading to the wrinkles of the black matrix with the ink itself is a more desirable method from the viewpoint of preventing ink from flowing out and preventing color mixing between two or more types of ink. The viscosity of the second solvent at 23 ° C. is preferably 0.5 to 3 mPa · s. When two or more kinds of second solvents are used in combination, they are suitably used as long as the viscosity of the mixed solvent is within the above range even if it is outside the above range. Here, the viscosity at 23 ° C. in the present invention can be measured by a rotational vibration type viscometer (for example, a rotational vibration type viscometer Viscomate VM-1G manufactured by Yamaichi Electronics Co., Ltd.).

Moreover, as said 2nd solvent, what is necessary is just a solvent which has the said boiling point, However, It is preferable to select and use the solvent excellent in compatibility with a 1st solvent suitably.
Specifically, the second solvent includes ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dipropyl ether, propylene glycol monoethyl ether, propylene glycol mono Polyhydric alcohol ethers such as propyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, glycol ethers such as dipropylene glycol dimethyl ether, and glycerin ethers such as glycerin 1,3-dimethyl ether; ethylene glycol Monomethyl ether acetate, ethylene glycol Glycol esters, including glycol ether esters such as ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monomethoxymethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and glycerin 1-monoacetate Polyhydric alcohol esters such as glycerin esters; carboxylic acids such as isovaleric acid, isobutyric acid, propionic acid, butyric acid; ethyl isovalerate, hexyl formate, amyl acetate, isoamyl acetate, cyclohexyl acetate, ethyl lactate, lactic acid Aliphatic esters such as methyl, isoamyl propionate, butyl propionate, butyl butyrate, tributyl citrate, dimethyl oxalate; Alkoxycarboxylates such as ethyl xylpropionate; ketocarboxylates such as methyl acetoacetate; n-amyl alcohol, isoamyl alcohol, 2-ethylbutanol, glycidol, n-hexanol, 2-methylcyclohexanol, 4 Monohydric alcohols such as methyl-2-pentanol, 2-octanol, cyclohexanol, 2-heptanol, 3-heptanol, n-heptanol; diisoamyl ethers and ethers such as 1,8-cineol; Ketones such as ethyl-n-butyl ketone, diisobutyl ketone, di-n-propyl ketone, methylcyclohexanone, methyl-n-hexyl ketone, acetylacetone and diacetone alcohol; alkanes such as nonane and decane It is.

  Among them, ethers including polyhydric alcohol ethers such as glycol ethers and glycerin ethers, polyhydric alcohol esters such as glycol esters and glycerin esters, aliphatic esters, alkoxycarboxylic esters, ketocarboxylic acids It is preferable to use one or more selected from the group consisting of esters including esters. When using the esters and ethers as described above, even when a highly reactive resin is used for the binder component, etc., the ink will maintain good stability over time and be ejected from the inkjet head. There is an advantage that stability is improved. Also, when glycol ethers or glycol esters are used, the wettability with respect to the glass substrate is improved, and the ink layer formation region is easily spread to every corner, which is effective in preventing color loss of pixels. .

  As the second solvent, among others, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, glycerin 1,3-dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monomethoxymethyl ether, propylene Glycol monomethyl ether acetate, methyl acetoacetate, hexyl formate, cyclohexyl acetate, ethyl lactate, isoamyl propionate, butyl propionate, butyl butyrate, tributyl citrate, dimethyl oxalate, ethyl 3-ethoxypropionate, diisoamyl ether, and A solvent that is at least one selected from the group consisting of 1,8-cineole is preferably used.

  In the inkjet ink for a color filter according to the present invention, the content of the second solvent is 5 to 30% by weight, more preferably 5 to 25% by weight, and particularly 8 to 20% by weight, based on the total amount of the solvent. However, it is excellent in stability when ejected from an ink jet head without impeding the effect of the first solvent, can be dried more efficiently, does not easily form a thick film portion at the end, and has surface unevenness. This is preferable from the viewpoint of easily forming a reduced good pixel or the like.

  An ink to be ejected is prepared by using the above solvent in a proportion of usually 40 to 95% by weight with respect to the total amount of the ink containing the solvent. If the amount of the solvent is too small, the viscosity of the ink is high and it becomes difficult to discharge from the inkjet head. Also, if there is too much solvent, the ink film deposited on the wettability change site will be broken before the ink deposit (ink deposition amount) for the predetermined wettability change site (ink layer formation site) is not sufficient. , It protrudes to the surrounding non-exposed areas and further spreads to the adjacent wettability changing part (ink layer forming part). In other words, the amount of ink that can be deposited without sticking out from the wettability change site (ink layer forming site) to which the ink is to be attached becomes insufficient, the film thickness after drying is too thin, The transmission density cannot be obtained.

(Other ingredients)
One or more other additives can be blended in the ink-jet ink for color filter used in the production method of the present invention, if necessary. The following can be illustrated as such an additive.
a) Pigment dispersion aid: For example, blue pigment derivatives such as copper phthalocyanine derivatives, yellow pigment derivatives, and the like.
b) Filler: For example, glass, alumina and the like.
c) Adhesion promoter: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
d) Antioxidant: For example, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.
e) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
f) Anti-aggregation agent: for example, sodium polyacrylate or various surfactants.

  In the ink-jet ink used in the present invention, the blending weight ratio (P / V) of the pigment (P) and the solid content (V) other than the pigment is 0.3 to 1.2. This is preferable from the viewpoint of the balance between ejection performance, ink breakage prevention, and film properties obtained. If the P / V ratio is too low, in order to obtain sufficient coloring power, it is necessary to increase the amount of ink droplets that adhere to the pixel formation region, which causes problems such as ink breaking from the pixel formation region. There is a case. On the other hand, if the P / V ratio is too high, there are cases where ejection performance such as clogging or flight bending occurs in the ink-jet head, or problems such as rough film surfaces occur.

(Ink preparation method)
The ink-jet ink used in the present invention may be prepared by adding and mixing the respective components into the solvent and dissolving or dispersing the solid components.
However, when the pigment is directly put into the whole solvent together with other components such as a binder component and stirred and mixed, the pigment cannot often be sufficiently dispersed in the solvent. Therefore, for example, a solvent having good dispersibility and dispersion stability of the pigment is prepared, and the pigment is added thereto together with the pigment dispersant and, if necessary, a pigment dispersion auxiliary agent, and sufficiently stirred by a dissolver or the like. Is preferably prepared. Then, the obtained pigment dispersion, together with the components other than the pigment, is put into a solvent consisting almost of the first solvent or consisting of only the first solvent, and sufficiently stirred and mixed by a dissolver or the like, and finally the second solvent. Ink jet ink used in the present invention can be prepared by adding. Alternatively, the obtained pigment dispersion, together with the components other than the pigment, is put into a mixed solvent in which the second solvent is added to the solvent consisting essentially of the first solvent or consisting of only the first solvent, and is sufficiently removed by a dissolver or the like. The ink-jet ink used in the present invention can be prepared by stirring and mixing.

(2) Second Aspect In the second aspect, when replacing the inkjet ink in the inkjet ink supply system, the zeta potentials of the ink before and after replacement are controlled to the same sign.
First, zeta potential is measured for the ink existing in the ink supply system before the replacement and the ink after the replacement. If the measured zeta potentials have the same sign, they can be exchanged as they are. On the other hand, when the measured zeta potentials are different from each other, the zeta potential of the ink after replacement is adjusted, for example, by changing the component that contributes to charging such as the pigment dispersant as in the first embodiment. Then, the ink is replaced after the same sign as that of the ink existing in the ink supply system before the replacement. Alternatively, if the measured zeta potentials are different from each other, are the ink exchanges performed using the supply system having the same zeta potential without using the supply system having the different zeta potential? Use a new supply system.

  The inkjet ink used in the second aspect can be the same inkjet ink as described in the first aspect, with the zeta potential adjusted in the same manner. It is omitted here.

  In the second aspect, it is preferable to control the zeta potential of the ink before and after replacement to be negative. When each zeta potential is controlled to be negative, it becomes possible to further suppress aggregation between pigments, and after the ink-jet ink is newly replaced in the ink-jet ink supply system, the components in the ink are aggregated. In addition, the increase in viscosity is less likely to occur, and clogging of the inkjet head is further reduced.

  In the second aspect, it is preferable that the pigment dispersant contained in the ink before and after replacement is independently one or more selected from the group consisting of a polyethyleneimine derivative and a polyallylamine derivative. In such a case, aggregation of pigments can be further suppressed, and aggregation of ink components and increase in viscosity are less likely to occur after a new replacement of the inkjet ink in the inkjet ink supply system. The clogging of the ink jet head is further reduced.

(Ink replacement)
The ink replacement is not particularly limited. When an ink layer is formed by selectively adhering ink jet ink to a predetermined area on a substrate by an ink jet method, an ink supply system used, that is, an ink jet apparatus, generally supplies ink to an ink jet head. An ink supply head that discharges ink supplied from the ink supply unit; an ink supply pipe that is connected to the ink supply unit and the ink jet head and supplies ink from the ink supply unit to the ink jet head; With.

  Examples of a method for exchanging ink in such an ink supply system include the following methods. First, in all the lines of the supply system, the ink that was present in the ink supply system before replacement is pushed out by air or the like and discharged. When removing a part of the ink supply unit such as a supply tank from the line at the time of ink replacement, the ink that was present in the ink supply system before replacement in all the lines of the supply system other than the removed one in the same manner. The air is discharged by extruding it with air. Second, using the ink solvent before the replacement, the entire supply system line or the entire supply system line except a part of the ink supply unit such as a supply tank is washed. The cleaning can be performed by visual inspection until the cleaning solvent is no longer colored. Third, a new ink after replacement is supplied to the ink supply unit, or the supply tank is replaced with a new ink supply tank after replacement. Fourth, in all lines of the supply system, new ink after replacement is fed to the inkjet head. Ink is discharged from all holes in the inkjet head, and until the discharge amount reaches a predetermined weight, the ink is continuously supplied to the inkjet head, stabilizing the ink ejection from the inkjet head, and completing the ink replacement. To do.

  If the zeta potential of the ink before and after replacement is not controlled to the same sign, even if new ink after replacement is sent to the inkjet head in all lines of the supply system in the fourth step, The ink does not discharge from some holes in the inkjet head, and the discharge amount does not reach a predetermined weight. It may cause clogging.

2. Colored layer forming step The color filter manufacturing method according to the present invention is a method of selectively attaching an ink for color filter prepared by adjusting the zeta potential as described above to a predetermined region on a substrate by an ink jet method. A colored layer forming step of forming a layer is included.
The method of selectively attaching by the ink jet method is not particularly limited as long as it can form a colored layer having a desired thickness on the surface of each pixel. As such a method, a method is generally used in which an inkjet head is used and the inkjet ink for a color filter is dropped on the pixel surface while moving the inkjet head or the substrate.

(1) Inkjet head The inkjet head used in this step is not particularly limited as long as a desired amount of inkjet ink can be dropped onto the surface of the base material in the opening provided in the light shielding portion described later. As such an inkjet head, for example, a discharge type that discharges charged inkjet ink continuously and controls the discharge amount by a magnetic field, a discharge type that discharges inkjet ink intermittently using a piezoelectric element, Alternatively, it is possible to use a general ink jet head such as a discharge type that heats ink jet ink and intermittently discharges using the foaming phenomenon.

(2) Color filter substrate Next, the color filter substrate used in this step will be described. The color filter substrate used in this step has a base material and a light-shielding portion formed on the base material.
a. First, the light shielding part will be described. The said light-shielding part is formed on the base material mentioned later, and has an opening part.
As the light-shielding portion used in this step, those in which openings having the same shape are regularly formed at regular intervals are usually used. Here, the specific size and arrangement mode of the opening are not particularly limited, and can be arbitrarily determined according to the use of the color filter manufactured according to the present invention.
The light-shielding part is not particularly limited as long as it is made of a material having a desired light-shielding property, but usually a light-shielding material and a resin, or a metal material is used. .

  When the light-shielding part is composed of a light-shielding material and a resin, as the light-shielding material, a material generally used for a resin light-shielding part used for a color filter can be used. Examples of such light shielding materials include light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments.

  Examples of the resin include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene-methacrylic acid. Acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether Ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamide Resins, polyamic acid resins, polyetherimide resins, and phenolic resin, urea resin and the like.

  On the other hand, when the light shielding part is made of a metal material, the metal material is not particularly limited as long as it has a desired light shielding property, but a chromium material is generally used.

The light shielding part may contain a liquid repellent material exhibiting liquid repellency. By including such a liquid repellent material, a color filter substrate having a light-shielding portion with excellent liquid repellency can be obtained without performing a liquid repellent step described later.
The liquid repellent material used in the present invention is not particularly limited as long as it can exhibit a desired liquid repellent property when the light shielding portion is formed. Examples of such a liquid repellent material include a fluorine-containing compound and fine particles of a low surface energy substance.

Examples of the fluorine-containing compound include monomers or oligomers of compounds represented by the following formula (1) or (2).
General formula (1): Rf-X-Rf '
General formula (2): (Rf-XR) -Y- (R'-X'-Rf ')
In the above formula (1) or (2), Rf and Rf ′ represent a fluoroalkyl group, R and R ′ represent an alkylene group, Rf and Rf ′, and R and R ′ may be the same or different. good. X, X ′ and Y are —COO—, —OCOO—, —CONR ″ —, —OCONR ″ —, —SO ₂ NR ″ —, —SO ₂ —, —SO ₂ O—, —O—, It represents any one of —NR ″ —, —S—, —CO—, OSO ₂ O—, —OPO (OH) O—, and X, X ′ and Y may be the same or different. R ″ represents an alkyl group or hydrogen.

  In addition, as the fluorine-containing compound, polytetrafluoroethylene, perfluoroethylenepropylene resin, perfluoroalkoxy resin, or the like can also be used.

  On the other hand, examples of the fine particles of the low surface energy material include fine particles composed of polyvinylidene fluoride, a fluoroolefin vinyl ether copolymer, a trifluoroethylene-vinylidene fluoride copolymer, and silicone fine particles. it can.

  The method for producing the light shielding part is not particularly limited as long as it can form the light shielding parts arranged in a desired manner. As such a method, for example, a method of forming by a sputtering method using a metal such as chromium, a photolithography method using a resin composition containing light shielding particles, and the above resin composition were used. The thermal transfer method etc. can be mentioned.

b. Base material The base material used for the color filter substrate is not particularly limited as long as it can form the light-shielding portion and the colored layer, and those conventionally used for color filters are used. Can do. Examples of such a base material include, for example, inflexible transparent rigid materials such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plates, or flexibility such as transparent resin films and optical resin plates. Examples thereof include a transparent flexible material. Among these, it is preferable to use Corning 7059 glass in this step. The 7059 glass is excellent in dimensional stability and workability in high-temperature heat treatment, and is a non-alkali glass that does not contain an alkali component in the glass, so it is suitable for a color filter for an active matrix color liquid crystal display device. It is because it can be used for.

  The substrate may be a transparent substrate, or may be a reflective substrate or a white colored one, but a transparent one is usually used in this step.

  The base material may be subjected to surface treatment for preventing alkali elution, imparting a gas barrier property, or other purposes as required. As such surface treatment, for example, in order to make the surface lyophilic, a treatment of irradiating plasma or the like using oxygen gas as an introduction gas can be mentioned.

(3) Formation of colored layer An ink-jet ink for a color filter of each color prepared in the ink preparation step is prepared. Then, as shown in FIG. 1A, the colored layer forming regions 4R, 4G, and 4B of the respective colors defined in the color filter substrate 3 having the light shielding portion 2 formed on the base material 1 are formed. The ink layer is formed by spraying the inkjet ink for forming the colored layer of the corresponding color by the inkjet method. In this ink spraying step, the colored layer forming inkjet ink prepared in the ink preparation step is unlikely to increase in viscosity at the tip of the head 5 and can continue to maintain good ejection properties. Therefore, the ink of the corresponding color can be adhered accurately and uniformly in the predetermined colored layer forming region, and a pixel portion with no color unevenness or color loss can be formed with an accurate pattern. Moreover, since the colored layer forming inkjet ink of each color can be simultaneously sprayed onto the substrate using a plurality of heads, the working efficiency can be improved as compared with the case of forming a colored layer for each color.

  Next, as shown in FIG. 1B, the ink layers 6R, 6G, and 6B of each color are dried and pre-baked as necessary, and then cured by exposure and / or heating as appropriate. In particular, in the present invention, it is preferable that the method further includes a step of drying the ink layer under reduced pressure before the normal pre-bake stage, because the surface shape of the ink layer can be improved. Examples of the conditions for drying under reduced pressure include drying under reduced pressure at 0.1 to 20 Torr for 1 to 20 minutes. At that time, it is preferable to control the substrate temperature within a temperature range of 20 ° C to 60 ° C. Then, after drying under reduced pressure, for example, prebaking is performed on a hot plate at 60 to 165 ° C. for 3 to 80 minutes. Moreover, you may perform a heating and pressure reduction drying simultaneously. Thereafter, when the ink layer is appropriately exposed and / or heated, the crosslinking element of the curable resin contained in the inkjet ink causes a crosslinking reaction, and the ink layer is cured to form a colored cured layer.

The thickness of the pixel is usually about 0.5 to 2.5 μm. Alternatively, the thickness of each color pixel may be changed so that the red pixel 6R is the thinnest, and the green pixel 6G and the blue pixel 6B become thicker in this order, and the optimum thickness may be set for each color.
In the color filter manufactured in the present invention, the maximum value of the film thickness of the pixel is preferably 3.5 μm or less, more preferably 3 μm or less. In the color filter manufactured in the present invention, the difference between the maximum value of the pixel film thickness and the average film thickness is preferably 1 μm or less, more preferably 0.7 μm or less. In such a case, there is no problem in that the pixel in the thick film portion becomes dark or the ITO film formation failure due to the crack occurs to cause disconnection or the like, so that the display failure is reduced. Further, there is no problem that the gap of the liquid crystal layer cannot be accurately obtained. The film thickness refers to the height from the substrate. Further, the average film thickness of the pixel is calculated by dividing the coating film volume in the pixel by the pixel area. Furthermore, the maximum value of the film thickness at the end portion means the value of the film thickness at the highest film thickness in the end bulge portion.

3. Other Steps The color filter manufacturing method of the present invention may have other steps in addition to the colored layer forming step. Such other steps can be arbitrarily determined according to the use etc. of the color filter produced by the present invention. In particular, in the present invention, before the colored layer forming step, It is preferable to have a lyophilic step of making the surface of the base material used for the substrate lyophilic. By having such a lyophilic step, it becomes easy to uniformly spread the ink-jet ink into the opening provided in the light shielding portion in the colored layer forming step, and therefore there is a portion where the colored layer is not formed in the opening. This is because it can be prevented from occurring.
Hereinafter, the lyophilic process used in the present invention will be described.

  The method for making the surface of the substrate lyophilic in the lyophilic step used in the present invention is not particularly limited as long as it can improve the lyophilicity of the surface of the substrate with respect to the inkjet ink. Examples of such a method include a method of forming a highly lyophilic layer on the surface of the substrate and a method of increasing the liquid repellency of the substrate surface itself.

  The method for forming the highly lyophilic layer on the substrate surface is not particularly limited as long as it can form a layer showing a desired lyophilic property with respect to the inkjet ink on the substrate surface. In particular, in this step, after forming a photocatalyst and a photocatalyst-containing layer containing an organopolysiloxane so as to cover the light shielding portion of the color filter substrate and the surface of the base material, a method of irradiating energy from the base material side. Can be mentioned. According to such a method, the photocatalyst-containing layer has a function of reducing the contact angle with the liquid by the action of the photocatalyst accompanying energy irradiation, and by performing energy irradiation from the substrate side, Since energy irradiation can be performed only on the photocatalyst-containing layer formed on the opening, only the photocatalyst-containing layer formed on the substrate surface can improve the lyophilicity with respect to the inkjet ink. A photocatalyst-containing layer having excellent wettability with respect to the inkjet ink can be formed on the substrate surface.

  Here, the photocatalyst-containing layer, the energy irradiation method, and the like can be the same as those described in Japanese Patent Application Laid-Open No. 2004-361426, and thus detailed description thereof is omitted here.

  On the other hand, examples of a method for increasing the lyophilicity of the surface of the substrate itself include a method of irradiating the substrate surface with plasma or the like. The method of irradiating such plasma is not particularly limited as long as it is a method that can remove the residue present on the base material in the opening of the light-shielding portion by dry etching. Generally, organic materials are removed by dry etching. A plasma irradiation method used for removal can be used. In particular, in this step, it is desirable to use a method in which plasma is irradiated in the presence of oxygen and at least one gas selected from the group consisting of nitrogen, helium, or nitrogen as the plasma irradiation method.

  The degree of lyophilicity of the substrate surface in the lyophilic step used in the present invention is preferably such that the contact angle with a liquid having a surface tension of 40 mN / m is less than 10 °, particularly the surface. The contact angle with a liquid having a tension of 50 mN / m is preferably about 10 ° or less, and in particular, the contact angle with a liquid having a surface tension of 60 mN / m is preferably about 10 ° or less.

In addition to the lyophilic step, the other step used in the present invention may include a lyophobic step of lyophobizing the light shielding portion of the color filter substrate before the colored layer forming step. By having such a liquid repellency step, it is possible to effectively prevent the inkjet ink discharged to the opening surrounded by the light shielding portion in the colored layer forming step from leaking to the adjacent opening. Color mixing can be prevented from occurring in the color filter produced by the present invention.
Hereinafter, such a liquid repellency process will be described.

  In the liquid repellency process used in the present invention, the method of making the light shielding part liquid repellent can make the liquid shielding property of the light shielding part relatively higher than the liquid repellency of the substrate surface used for the color filter substrate. The method is not particularly limited. Here, the liquid repellency means liquid repellency with respect to the inkjet ink.

  Examples of such a liquid repellency method include a method of increasing the liquid repellency of the light shielding part itself and a method of forming a layer having a high liquid repellency on the light shielding part.

  Examples of a method for increasing the liquid repellency of the light shielding part itself include a method of introducing fluorine into the light shielding part. Such a method is not particularly limited as long as it is a method capable of relatively introducing a larger amount of fluorine into the light shielding portion than the substrate surface in the opening, but for example, a material constituting the light shielding portion. And a method of irradiating plasma using a fluorine compound as an introduction gas from above the light shielding part, using a resin material and a color filter substrate using an inorganic material as a material constituting the substrate. it can. In such a method, the fluorine compound can be introduced only into the organic substance, and as a result, fluorine can be selectively introduced only into the light shielding portion. As a result, the liquid repellency of the light shielding portion can be made higher than that of the substrate surface in the opening. Can also be easily increased.

  Here, the presence of fluorine in the light-shielding part when the plasma irradiation is performed is present in all the elements detected from the surface of the light-shielding part in the analysis by an X-ray photoelectron spectrometer (XPS: ESCALAB 220i-XL). This can be confirmed by measuring the ratio of the fluorine element.

Further, examples of the fluorine compound of the introduction gas used for the plasma irradiation include carbon fluoride (CF ₄ ), fluorine nitride (NF ₃ ), sulfur fluoride (SF ₆ ), and the like.

  The plasma irradiation method is not particularly limited as long as it can irradiate the plasma using a fluorine compound as an introduction gas and make the light shielding part liquid repellent. Plasma irradiation is performed under reduced pressure. Alternatively, plasma irradiation may be performed under atmospheric pressure. Among these, in the present invention, it is particularly preferable that the plasma irradiation is performed under atmospheric pressure. This is because an apparatus for decompression or the like is not necessary, which can be preferable in terms of cost, manufacturing efficiency, and the like.

Examples of the atmospheric pressure plasma irradiation conditions include the following. The power output can be the same as that used in a general atmospheric pressure plasma irradiation apparatus. At this time, the distance between the plasma electrode to be irradiated and the light shielding portion is preferably about 0.2 mm to 20 mm, and more preferably about 0.4 mm to 5 mm.
The flow rate of the fluorine compound used as the introduction gas is preferably in the range of 1 L / min to 100 L / min, and more preferably in the range of 3 L / min to 50 L / min.

  On the other hand, the method for forming a layer having high liquid repellency on the light shielding part is particularly limited as long as it can form a layer having relatively higher liquid repellency on the light shielding part than the surface of the substrate. Is not to be done. Examples of such a method include a method of forming the above-described photocatalyst-containing layer.

  In the liquid repellency step, the degree of repellency of the light shielding portion is not particularly limited as long as the liquid repellency is relatively higher than that of the opening. In particular, in the present invention, the contact angle with a liquid having a liquid repellency of 40 mN / m is preferably about 10 ° or more, and the contact angle with a liquid having a surface tension of 30 mN / m is particularly 10 ° or more. It is preferable that the contact angle with a liquid having a surface tension of 20 mN / m is 10 ° or more. Moreover, it is preferable that the contact angle with pure water is about 11 ° or more.

  On the other hand, the liquid repellency of the opening is not particularly limited as long as it is lower than the liquid repellency of the light shielding part, but it is preferable that the contact angle with a liquid of 40 mN / m is less than 10 °. In particular, the contact angle with a liquid having a surface tension of 50 mN / m is preferably about 10 ° or less, and further the contact angle with a liquid having a surface tension of 60 mN / m is about 10 ° or less. preferable.

  In addition, the contact angle with the liquid is measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) with a liquid having various surface tensions. The value taken 30 seconds after dropping) is used. Further, as the liquid having various surface tensions used for the measurement, a wetting index standard solution manufactured by Junsei Chemical Co., Ltd. is used.

  The method for producing a color filter of the present invention may include a step usually used in producing a color filter as the other step, in addition to the lyophilic step and the liquid repellency step. Examples of such a process include an overcoat layer forming process for forming an overcoat layer on the colored layer formed by the colored layer forming process.

B. Method for Manufacturing Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention includes a step of manufacturing a color filter using the method for manufacturing a color filter according to the present invention, and the manufactured color filter and liquid crystal driving side substrate. And assembling them so that they face each other.
According to the method for manufacturing a liquid crystal display device according to the present invention, the method using the above-described color filter manufacturing method according to the present invention, in which a color filter with higher performance is obtained using the inkjet ink, has a high quality. Liquid crystal display device.

  When the color filter manufactured as described above and the liquid crystal driving side substrate (TFT array substrate) are made to face each other and the inner peripheral side edge portions of both the substrates are bonded with a sealant, both substrates maintain a cell gap of a predetermined distance. Pasted in state. An active matrix color liquid crystal display device belonging to the liquid crystal display device manufactured by the manufacturing method according to the present invention is obtained by filling the gap between the substrates with liquid crystal and sealing it.

As other manufacturing methods and configurations in the liquid crystal display device, methods and configurations that are usually used can be used, and thus description thereof is omitted here.
The liquid crystal display device obtained by the production method according to the present invention is not particularly limited as long as it has the above-described color filter, and includes known liquid crystal display devices. Specifically, IPS (In-Plane Switching) type, STN (Super Twisted Nematic) type, TN (Twisted Nematic) type, ferroelectric type, antiferroelectric type, MVA mode type and the like can be mentioned.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Production Example 1: Synthesis of binder epoxy compound)
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, the solvent diethylene glycol monobutyl ether acetate (also called butyl carbitol acetate, hereinafter referred to as BCA) does not contain a hydroxyl group according to the blending ratio shown in Table 1. 40.7 parts by weight were charged and heated with stirring to 140 ° C. Next, 54.7 parts by weight of a mixture (dropping component) of a monomer having a composition described in Table 1 and a polymerization initiator at 140 ° C. was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was lowered to 110 ° C., 4.6 parts by weight of a mixture of polymerization initiator and solvent-free diethylene glycol monobutyl ether acetate (BCA) (additional catalyst component) was added, and the temperature at 110 ° C. was maintained for 2 hours. By the way, by terminating the reaction, a binder epoxy compound having the characteristics shown in Table 1 was obtained.

(Production Example 2: Synthesis of binder epoxy compound)
Except for changing the solvent diethylene glycol monobutyl ether acetate (also called butyl carbitol acetate, hereinafter may be referred to as BCA) to the solvent diethylene glycol monoethyl ether acetate (hereinafter sometimes referred to as ECA), Production Example 1 and Similarly, a binder epoxy compound was obtained.

＊１）表中の略号は以下の通りである。
ＧＭＡ：グリシジルメタクリレート
ＭＭＡ：メチルメタクリレート
パーブチルＯ：ｔ−ブチルパーオキシ２−エチルヘキサノエート（日本油脂（株）製商品名）
＊２）重量平均分子量：ゲル浸透クロマトグラフィーによるポリスチレン換算の値である。

* 1) Abbreviations in the table are as follows.
GMA: Glycidyl methacrylate MMA: Methyl methacrylate Perbutyl O: t-Butylperoxy 2-ethylhexanoate (trade name, manufactured by NOF Corporation)
* 2) Weight average molecular weight: A value in terms of polystyrene by gel permeation chromatography.

(Production Examples R1 to R3: Preparation of red inkjet ink for color filter)
(1) Preparation of pigment dispersion A pigment, a pigment dispersant, and an organic solvent are mixed at a ratio shown in Table 2, 300 parts by weight of zirconia beads having a diameter of 0.5 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. For 3 hours. After dispersion, the mixture was filtered through a 5.0 micron membrane filter to obtain red pigment dispersions DR1 to DR9.

＊表２〜７において、略号は以下のとおりである。
アジスパーＰｂ８２１：商品名、味の素ファインテクノ（株）製
Ｓｏｌｓｐｅｒｓｅ３３５００：商品名、日本ルーブリゾール社製
Ｄｉｓｐｅｒｂｙｋ１６１：商品名、ビックケミー・ジャパン（株）製
Ｄｉｓｐｅｒｂｙｋ２０００：商品名、ビックケミー・ジャパン（株）製
ＥＨＰＥ−３１５０：商品名、ダイセル化学工業（株）製
ＢＣＡ：ジエチレングリコールモノブチルエーテルアセテート
ＥＣＡ：ジエチレングリコールモノエチルエーテルアセテート
ＥＥＰ：３−エトキシプロピオン酸エチル

* In Tables 2 to 7, abbreviations are as follows.
Addisper Pb821: trade name, Solsperse 33500 manufactured by Ajinomoto Fine Techno Co., Ltd .: trade name, Dispersbyk 161 manufactured by Nihon Lubrizol Co., Ltd .: trade name, Disperbyk 2000 manufactured by Big Chemie Japan Co., Ltd .: EHPE-3150 manufactured by Big Chemie Japan Co., Ltd. : Trade name, Daicel Chemical Industries, Ltd. BCA: Diethylene glycol monobutyl ether acetate ECA: Diethylene glycol monoethyl ether acetate EEP: Ethyl 3-ethoxypropionate

(2) Preparation of binder solution A Teflon (registered trademark) -coated rotor was placed in a sample bottle and placed on a magnetic stirrer. In this sample bottle, add the binder epoxy compound described in Preparation Example 1, the polyfunctional epoxy resin, etc. according to the following ratio, sufficiently dissolve with stirring at room temperature, and then add the diluent solvent BCA for viscosity adjustment. In addition, after stirring and dissolving, this was filtered to obtain a binder composition. In Production Example R2, the binder epoxy compound of Production Example 2 was used in place of the binder epoxy compound of Production Example 1, and ECA (diethylene glycol monoethyl ether) was used as a diluent solvent instead of BCA (diethylene glycol monobutyl ether acetate). Acetate) was used.

[Binder solution mixing ratio]
-Binder epoxy compound of Production Example 1 (solid content 30% by weight in solvent BCA): 62.5 parts by weight-Multifunctional epoxy resin (trade name jER157S70, manufactured by Japan Epoxy Resins Co., Ltd.): 12.5 parts by weight Neopentyl glycol glycidyl ether: 6.25 parts by weight Trimellitic acid: 12.5 parts by weight BCA (diethylene glycol monobutyl ether acetate): 6.25 parts by weight

(3) Preparation of inkjet ink Using the DR1 to DR9 red pigment dispersions obtained above, the binder solution and a solvent were added so that the blending ratios shown in Table 3 were obtained. And sufficiently mixed to obtain red inkjet inks for color filters of Production Examples R1 to R3. The viscosity, average particle diameter, and zeta potential immediately after ink preparation were measured by the following evaluation methods. The measurement results are also shown in Table 3.

[Evaluation method]
(1) Viscosity Viscosity was measured at 23 ° C. with a rotational vibration type viscometer Viscomate VM-1G manufactured by Yamaichi Electronics.
(2) Average particle diameter The average particle diameter was measured at 23 ° C. by a dynamic light scattering method using a particle size distribution meter (MICROTRAC UPA, manufactured by Nikkiso Co., Ltd.) after the ink was diluted 100 times with a main solvent. Time was measured as 360 seconds. The average particle diameter here is a 50% average particle diameter, that is, a volume-based median diameter.
(3) Zeta potential The zeta potential was measured using a Zetasizer Nano ZS manufactured by Malvern, and production examples R1 and R3 were a dispersion medium diethylene glycol monobutyl ether acetate (dispersion medium relative dielectric constant 6.2, dispersion medium viscosity 3.56 mPa · s), Production Example R2 is a sample diluted 10000 times with a dispersion medium diethylene glycol monoethyl ether acetate (dispersion medium relative dielectric constant 7.7, dispersion medium viscosity 2.79 mPa · s) into a non-aqueous dip cell, and the measurement temperature Measured at 25 ° C. The applied voltage was 40 V, the electrophoretic mobility was measured by a laser Doppler velocity measurement method, and the zeta potential was calculated using the Huckle equation.
Huckel's equation u = 2ε ₀ ε _r ζ / 3η
u: electrophoretic mobility ε ₀ : dielectric constant of vacuum ε _r : relative permittivity of dispersion medium ζ: zeta potential η: viscosity of dispersion medium

(Production Examples G1 to G2: Preparation of green inkjet ink for color filter)
(1) Preparation of pigment dispersion A pigment, a pigment dispersant, and an organic solvent are mixed at a ratio shown in Table 4, 300 parts by weight of zirconia beads having a diameter of 0.5 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. For 3 hours. After the dispersion, the mixture was filtered through a 5.0 micron membrane filter to obtain green pigment dispersions DG1 to DG8.

(2) Preparation of inkjet ink The binder solution having the same composition as the binder solution used in the red inkjet ink of Production Example R1 was used.
Using each of the DG1 to DG8 green pigment dispersions obtained above, the binder solution and a solvent are further added and mixed well so that the blending ratio shown in Table 5 is obtained. The green inkjet ink for color filters of Examples G1 to G2 was obtained. The viscosity, average particle diameter, and zeta potential immediately after ink preparation were measured by the following evaluation methods. The measurement results are also shown in Table 5.

（製造例Ｂ１〜Ｂ３：カラーフィルター用青色インクジェットインクの調製）
（１）顔料分散液の調製
顔料、顔料分散剤、及び有機溶剤を表６に示す割合で混合し、直径０．５ｍｍのジルコニアビーズを３００重量部加え、ペイントシェーカー（浅田鉄鋼社製）を用いて３時間分散を行った。分散後、５．０ミクロンのメンブランフィルターで濾過し、青色顔料分散液ＤＢ１〜ＤＢ６を得た。

(Production Examples B1 to B3: Preparation of blue inkjet ink for color filter)
(1) Preparation of pigment dispersion A pigment, a pigment dispersant, and an organic solvent are mixed at a ratio shown in Table 6, 300 parts by weight of zirconia beads having a diameter of 0.5 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. For 3 hours. After dispersion, the mixture was filtered through a 5.0 micron membrane filter to obtain blue pigment dispersions DB1 to DB6.

(2) Preparation of inkjet ink The binder solution having the same composition as the binder solution used in the red inkjet ink of Production Example R1 was used.
Using the blue pigment dispersions of DB1 to DB6 obtained above, the binder solution and a solvent are further added and mixed well so that the blending ratio shown in Table 7 is obtained. The blue inkjet ink for color filters of Examples B1 to B3 was obtained. The viscosity, average particle diameter, and zeta potential immediately after ink preparation were measured by the following evaluation methods. The measurement results are also shown in Table 7.

Example 1
Production Example R1 (Zeta potential; −61.1 mV) as a red ink, Production Example G1 (Zeta potential; −113 mV) as a green ink, Production Example B1 (Zeta potential; −84.8 mV) as a blue ink, and all the inks The color filters were manufactured using the zeta potentials of the negative zeta potentials set to be negative.
First, EAGLE 2000 made by Corning having a thickness of 0.7 mm, a width of 370 mm, and a length of 470 mm, which is used as a glass material for a color filter, is prepared, and a resin black matrix is formed on the glass substrate by a photolithography method. Thus, a color filter substrate was produced. At this time, the black matrix is formed so that the opening is 100 μm × 300 μm and the line width of the light-shielding portion is 20 μm, and the vertical matrix is arranged at 120 μm pitch and 320 μm pitch in the vertical direction with 480 pixels and 1320 pixels in the horizontal direction. It was supposed to be. At this time, the thickness of the light shielding portion was set to an average of 2.2 μm.

  By applying a plasma treatment using a fluorine compound as an introduction gas to the color filter substrate, the surface of the black matrix was made lyophobic and the other region (colored layer forming region) was made lyophilic. At this time, the contact angle with a liquid having a surface tension of 40 mN / m was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Chemical Co., Ltd.). It was 9 °.

  The blue inkjet ink of Production Example B1 was accurately and uniformly attached to the blue pixel forming portion partitioned by the black matrix of the substrate by an inkjet method. Next, the green inkjet ink of Production Example G1 was accurately and uniformly attached to the green pixel forming portion of the same substrate by the inkjet method. Next, the red inkjet ink of Production Example R1 was accurately and uniformly attached to the red pixel forming portion of the same substrate by the inkjet method.

  Then, it dried under reduced pressure on a 25 degreeC hotplate for 120 seconds at 10 Torr, and also prebaked for 10 minutes on the 80 degreeC hotplate. Then, in a clean oven, post-baking is performed by heating at 200 ° C. for 30 minutes, and further, post-baking is performed by heating at 240 ° C. for 30 minutes. The average film thickness after drying and curing on the substrate is 2. An RGB three-color pixel pattern having 1 μm and G and B of 2.15 μm was formed. The average film thickness is measured by measuring the film thickness of the entire area of the pixel formation region (one pixel) every 1 μm using an optical interference type three-dimensional non-contact surface shape measuring device (product name Micromap 557N manufactured by Micromap USA). Is the average. The following evaluation was performed using the substrate on which the RGB pixel pattern was formed.

[Evaluation]
In order to confirm the occurrence of protrusions at a portion (mixed color portion) where some ink was scattered and mixed color was generated, the height from the average film thickness of the mixed color portion was measured. The film thickness of the color mixture part was also measured using a light interference type three-dimensional non-contact surface shape measuring device (product name Micromap 557N manufactured by Micromap, USA). The results are shown in Table 8. A photograph of the color mixture portion is shown in FIG. As apparent from FIG. 2, no protrusion was generated in the color mixture portion of Example 1.

Next, the substrate on which the RGB pixel pattern is formed is immersed in IPA for 5 minutes, and then dried and washed with IPA vapor, and then cleaned at a substrate setting temperature of 200 ° C. under a vacuum of 6 × 10 ⁻³ Torr. An (indium tin oxide) electrode was formed to a thickness of 120 nm. The substrate on which this ITO film was formed was further immersed in IPA for 5 minutes, steam-washed with IPA, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. Got.

(Example 2)
Production Example R2 (Zeta potential; −90.2) as a red ink, Production Example G1 (Zeta potential; −113) as a green ink, Production Example B2 (Zeta potential; −113) as a blue ink, and all zeta inks A color filter was produced in the same manner as in Example 1 except that the potentials were used with the same sign (minus).
In the same manner as in Example 1, the height from the average film thickness of the color mixture portion was measured. The results are also shown in Table 8.

(Example 3)
Production Example R3 (Zeta potential; +30.5) as a red ink, Production Example G2 (Zeta potential; +19) as a green ink, and Production Example B3 (Zeta potential; +33.3) as a blue ink, and the zeta potential of all the inks A color filter was produced in the same manner as in Example 1 except that these were used in a positive manner.
In the same manner as in Example 1, the height from the average film thickness of the color mixture portion was measured. The results are also shown in Table 8.

(Comparative Example 1)
Production Example R3 (zeta potential; +30.5) as a red ink, Production Example G1 (zeta potential; −113) as a green ink, and Production Example B3 (zeta potential; +33.3) as a blue ink, and all zeta inks A color filter was produced in the same manner as in Example 1 except that the potentials were used without being aligned with each other.
Using the substrate on which the RGB pixel pattern was formed, the height from the average film thickness of the color mixture portion was measured in the same manner as in Example 1. The results are also shown in Table 8. Further, a photograph of the color mixture portion is shown in FIG. As apparent from FIG. 3, the color mixture portion of Comparative Example 1 has projections between the color mixture portions of Production Example R3 and Production Example G1 having different zeta potential signs and between the color mixture portions of Production Example B3 and Production Example G1. Had occurred. No protrusion was produced in the mixed color portion of Production Example R3 and Production Example B3 having the same zeta potential sign.

(Comparative Example 2)
Production Example R1 (Zeta potential; −61.1) as a red ink, Production Example G2 (Zeta potential; +19) as a green ink, and Production Example B2 (Zeta potential; −113) as a blue ink, and the zeta potential of all inks Were used in the same manner as in Example 1 except that they were used without having the same reference numerals.
In the same manner as in Example 1, the height from the average film thickness of the color mixture portion was measured. The results are also shown in Table 8.

Example 4
The production example R1 (zeta potential; −61.1) was replaced with the production example R2 (zeta potential; −90.2) as a red ink, and the production example B1 (zeta potential; −84.8) was produced as a blue ink. The color filter was manufactured by replacing with Example B2 (Zeta potential; −113) and using the zeta potentials of the inks before and after the replacement in a negative manner.
As a result, neither the red ink jet head nor the blue ink ink jet head was clogged.

(Comparative Example 3)
The production example R1 (zeta potential; −61.1) was replaced with production example R3 (zeta potential; +30.5) as a red ink, and the production example G1 (zeta potential; −113) to production example G2 (zeta) as a green ink. The potential was changed to +19), and the blue ink was changed from Production Example B1 (Zeta potential; −84.8) to Production Example B3 (Zeta potential; +33.3), and the zeta potentials of the ink before and after replacement were aligned with each other. The color filter was manufactured without using.
As a result, the red ink jet head, the green ink ink jet head, and the blue ink ink jet head were clogged.

(Comparative Example 4)
The production example R3 (zeta potential; +30.5) was replaced with the production example R2 (zeta potential; −90.2) as a red ink, and the production example G2 (zeta potential; +19) was changed to the production example G1 (zeta potential) as a green ink. -113) and the blue ink as Production Example B3 (Zeta potential; +33.3) to Production Example B2 (Zeta potential; -113) without changing the zeta potentials of the ink before and after the exchange. Used to produce a color filter.
As a result, the red ink jet head, the green ink ink jet head, and the blue ink ink jet head were clogged.

<Test example>
As shown in Table 9, the same volume of each inkjet ink was mixed, and the viscosity and average particle size after mixing (immediately after 5 minutes) were measured. The viscosity and the average particle diameter are the same measurement methods as described in the production examples.

It is the schematic which shows an example of the manufacturing method of the color filter of this invention. 2 is a photograph of a color mixture portion in Example 1. FIG. 6 is a photograph of a color mixture portion in Comparative Example 1. It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Light-shielding part 3 Color filter substrate 4 (4R, 4G, 4B) Colored layer formation area 5 Inkjet head 6 (6R, 6G, 6B) Ink layer 31 Color filter 32 Electrode substrate 33 Gap part 34 Sealing material 35 Transparent Substrate 36 Black matrix layer 37 (37R, 37G, 37B) Pixel 38 Protective film 39 Transparent electrode film 40 Alignment film 41 Pearl 42 Columnar spacer 101, 102 Color filter

Claims (9)

Two or more types of inkjet inks for color filters containing a pigment, a pigment dispersant, a binder component containing at least one selected from a thermosetting binder component and a photocurable binder component, and a solvent are used as a color filter substrate. A method for producing a color filter including a colored layer forming step of forming a colored layer by selectively adhering to an upper predetermined region by an inkjet method,
A method for producing a color filter, comprising: an ink preparation step for controlling zeta potentials of the color filter inkjet inks to have the same sign.   2. The method for producing a color filter according to claim 1, wherein the zeta potential of each of the color filter inkjet inks is controlled to be negative. The pigment dispersants contained in the two or more types of inkjet inks are each independently one or more selected from the group consisting of a polyethyleneimine derivative and a polyallylamine derivative, and the polyethyleneimine derivative is a polyethyleneimine group. 6-hydroxyhexanoic acid and at least one hydroxycarboxylic acid selected from ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, and 4-hydroxydecanoic acid A polyethylenimine derivative having a poly (carbonylalkyleneoxy) chain derived by acid polymerization, wherein the polyallylamine derivative is a polyallylamine derivative represented by the following general formula (I): Claim 1 or 2 The color filter manufacturing method as set forth.

(Wherein X and Y are each independently hydrogen, a polymerization initiator residue or a chain transfer catalyst residue, R ¹ is a free amino group, represented by the following general formula (II) or (III) Wherein n represents an integer of 2 to 1,000, provided that at least one of n R ¹ represents a group represented by the general formula (III).

(In the formula, R ² represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.)   The method for producing a color filter according to any one of claims 1 to 3, further comprising a lyophilic step of making the surface of a predetermined region of the substrate surface lyophilic before the colored layer forming step. Two or more types of inkjet inks for color filters containing a pigment, a pigment dispersant, a binder component containing at least one selected from a thermosetting binder component and a photocurable binder component, and a solvent are used as a color filter substrate. A method for producing a color filter including a colored layer forming step of forming a colored layer by selectively adhering to an upper predetermined region by an inkjet method,
A method for producing a color filter, comprising: an ink preparation step for controlling zeta potentials of ink before and after replacement with the same sign when the ink-jet ink is replaced in the ink-jet ink supply system.   6. The method for producing a color filter according to claim 5, wherein the zeta potential of the ink before and after replacement is controlled to be negative. The pigment dispersant contained in the ink before and after replacement is independently one or more selected from the group consisting of a polyethyleneimine derivative and a polyallylamine derivative, wherein the polyethyleneimine derivative is a polyethyleneimine group, 6- Polymerization of hydroxyhexanoic acid with at least one hydroxycarboxylic acid selected from ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, and 4-hydroxydecanoic acid 6. A polyethylenimine derivative having a poly (carbonylalkyleneoxy) chain derived from, wherein the polyallylamine derivative is a polyallylamine derivative represented by the following general formula (I): Or the color fill described in 6 Method of manufacturing over.

(Wherein X and Y are each independently hydrogen, a polymerization initiator residue or a chain transfer catalyst residue, R ¹ is a free amino group, represented by the following general formula (II) or (III) Wherein n represents an integer of 2 to 1,000, provided that at least one of n R ¹ represents a group represented by the general formula (III).

(In the formula, R ² represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.)   The method for producing a color filter according to any one of claims 5 to 7, further comprising a lyophilic step of making the surface of a predetermined region of the substrate surface lyophilic before the colored layer forming step.   A liquid crystal display comprising: a step of producing a color filter using the method for producing a color filter according to any one of claims 1 to 8; and a step of assembling the produced color filter and a liquid crystal driving side substrate to face each other. Device manufacturing method.

Images