JP2008076855A - Ink-jet ink for color filter, method for manufacturing the color filter, and method for manufacturing liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink-jet ink for a color filter, the ink having superior pigment dispersibility and stability of pigment dispersion with time and hardly causing wrinkles or cracks in a cured film, after ink is prepared, and to provide a method for manufacturing a color filter that uses the ink. <P>SOLUTION: The ink-jet ink for a color filter contains: (A) a pigment; (B) a pigment dispersant; (C) a dispersion assistant resin comprising a specified alicyclic epoxy resin; (D) an epoxy compound having two or more epoxy groups in one molecule, different from the above dispersion assistant resin (C); (E) a polyvalent carboxylic acid derivative of a carboxylic acid (e1), having a specified structure concealed by a vinyl ether compound (e2); and (F) a solvent. The ink is used for the method for manufacturing color filters. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an inkjet ink for a color filter used for forming a colored layer having a predetermined pattern such as a pixel portion, a method for producing a color filter using the inkjet ink, and a liquid crystal display device using the color filter. It relates to a manufacturing method.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction. In particular, there is a high demand for cost reduction for a color filter having high specific gravity.
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 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 dyeing 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 a decrease in yield 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 a substrate surface by an ink jet method has been proposed (Patent Document 1).
JP 59-75205 A JP 2003-113224 A

In order to form pixels by spraying ink in accordance with an accurate pattern using an inkjet method, straightness and stability when ejected from the ejection head are required. A pigment is often used as a colorant for the color filter. However, when the pigment dispersibility of the color filter inkjet ink is poor, clogging occurs in the nozzle portion of the ejection head due to aggregation of pigment particles. Therefore, when a pigment is used as the colorant, the pigment dispersibility and the stability over time affect the ink ejection performance. In addition, when the pigment dispersibility is insufficient, brightness and contrast may be lowered after the color filter is formed.
In order to improve pigment dispersibility, a pigment dispersion is prepared by previously dispersing a pigment with a pigment dispersant, and then a binder component is mixed with the pigment dispersion to form an ink. However, depending on the pigment dispersant used, there is a problem that wrinkles and cracks are likely to occur when a cured layer (hereinafter referred to as a cured layer) such as a colored layer is prepared using the ink after the ink is prepared. there were. In particular, when a colored layer of a color filter for a display panel such as a liquid crystal display panel is formed using inkjet ink, after forming the colored layer on the substrate, a protective film is formed thereon if necessary, and then Although the transparent electrode film is formed, there arises a problem that wrinkles are generated on the surface of the transparent electrode film. As a method for forming the transparent electrode film, it is necessary to heat the substrate under a reduced pressure atmosphere such as a vacuum deposition method, a sputtering method, or an ion plating method. For example, when a typical ITO film is vacuum-deposited as a transparent electrode film, the underlying colored layer and protective film are exposed to a high temperature and an ultra-low pressure due to vacuum. When a cured layer such as a colored layer formed from ink is exposed to such ultra-low pressure and high temperature conditions, the cured layer thermally expands and contracts to generate wrinkles, which distorts adjacent layers such as a transparent electrode film. It is thought that wrinkles and cracks occur on the surface. When wrinkles or cracks occur on the surface of the transparent electrode film, the local resistivity is increased at the location where the transparent electrode film is generated, resulting in disconnection, resulting in an afterimage or eventually causing a display defect.

  On the other hand, Patent Document 2 discloses a photocurable composition containing a polyfunctional alicyclic epoxy compound as a thermal polymerization crosslinking agent. However, Patent Document 2 does not describe anything about using a polyfunctional alicyclic epoxy compound in a pigment dispersion, improving the pigment dispersibility, and preventing wrinkles or cracks in the cured layer.

The present invention has been achieved in view of the above-mentioned actual condition, and the first object thereof is excellent in pigment dispersibility and stability over time, hardly causes wrinkles and cracks in the cured layer, and causes wrinkles and cracks in adjacent layers. An object of the present invention is to provide an ink-jet ink for a color filter which is difficult to generate and a method for producing the same.
In addition, the second object of the present invention is to provide a method for producing a color filter, which is capable of obtaining a color filter with improved brightness and contrast, which is less likely to cause display defects, using an inkjet ink that achieves the above object. There is to do.
A third object of the present invention is to provide a liquid crystal display device using a color filter manufacturing method that achieves the above object.

As a result of intensive studies to solve the above problems, the present inventors have used the above specific epoxy resin as a pigment dispersion auxiliary resin, and further combined an epoxy compound and a specific polyvalent carboxylic acid derivative as a binder component. Ink-jet ink for color filter used has excellent pigment dispersibility and stability over time. The present invention has been completed by obtaining knowledge that a simple color filter can be obtained.
That is, the present invention includes the following [1] to [12].

[1] (A) pigment,
(B) a pigment dispersant,
(C) A dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1):
(D) An epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C),
(E) An inkjet ink for a color filter, comprising a polycarboxylic acid derivative in which a carboxylic acid (e1) having a structure represented by the following formula (11) is latentized by a vinyl ether compound (e2), and (F) a solvent.

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

[2] (A) pigment,
(B) a pigment dispersant,
(C) After preparing a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1), and (F) a pigment dispersion containing a solvent, at least (D) different from the dispersion auxiliary resin (C), Addition of an epoxy compound having two or more epoxy groups in one molecule, and (E) a polyvalent carboxylic acid derivative in which a carboxylic acid (e1) having a structure of the following formula (11) is latentized by a vinyl ether compound (e2) An ink-jet ink for color filters.

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

[3] The inkjet ink for a color filter as described in [1] above, wherein the pigment has a dispersion average particle diameter of 100 nm or less.
[4] The inkjet ink for a color filter according to any one of [1] to [3], wherein a sum of n1 to nk in the epoxy resin represented by the formula (1) is 4 to 30.
[5] The color filter according to any one of [1] to [4], wherein the dispersion auxiliary resin (C) is 5 to 80 parts by weight with respect to 100 parts by weight of the pigment dispersant (B). Inkjet ink.
[6] The above [1], wherein the dispersion auxiliary resin (C) is 5 to 70 parts by weight with respect to 100 parts by weight of the total amount of the epoxy compound (D) and the polyvalent carboxylic acid derivative (E). Thru | or the inkjet ink for color filters in any one of [5].
[7] The above-mentioned solvent contains a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 0.5 mmHg or less as a main solvent in a proportion of 60% by weight or more based on the total amount of the solvent. The inkjet ink for color filters according to any one of [1] to [6].
[8] The main solvent is 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, dimethyl succinate, and The inkjet ink for a color filter according to the above [7], which is at least one selected from the group consisting of diethyl succinate.

  [9] At least (A) a pigment, (B) a pigment dispersant, (C) a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1) is mixed with (F) a solvent, and dispersed to disperse the pigment. A step of preparing a liquid;

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

少なくとも（Ｄ）前記分散補助樹脂（Ｃ）とは異なる、１分子中にエポキシ基を２個以上有するエポキシ化合物、及び（Ｅ）下記式（１１）の構造を有するカルボン酸（ｅ１）がビニルエーテル化合物（ｅ２）により潜在化された多価カルボン酸誘導体を含有するバインダー系を、前記顔料分散液と混合する工程を有する、カラーフィルター用インクジェットインクの製造方法。

At least (D) an epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C), and (E) a carboxylic acid (e1) having a structure of the following formula (11) is a vinyl ether compound The manufacturing method of the inkjet ink for color filters which has the process of mixing the binder system containing the polyhydric carboxylic acid derivative latentized by (e2) with the said pigment dispersion liquid.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

[10] A colored layer forming step of forming a colored layer by selectively attaching the color filter inkjet ink according to any one of [1] to [8] to a predetermined region on a substrate by an inkjet method. A method for producing a color filter, comprising:
[11] The method for producing a color filter according to [10], further comprising a lyophilic step of making the surface of a predetermined region of the substrate surface lyophilic before the colored layer forming step.

  [12] A step of manufacturing a color filter using the method for manufacturing a color filter according to [10] or [11], and a step of assembling the manufactured color filter and the liquid crystal driving side substrate to face each other. And manufacturing method of liquid crystal display device.

The ink-jet ink used for the color filter according to the present invention is excellent in the temporal dispersion of ink properties including pigment dispersibility and pigment dispersion, hardly causes wrinkles and cracks in the cured layer, and wrinkles and cracks in adjacent layers such as an ITO film. It is difficult to generate. Further, the cured layer is excellent in solvent resistance and adhesion, and the film physical properties of the pixel can be improved. The ink-jet ink according to the present invention is less likely to cause wrinkles or cracks in the cured layer of the ink due to the action of the dispersion assisting resin, even when a pigment dispersant that cannot be used because wrinkles are generated in the cured layer. For this reason, there is an advantage that the range of selection of the pigment dispersant is widened. In addition, the inkjet ink for a color filter according to the present invention has excellent yellowing resistance, color purity when applied to a color filter, and excellent pigment dispersibility. Therefore, brightness and contrast when applied to a color filter. Will improve. Furthermore, the inkjet ink for a color filter according to the present invention uses the polyvalent carboxylic acid derivative (E) as a binder-based curing agent component, so that the reactive site of the carboxyl group coexists with the epoxy group at a high concentration in the ink. However, the straightness of the ejection direction from the inkjet head and the stability of the ejection amount can be made extremely excellent.
In addition, according to the method for producing a color filter of the present invention, it is possible to obtain a color filter with improved brightness and contrast by using an ink-jet ink that achieves the above-described object, in which the problem of display failure hardly occurs. In addition, since the manufacturing method uses an inkjet method, cost reduction and yield improvement can be realized.
In addition, according to the method for manufacturing a liquid crystal display device of the present invention, a high quality liquid crystal display device can be obtained because a process for obtaining a color filter with reduced display defects and improved brightness and contrast is used.

The present invention is described in detail below.
1. Ink-jet ink for color filter The ink-jet ink for color filter of the present invention comprises (A) a pigment, (B) a pigment dispersant, (C) a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1), (D) Different from the dispersion assisting resin (C), an epoxy compound having two or more epoxy groups in one molecule, (E) a carboxylic acid (e1) having a structure of the following formula (11) is latent by the vinyl ether compound (e2) Containing a converted polycarboxylic acid derivative and (F) a solvent.
The inkjet ink for a color filter of the present invention comprises (A) a pigment, (B) a pigment dispersant, (C) a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1), and (F) a solvent. After preparing the pigment dispersion to be contained, at least (D) an epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C), and (E) a structure of the following formula (11) The carboxylic acid (e1) possessed by adding a polyvalent carboxylic acid derivative made latent by the vinyl ether compound (e2).

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

The ink-jet ink used in the color filter according to the present invention is excellent in pigment dispersibility and stability due to the action of the dispersion auxiliary resin, and further, the dispersion auxiliary resin (C) and the specific binder system (D) and (E). In combination, the combined effect of the ink characteristics including pigment dispersion is excellent over time, the cured layer is less likely to cause wrinkles and cracks, and the ITO layer and other adjacent layers are less likely to cause wrinkles and cracks. is there. Further, the cured layer is excellent in solvent resistance and adhesion, and the film physical properties of the pixel can be improved. The ink-jet ink according to the present invention is less likely to cause wrinkles or cracks in the cured layer of the ink due to the action of the dispersion assisting resin, even when a pigment dispersant that cannot be used because wrinkles are generated in the cured layer. For this reason, there is an advantage that the range of selection of the pigment dispersant is widened.
In addition, the inkjet ink for a color filter according to the present invention has excellent yellowing resistance, color purity when applied to a color filter, and excellent pigment dispersibility. Therefore, brightness and contrast when applied to a color filter. Will improve. Furthermore, the inkjet ink for a color filter according to the present invention uses the polyvalent carboxylic acid derivative (E) as a binder-based curing agent component, so that the reactive site of the carboxyl group coexists with the epoxy group at a high concentration in the ink. However, the straightness of the ejection direction from the inkjet head and the stability of the ejection amount can be made extremely excellent.

  The effect of improving the pigment dispersibility and the pigment dispersion aging stability by the dispersion auxiliary resin (C) is not clear, but the acid is blocked as a curing agent component of the dispersion auxiliary resin having an epoxy group and the binder system. Since the polyvalent carboxylic acid derivative (E) is used in combination, it achieves excellent temporal stability of ink characteristics including pigment dispersibility while coexisting with the epoxy group at a high concentration of the carboxyl group in the ink. It will be possible. In addition, the dispersion auxiliary resin (C) has an excellent thermosetting property because it has a highly reactive terminal epoxy group, and the function that the cured layer is difficult to thermally expand and contract, and in combination with the above specific binder system Because of the synergistic effect, it becomes possible to increase the number of crosslinking points by coexisting with the epoxy group at a high concentration in the ink as described above, so that the solid content other than the pigment (P) and the pigment ( Even when the blending weight ratio (P / V ratio) of V) is increased, it is considered that the solvent resistance of the cured layer, adhesion, and the effect of preventing wrinkles and cracks from occurring even under ultra-low pressure and high temperature are improved. .

Hereinafter, components used in the inkjet ink for a color filter of the present invention will be described.
<(A) Pigment>
The pigment (A) as the colorant can be selected from organic colorants and inorganic colorants according to the color required by the light-shielding part, such as R, G, B, etc. of the colored layer (pixel part). can do. 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; published by The Society of Dyers and Colourists), 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.
When forming the pattern of the light-shielding part on the substrate of the color filter using the ink-jet ink of the present invention, a black pigment having a high light-shielding property is blended in the ink-jet ink. As the black pigment having a high light shielding property, for example, an inorganic colorant such as carbon black or iron trioxide or an organic colorant such as cyanine black can be used.

  When forming a pixel, the pigment (A) 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. When the pigment (A) is less than 1% by weight, the light 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. Further, when the pigment (D) exceeds 60% by weight, it is a coating film such as adhesion to the substrate when the ink-jet ink is applied on the substrate and cured, surface roughness of the cured layer, coating film hardness, etc. There is a risk that the characteristics of the above will be insufficient.

Moreover, in the inkjet ink used for the color filter according to the present invention, the dispersion average particle diameter of the pigment is preferably 100 nm or less. In such a case, the pigment dispersibility and the pigment dispersion stability over time are good, and the brightness and contrast are improved when the ink-jet ink is applied to a color filter after preparation. Also, the ejection stability when ink is used is improved. By using the dispersion auxiliary resin (C) described later in the present invention at the time of pigment dispersion, such a dispersion average particle diameter can be achieved.
Here, the dispersion average particle diameter of the pigment is measured at 23 ° C. by a dynamic light scattering method (Doppler scattered light analysis) with a particle size distribution meter (for example, MICROTRAC UPA MODEL 9230 manufactured by Nikkiso Co., Ltd.). Moreover, the average particle diameter here is a volume-based median diameter.

<(B) Pigment dispersant>
The pigment dispersant is blended in the inkjet ink in order to disperse the pigment satisfactorily, and is used when the pigment is dispersed. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.
That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

As commercially available pigment dispersants, 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, 5071, 5207, 244, 5744 and the like (manufactured by Efka CHEMICALS); , 32500, 32550, 32600, 33500, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, etc. (manufactured by Nihon Lubrizol Co., Ltd.); # 7004, # 1830, # 1850, # 1860, DA-400, DA703-50, DA-705, DA-725, etc. Or more, manufactured by Kusumoto Kasei Co., Ltd.); Adisper PB-821, PB-822, PB-824, PB-827, and the like (Ajinomoto Fine-Techno Co., Ltd.), and the like.
The content of the pigment dispersant is preferably 5 to 50% by weight based on the entire solid content, and more preferably 8 to 40% by weight based on the entire solid content.

<(C) Dispersion auxiliary resin>
In the inkjet ink according to the present invention, an epoxy resin represented by the following formula (1) is used as the dispersion auxiliary resin (C) in addition to the pigment dispersant.

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

  Here, the dispersion auxiliary resin has a function of enhancing the action of the pigment dispersant and has an auxiliary function of improving the pigment dispersibility as compared with the case of using only the pigment dispersant. The dispersion auxiliary resin used in the present invention enhances the action of various pigment dispersants, has a function capable of achieving high pigment dispersibility, and has a highly reactive terminal epoxy group, and thus has high reactivity. It has a function as a curable resin. Further, the cured layer has little thermal expansion and contraction. Therefore, when only the pigment dispersant is used, the generation of the wrinkles and cracks can be prevented even when used together with the pigment dispersant that causes wrinkles and cracks in the cured layer. Moreover, since the said specific epoxy resin has an alicyclic skeleton, yellowing-proof property improves compared with the case where it has an acrylic skeleton which has a double bond, and an aromatic ring skeleton.

R ^a in the above formula (1) is a residue obtained by removing active hydrogen in an organic compound having active hydrogen, and examples of the organic substance having active hydrogen that is a precursor thereof include alcohols, phenols, and carboxylic acids. , Amines, thiols and the like. The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, aliphatic alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol, aromatic alcohol such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1 , 3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane And polyhydric alcohols such as trimethylolethane, pentaerythritol and dipentaerythritol.
Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4′-dihydroxybenzophenone, bisphenol S, phenol resin, and cresol novolac resin.
Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, terephthalic acid There are acids.
Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.
Examples of amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4′-diaminodiphenylmethane, isophoronediamine, There are toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine and the like.
Examples of thiols include mercaptos such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyvalent alcohol esters of mercaptopropionic acid, such as ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, Examples include pentaerythritol tetramercaptopropionic acid.

In addition, other active hydrogen-containing compounds include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, and styrene-maleic acid. Examples include acid copolymer resins, alkyd resins, polyester polyol resins, polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, and polytetramethylene glycol.
The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like. is there.
Any compounds having these active hydrogens can be used, and two or more of them may be mixed.

  In the general formula (1), n1, n2... Nk are each 0 or an integer of 1 to 100, and the sum thereof is 1 to 100. When the sum exceeds 100, there is a possibility that a problem may occur in productivity and storage stability of the dispersion. k represents an integer of 1 to 100. n1, n2... nk are each 2 to 10, more preferably 3 to 6, and k is preferably 2 to 6. The sum of n1 to nk is preferably 4 to 30. When the sum of n1 to nk is less than 4, the crosslink density after curing becomes low and it is difficult to obtain sufficient film strength. On the other hand, if the sum of n1 to nk is more than 30, there is a tendency that it is difficult to dissolve in a solvent, and the handling property of the material may be deteriorated. Further, 4 to 20 is preferable from the viewpoint of film strength and dispersibility. The k A's may be the same or different.

  Moreover, as A, it is more preferable that it is a structure of Formula (3).

  Among the substituents X of A in the general formula (1), it is essential that at least one structure of the formula (4) is contained in the resin, but the more is more preferable. In particular, the smaller the structure of formula (6), the better. That is, in the present invention, the substituent X mainly has the structure of the formula (4).

The epoxy resin represented by the above formula (1) used in the present invention is a 5-vinylbicyclo [2.2.1] using the compound having active hydrogen as an initiator, as in JP-B-7-119270. Polyether resin obtained by ring-opening polymerization of a mixture of hept-2-ene-2-oxide or 4-vinylcyclohexene-1-oxide and a compound having one epoxy group, that is, vinyl group side chain and norbornene It is produced by epoxidizing a polyether resin having a skeleton or vinyl group side chain and a cyclohexane skeleton with peracetic acid or hydrogen peroxide.
As a commercial item of the epoxy resin represented by the above formula (1) used in the present invention, Daicel Chemical Industries, Ltd., EHPE3150 (the sum of n1 to nk is an average of 15) can be mentioned as a suitable one.

  The dispersion auxiliary resin is preferably 5 to 80 parts by weight, and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the pigment dispersant. If the dispersion auxiliary resin is less than 5 parts by weight with respect to 100 parts by weight of the pigment dispersant, there is a possibility that the effect of improving the pigment dispersibility and the film strength after forming a cured layer as an ink may be insufficient. On the other hand, if the dispersion auxiliary resin exceeds 80 parts by weight with respect to 100 parts by weight of the pigment dispersant, the pigment dispersibility and the pigment dispersion stability over time may be deteriorated. Moreover, it is preferable that content of dispersion | distribution auxiliary resin is 5-70 weight part with respect to 100 weight part of binder systems mentioned later.

<Binder system>
In the present invention, the epoxy compound (D) having two or more epoxy groups in one molecule and the polyvalent carboxylic acid derivative (E) are essential components, and other components may be added as necessary within the range not impairing the effects of the present invention. A binder system containing these components is used. This binder system has excellent storage stability despite the presence of a high concentration of carboxyl group reactive sites in the presence of an epoxy group, so that excellent pigment dispersibility can be maintained as it is. During this time, it is difficult for the viscosity to increase, and stable ejection can be performed, and flight bending in the ejection direction and clogging of the ejection head are unlikely to occur.

<(D) Epoxy compound having two or more epoxy groups in one molecule>
(D) An epoxy compound having two or more epoxy groups in one molecule (hereinafter referred to as epoxy compound (D)) has a structure different from that of the dispersion auxiliary resin (C), and has an epoxy group. It is an epoxy compound (including what is called an epoxy resin) having 2 or more, preferably 2 to 50, more preferably 2 to 20 in one molecule. The epoxy group may be a structure having an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group.
As the epoxy compound (D), an epoxy group-containing polymer (D1) polymerized using at least a monomer containing a carbon-carbon unsaturated bond and an epoxy group, an epoxy group-containing compound (D2) having two or more epoxy groups ).

  The epoxy group-containing polymer (D1) used in the present invention is a polymer using at least a monomer containing a carbon-carbon unsaturated bond and an epoxy group (hereinafter sometimes referred to as an epoxy group-containing monomer). It can be obtained by polymerizing the containing monomer alone or by copolymerizing an epoxy group-containing monomer and another monomer. The molecular form may be linear or may have a branched structure, and may be any form such as a random copolymer, a block copolymer, or a graft copolymer.

The epoxy group-containing polymer (D1) used in the present invention can be polymerized by an ordinary polymerization method. That is, the polymerization method is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be employed. More specifically, in the presence of a polymerization initiator, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, A polymerization method such as an emulsion polymerization method can be employed. Depending on the polymerization method, a large amount of monomer may remain, but when this monomer affects the physical properties of the cured layer, the monomer may be removed by a vacuum distillation method, a reprecipitation purification method, or the like.
Preferred examples of the epoxy group-containing polymer (D1) used in the present invention include those having structural units represented by the following formulas (12) to (14) as epoxy group-containing structural units.

（式中のＲ^３は水素原子又は炭素数１〜５のアルキル基、Ｒ^４は水素原子又は炭素数１〜２のアルキル基であり、ｐ１＝１〜８の整数である。）

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p1 = 1 to 8 is an integer.)

（式中のＲ^５は水素原子又は炭素数１〜５のアルキル基、Ｒ^６は−ＣＨ_２Ｏ−基又は−ＣＨ_２−基、Ｒ^７は水素原子又は炭素数１〜２のアルキル基であり、ｑ１＝０〜７の整数である。）

(In the formula, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁶ is a —CH ₂ O— group or —CH ₂ — group, and R ⁷ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Yes, and q1 is an integer of 0 to 7.)

（式中のＲ^８は水素原子又は炭素数１〜５のアルキル基であり、ｒ１＝１〜８の整数である。）

(R ⁸ in the formula is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r1 = 1 to 8 is an integer.)

  The epoxy group-containing polymer (D1) used in the present invention may further have a structure represented by the following formulas (15) to (17) as its structural unit.

（式中のＲ^９は水素原子又は炭素数１〜１２のアルキル基であり、Ｒ^１０は炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリール基、アリールオキシ基、又は芳香族ポリアルキレングリコール残基である。）

(In the formula, R ⁹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms in the main ring, and aromatic. An aromatic hydrocarbon group, an aryl group, an aryloxy group, or an aromatic polyalkylene glycol residue.)

（式中のＲ^１１は水素原子又は炭素数１〜１２のアルキル基であり、Ｒ^１２は水素原子、炭素数１〜１２のアルキル基、アルコキシ基、シロキシアルキル基、又は芳香族炭化水素基である。）

(In the formula, R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a siloxyalkyl group, or an aromatic hydrocarbon group. is there.)

（式中のＲ^１３は、炭素数１〜１２のアルキル基、脂環式炭化水素基、又は芳香族炭化水素基である。）
前記式（１２）〜（１４）で表される構成単位は、それぞれ下記式（１８）〜（２０）で表されるモノマーから誘導される。

(R ¹³ in the formula is an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.)
The structural units represented by the formulas (12) to (14) are derived from monomers represented by the following formulas (18) to (20), respectively.

（式中のＲ^１４は水素原子又は炭素数１〜５のアルキル基、Ｒ^１５は水素原子又は炭素数１〜２のアルキル基であり、ｐ２＝１〜８の整数である。）
前記式（１８）において、Ｒ^１４，及びＲ^１５として好ましいのは、それぞれ独立に水素原子又はメチル基であり、またｐ２として好ましいのは１〜３の整数である。式（１８）で表されるモノマーとしては、具体的には、グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレートを例示することができ、その中ではグリシジルメタクリレート（以下、ＧＭＡ）が入手性の面等から好ましい。なお、本発明において、（メタ）アクリレートとは、アクリレート又はメタクリレートのいずれであっても良いことを意味する。

(In the formula, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p2 = 1 to 8 is an integer.)
In the formula (18), R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom or a methyl group, and p2 is preferably an integer of 1 to 3. Specific examples of the monomer represented by the formula (18) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (hereinafter referred to as GMA) is available. It is preferable from the aspect of property. In the present invention, (meth) acrylate means that either acrylate or methacrylate may be used.

（式中のＲ^１６は水素原子又は炭素数１〜５のアルキル基、Ｒ^１７は−ＣＨ_２Ｏ−基又は−ＣＨ_２−基、Ｒ^１８は水素原子又は炭素数１〜２のアルキル基であり、ｑ２＝０〜７の整数である。）
前記式（１９）において、Ｒ^１６，及びＲ^１８として好ましいのは、それぞれ独立に水素原子又はメチル基であり、Ｒ^１７として好ましいのは−ＣＨ_２Ｏ−基であり、ｑ２として好ましいのは１〜３の整数である。式（１９）で表されるモノマーとしては、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテルが入手性の面等から好ましい。

(In the formula, R ¹⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁷ is a —CH ₂ O— group or —CH ₂ — group, and R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Yes, and q2 is an integer from 0 to 7.)
In the formula (19), R ¹⁶ and R ¹⁸ are each independently preferably a hydrogen atom or a methyl group, R ¹⁷ is preferably a —CH ₂ O— group, and q 2 is preferably 1. It is an integer of ~ 3. As the monomer represented by the formula (19), o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable from the viewpoint of availability.

（式中のＲ^１９は水素原子又は炭素数１〜５のアルキル基であり、ｒ２＝１〜８の整数である。）
前記式（２０）において、Ｒ^１９として好ましいのは、水素原子又はメチル基である。式（２０）で表されるモノマーとしては３，４−エポキシシクロヘキシルメチルメタクリレートが硬度等の硬化層特性の面から好ましい。
また前記式（１５）〜（１７）で表される構成単位は、下記式（２１）〜（２３）で表されるモノマーから誘導される。

(In the formula, R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r2 = 1 to 8 is an integer.)
In the formula (20), R ¹⁹ is preferably a hydrogen atom or a methyl group. As the monomer represented by the formula (20), 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of cured layer properties such as hardness.
The structural units represented by the formulas (15) to (17) are derived from monomers represented by the following formulas (21) to (23).

（式中のＲ^２０は水素原子又は炭素数１〜１２のアルキル基であり、Ｒ^２１は炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリール基、アリールオキシ基、又は芳香族ポリアルキレングリコール残基である。）
前記式（２１）において、Ｒ^２１が主環構成炭素数３〜１２の脂環式炭化水素基で表される場合、該脂環式炭化水素基は、付加的な構造、例えば環内二重結合、炭化水素基の側鎖、スピロ環の側鎖、環内架橋炭化水素基等を含んでいてもよい。

(In the formula, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ²¹ is an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms in the main ring, and aromatic. An aromatic hydrocarbon group, an aryl group, an aryloxy group, or an aromatic polyalkylene glycol residue.)
In the formula (21), when R ²¹ is represented by an alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring, the alicyclic hydrocarbon group has an additional structure, for example, an intracyclic double group. It may contain a bond, a hydrocarbon group side chain, a spiro ring side chain, an intra-ring bridged hydrocarbon group, and the like.

In the formula (21), R ²⁰ is preferably hydrogen or a methyl group, and R ¹⁹ is preferably a cyclohexyl group or a dicyclopentenyl group. Specifically, as a monomer represented by the formula (21), cyclohexyl methacrylate and dicyclopentenyl methacrylate are preferable from the viewpoint of cured layer properties such as hardness and heat resistance.

（式中のＲ^２２は水素原子又は炭素数１〜１２のアルキル基であり、Ｒ^２３は水素原子、炭素数１〜１２のアルキル基、アルコキシ基、シロキシアルキル基、又は芳香族炭化水素基である。）
前記の式（２２）において、Ｒ^２２としては好ましいのは水素又はメチル基であり、Ｒ^２３としては好ましいのはフェニル基である。式（２２）で表されるモノマーとしては、具体的には、スチレンが他種モノマーとの共重合性、及び入手性の面等から好ましい。

(In the formula, R ²² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ²³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a siloxyalkyl group, or an aromatic hydrocarbon group. is there.)
In the formula (22), R ²² is preferably hydrogen or a methyl group, and R ²³ is preferably a phenyl group. Specifically, as the monomer represented by the formula (22), styrene is preferable from the viewpoint of copolymerization with other monomers and availability.

（式中のＲ^２４は炭素数１〜１２のアルキル基、シクロアルキル基、又は芳香族炭化水素基である。）
前記式（２３）において、Ｒ^２４としては好ましいのはシクロヘキシル基、及びフェニル基である。式（２３）で表されるモノマーとしては、具体的には、Ｎ−シクロヘキシルマレイミド、及びＮ−フェニルマレイミドが硬度、耐熱性等の硬化層特性の面から好ましい。

(In the formula, R ²⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)
In the formula (23), R ²⁴ is preferably a cyclohexyl group or a phenyl group. Specifically, as the monomer represented by the formula (23), N-cyclohexylmaleimide and N-phenylmaleimide are preferable from the viewpoint of cured layer properties such as hardness and heat resistance.

  The epoxy group-containing polymer (D1) in the resin composition of the present invention is an epoxy group-containing structure represented by the above formulas (12) to (14) as long as the epoxy equivalent is in the range of 140 to 1000 g / mol. In the epoxy group-containing polymer (D1), at least one of the units is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, and particularly preferably 40 to 70% by weight. If the epoxy group-containing constitutional unit is less than 10% by weight, the cured layer may be poor in toughness.

  The weight average molecular weight of the epoxy group-containing polymer (D1) is preferably in the range of 2,000 to 20,000, and in the range of 3,000 to 15,000 when expressed in terms of polystyrene equivalent weight average molecular weight. It is more preferable. When the molecular weight of the epoxy group-containing polymer (D1) is less than 2,000, physical properties such as strength and solvent resistance required for the cured layer as details of the color filter tend to be insufficient, while the molecular weight is 20, If it exceeds 000, the viscosity tends to increase, and the stability of the ejection amount when ejected from the ejection head and the straightness in the ejection direction may be deteriorated, and the storage stability may be deteriorated.

  As a synthesis example of the epoxy group-containing polymer (D1), a solvent not containing a hydroxyl group was charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the temperature was raised to 115 ° C. while stirring. To do. The reason for using a solvent that does not contain a hydroxyl group is to avoid reaction and ring opening of the epoxy group during the synthesis reaction. Subsequently, the mixture (dropping component) of a monomer and a polymerization initiator is dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropwise addition, the mixture is maintained at 115 ° C. for 2 hours, then heated to 125 ° C., and the reaction is terminated when the temperature is maintained for 2 hours, whereby an epoxy group-containing polymer (D1) is obtained.

  The epoxy group-containing compound (D2) used in the present invention has two or more epoxy groups in the molecule. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy Resin, fluorene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, Hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester Epoxy resins, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins having a different structure from the a dispersing auxiliary resin (C).

Among these polyfunctional epoxy resins, bisphenol A type novolac epoxy resins such as trade name jER828 (made by Japan Epoxy Resin Co., Ltd.), trade name jER157S70 (made by Japan Epoxy Resin Co., Ltd.), and trade name YDCN- A cresol novolac type epoxy resin such as 701 (manufactured by Toto Kasei Co., Ltd.) is particularly preferred.
The epoxy group-containing compound (D2) used in the present invention can be used alone or in combination of two or more.

<(E) Multivalent carboxylic acid derivative>
The polyvalent carboxylic acid derivative (E) in the inkjet ink for a color filter of the present invention is a vinyl ether compound (e2) in which the carboxyl group of the carboxylic acid (e1) having the structure of the following formula (11) is represented by the following formula (24). ) (Compound containing vinyl group and ether group) is latent (hereinafter sometimes referred to as blocking).

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)

（式中のＲ^２５は炭素数１〜１０の炭化水素基である。）

(R ²⁵ in the formula is a hydrocarbon group having 1 to 10 carbon atoms.)

Of the carboxylic acid (e1) represented by the formula (11), examples of the compound in which R ¹ is other than a hydrogen atom include a half ester obtained by a reaction between an alcohol compound and an acid anhydride.
Examples of the alcohol compound used in this reaction include monovalent alcohol compounds such as ethanol, propanol, hexanol, octanol, and isopropyl alcohol; ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexanediol, and the like. Preferred examples include trivalent alcohol compounds such as glycerin, pentanetriol, hexanetriol, cyclohexanetriol, and trimethylolpropane; and tetravalent alcohol compounds such as pentaerythritol, more preferably hexanol. , Isopropyl alcohol, 1,2-propylene glycol, 1,3-propylene glycol, 1,6-hexanediol, glycerin, trimethylo Trimethylolpropane, pentaerythritol.

  In addition, examples of acid anhydrides used in this reaction include compounds represented by the following formula (25). Specifically, phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 1,2 Preferred examples include 1,4-benzenetricarboxylic anhydride (hereinafter sometimes referred to as trimellitic anhydride), 1,2,4-cyclohexanetricarboxylic anhydride, and methylhexahydrophthalic anhydride. In the above half ester body, a cured layer having a high crosslink density and high adhesion is obtained, so that a polyhydric alcohol having 3 to 6 carbon atoms and a trihydric anhydride or methylhexahydroanhydride is obtained. What is obtained by a combination with phthalic acid is preferably exemplified as (e1). Among them, methylhexahydrophthalic anhydride is preferably selected from the viewpoints of transparency and storage stability.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜２の整数であり、ｔ１は、０〜１の整数である。Ｒ²は、炭素数１〜５のアルキル基である。）

(6-membered ring in formula is an integer of .m1 is 0-2 aromatic or alicyclic hydrocarbons, t1 is an integer of 0 to 1 .R ² is C1-5 The alkyl group of

Among the carboxylic acids (e1) represented by the formula (11), examples of the compound in which R ¹ is a hydrogen atom include the formula (26) or the formula (27), and these polycarboxylic acids obtained by blocking these carboxylic acids. Since the acid derivative (E) has high dissolving power, it is preferably used in combination with (D1) or (D2) having low compatibility.

（式中のｍ２は０〜２の整数である。）

(In the formula, m2 is an integer of 0 to 2.)

（式中のｍ３は０〜２の整数であり、ｔ２は０〜１の整数である。Ｒ²は、炭素数１〜５のアルキル基である。）
上記式（２６）または（２７）で表されるカルボン酸（ｅ１）としては、フタル酸等の芳香族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；１，２，４−ベンゼントリカルボン酸（以下、トリメリット酸）等の芳香族トリカルボン酸；１，２，４−シクロヘキサントリカルボン酸（以下、ＣＨＴＡ）などの脂環式トリカルボン酸；ベンゼンテトラカルボン酸（ピロメリット酸）等の芳香族テトラカルボン酸；シクロヘキサンテトラカルボン酸などの脂環式テトラカルボン酸が挙げられる。中でもトリメリット酸、ＣＨＴＡ、ピロメリット酸が架橋密度、および密着性の高い硬化層が得られることから、カルボン酸（ｅ１）として好ましい。
本発明のカラーフィルター用インクジェットインクにおいて（ｅ１）として用いることができるカルボン酸は１種単独で、または２種以上を組み合わせて用いることができる。

(An integer of m3 is 0 to 2 in the formula, t2 is an integer of 0 to 1 .R ² is an alkyl group having 1 to 5 carbon atoms.)
Examples of the carboxylic acid (e1) represented by the above formula (26) or (27) include aromatic dicarboxylic acids such as phthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; 1,2,4-benzenetricarboxylic acid Aromatic tricarboxylic acids such as (hereinafter referred to as trimellitic acid); Alicyclic tricarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid (hereinafter referred to as CHTA); Aromatic tetracarboxylic acids such as benzenetetracarboxylic acid (pyromellitic acid) Carboxylic acid; alicyclic tetracarboxylic acid such as cyclohexanetetracarboxylic acid. Among these, trimellitic acid, CHTA, and pyromellitic acid are preferable as the carboxylic acid (e1) because a cured layer having a high crosslinking density and high adhesion can be obtained.
The carboxylic acid that can be used as (e1) in the inkjet ink for a color filter of the present invention can be used alone or in combination of two or more.

  On the other hand, examples of the vinyl ether compound (e2) represented by the formula (24) that is a raw material of the polyvalent carboxylic acid derivative (E) in the inkjet ink for a color filter of the present invention include isopropyl vinyl ether, n-propyl vinyl ether, n Examples thereof include alkyl vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. Examples of the vinyl ether compound (e2) that can be suitably used in the inkjet ink for a color filter of the present invention include isopropyl vinyl ether and n-propyl vinyl ether, which can be used alone or in combination of two or more. .

  The polyvalent carboxylic acid derivative (E) used in the present invention can be obtained by reacting the carboxylic acid (e1) with the vinyl ether compound (e2) at a temperature ranging from room temperature to 150 ° C. . Since the blocking reaction is an equilibrium reaction, the use of a slightly larger amount of the vinyl ether compound (e2) relative to the carboxylic acid (e1) promotes the reaction and can improve the yield. Specifically, the molar equivalent ratio of the vinyl group of the vinyl ether compound (e2) to the carboxyl group of the carboxylic acid (e1) is desirably 1/1 to 2/1. When this molar equivalent ratio exceeds 2/1, the reaction temperature cannot be increased and the reaction rate may be extremely low.

<Binder mix ratio>
The blending ratio of the epoxy group-containing polymer (D1), the epoxy group-containing compound (D2), and the polyvalent carboxylic acid derivative (E) is 10 to 80 parts by weight of the epoxy group-containing polymer (D1) in weight ratio, It is preferable to mix 10 to 60 parts by weight of the epoxy group-containing compound (D2) and 10 to 60 parts by weight of the polyvalent carboxylic acid derivative (E), and 20 to 60 parts of the epoxy group-containing polymer (D1). More preferably, 20 to 50 parts by weight of the epoxy group-containing compound (D2) and 20 to 50 parts by weight of the polycarboxylic acid derivative (E) are blended, and the epoxy group-containing polymer (D1). It is more preferable to mix 30 to 40 parts by weight, 25 to 35 parts by weight of the epoxy group-containing compound (D2), and 35 to 45 parts by weight of the polyvalent carboxylic acid derivative (E).

  The ratio of the total amount of the epoxy group-containing polymer (D1), the epoxy group-containing compound (D2), and the dispersion auxiliary resin (C) and the amount of the polyvalent carboxylic acid derivative (E) is in the following range. It is preferable. A molar concentration of carboxyl groups formed after elimination (delatentization, deblocking) of the vinyl ether compound of the polyvalent carboxylic acid derivative (E), an epoxy group-containing polymer (D1), an epoxy group-containing compound (D2), and The blending amount is preferably such that the ratio (carboxyl group / epoxy group) to the molar concentration of the epoxy group of the dispersion auxiliary resin (C) is 0.2 / 1.0 to 1.6 / 1.0, A more preferable molar concentration ratio is 0.5 / 1.0 to 1.2 / 1.0. If the molar concentration ratio between the carboxyl group and the epoxy group is less than 0.2 / 1.0, a large amount of the epoxy group remains after curing, so that the crosslinking density is lowered and the effect of the present invention may not be obtained. There is. On the other hand, if the molar concentration ratio between the carboxyl group and the epoxy group exceeds 1.6 / 1.0, the carboxyl group becomes excessive, and the physical properties of the resin are often lowered. In addition, as an additional component not included in (D1), (D2), (C) and (E), which is an essential component in the inkjet ink for a color filter of the present invention, it reacts with a carboxyl group and a carboxyl group containing an epoxy group. When the compound containing a functional group capable of being added is added, the ratio of the molar concentration of the carboxyl group in the composition to the molar concentration of the functional group capable of reacting with the carboxyl group containing an epoxy group is within the above range. It is preferable to blend in.

  Moreover, in order to give sufficient adhesion, strength, and hardness to the cured layer, the epoxy group-containing polymer (D1) and the epoxy group-containing compound (D2) occupying the total solid content of the ink including pigments and other components. ) And the polycarboxylic acid derivative (E) are preferably 15 to 95% by weight, more preferably 20 to 60% by weight. Here, the solid content of the ink for specifying the blending ratio includes all components except the solvent, and liquid polyfunctional epoxy resin and the like are also included in the solid content.

<(F) Solvent>
In order to prepare the ink for a color filter of the present invention so that the ink can be discharged from a high concentration liquid or immediately from the head, a solvent (F) is blended.
The inkjet ink of the present invention has a boiling point of 180 ° C. to 260 ° C., particularly 210 ° C. to 260 ° C., and a vapor pressure at room temperature (especially in the range of 18 ° C. to 25 ° C.) of 0.5 mmHg or less, particularly 0.1 mmHg or less. It is preferable to use a solvent component as a main solvent and to mix such a main solvent in a proportion of 60% by weight or more based on the total amount of the solvent. The surface tension of the main solvent is preferably 28 mN / m or more.

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. For this reason, if a single solvent or mixed solvent containing such a solvent component in a high blending ratio is used, the inkjet ink does not dry rapidly at the nozzle tip of the discharge head, causing a sudden increase in viscosity or clogging of the ink. Without adversely affecting the straightness and stability of the discharge. At the same time, since the drying proceeds at an appropriate speed after spraying on the surface to be ejected, the ink becomes familiar with the surface to be coated and the surface of the coating film becomes horizontal and smooth, followed by natural drying or a general heating process. The ink can be dried quickly and completely. Compared to the case of using a wetting agent or a solvent having a very high boiling point, there is less possibility that the solvent remains in the coating film after the drying step. The solvent component used as the main solvent may be one kind or a mixed solvent of two or more kinds as long as it has the above boiling point and vapor pressure.
In addition, the surface tension of the main solvent at 23 ° C. is preferably 28 mN / m or more from the viewpoint that the outflow of ink to the sparse ink portion during patterning can be reduced. In addition, when a main solvent is 2 or more types of mixed solvents, it is preferable to have the said surface tension as the whole mixed solvent.

  By forming a wettability variable layer on the surface of the substrate 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 inkjet ink of the present invention is selectively applied to the ink-philic region by the inkjet method. When adhering to the liquid, the standard solution shown in the wettability test specified in JIS K6768 is used as the main solvent, and the contact angle (θ) after 30 seconds is measured after contact with the liquid droplets. 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 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. As a result, a fine and precise ink layer pattern can be formed by the inkjet method.
Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. As a test piece showing a critical surface tension of 30 mN / m, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, the polymer, a surface modifier or the like was applied to a smooth glass surface. It is possible to select the relevant ones by actually conducting the above test from among those. 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 etc. which hydrophilized, etc., and the applicable thing can be selected.

The main solvent can be selected from the following solvents: glycol ethers such as ethylene glycol monohexyl ether and diethylene glycol monomethyl ether; glycols such as ethylene glycol monobutyl ether acetate and diethylene glycol monomethyl ether acetate Ether esters; aliphatic or aromatic esters such as ethyl acetate, propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate; Ketocarboxylic esters such as: ethanol, isopropanol, alcohols such as phenol, or phenols; aliphatic or aromatic such as diethyl ether, anisole Ethers; alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol; glycol oligomers such as diethylene glycol and tripropylene glycol; alkoxy alcohol esters such as 2-ethoxyethyl acetate; acetone and methyl Ketones such as isobutyl ketone.
Further, as the main solvent, it is preferable to use a solvent that does not contain a hydroxyl group from the viewpoint of the temporal stability of the ink.

  Preferred solvents include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, succinate Examples thereof include dimethyl acid and diethyl succinate. These solvents are preferable not only because they 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, but also have no hydroxyl group in the molecule. Furthermore, these solvents are mixed with or without mixing with highly dispersible solvents conventionally used for preparing pigment dispersions such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate (PGMEA). It can be used as a solvent to prepare an ink.

The above-mentioned solvent exemplified as a preferable example uses a standard solution shown in the wettability test specified in JIS K6768, measures the contact angle (θ) after 30 seconds of contact with a liquid droplet, The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the above is 25 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 Also meets the requirement to show below. Therefore, these solvents are also mainly used when a wettability variable layer is provided on the surface of a substrate for exposure, and ink jet ink is selectively adhered using the difference in wettability between the exposed and unexposed areas. It can be suitably used as a solvent.
Also, when water is mixed in the solvent, the hydroxyl group of the water molecule is present in the solvent, which may cause the same problem as when a solvent having a hydroxyl group is used. Accordingly, in order to substantially eliminate moisture, it is preferable to prepare an ink using an organic solvent having low miscibility with water. From this viewpoint, the solubility of the solvent for preparing the ink in water is preferably 20 parts by weight or less with respect to 100 parts by weight of water having a liquid temperature of 20 ° C.
Among the main solvents mentioned as specific examples, diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and the solubility in 100 parts by weight of water at a liquid temperature of 20 ° C. is low at 6.5 parts by weight. It is particularly preferable since it exhibits the property.

  The solvent may contain a solvent component (sub-solvent) other than the main solvent from the viewpoint of pigment dispersibility and performance after ink preparation. However, even in that case, it is preferable to use the main solvent having the above boiling point and vapor pressure at a ratio of 60% by weight or more based on the total amount of the solvent. When the ratio of the main 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.

As a secondary solvent used in combination with the above main solvent, a solvent component having a boiling point of 130 ° C. or higher and lower than 180 ° C., it is difficult to form a thick film portion at the end, and a good coating film with reduced surface unevenness is obtained. It is preferable because it is easily formed. The auxiliary solvent having such a boiling point has a boiling point appropriately lower than that of the main solvent. Therefore, when combined in an appropriate amount, it does not dry quickly at the nozzle tip of the inkjet head, but the solute flows when the ink layer is dried. It is a component that makes it possible to control the drying rate and appropriately adjust the drying rate. The solvent component used as the auxiliary solvent may be used alone or in combination of two or more as long as it has the above boiling point.
Especially, it is preferable that the boiling point of each solvent component used for a subsolvent is 140 to 180 degreeC, and it is especially preferable that it is 140 to 175 degreeC.

Moreover, it is preferable that the viscosity at 23 degreeC of the said auxiliary solvent is 0.5-6 mPa * s. In such a case, it is possible to appropriately reduce the viscosity of the ink without impairing the effect of the main solvent by including the sub-solvent, and as a result of improving the wetting and spreading property of the ink itself, The landed ink droplets are easily spread all over the corners 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 cracked portion of the black matrix, thereby preventing pixel color loss and luminance reduction. 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, it is a more desirable method that the ink itself is wetted and spread to the wrinkles of the black matrix as in the present invention without fear of ink leakage. The viscosity of the secondary solvent at 23 ° C. is preferably 0.5 to 3 mPa · s. When two or more sub-solvents are used in combination, they are preferably 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.).
If the surface tension of the secondary solvent at 23 ° C. is 35 mN / m or less, it can be suitably used. In particular, when the surface tension of the sub-solvent at 23 ° C. is 28 mN / m or less, the surface tension can be appropriately reduced without hindering the effect of the main solvent, and the ink itself is wetted. Since the spreadability is improved, the landed ink droplets are easily wetted and spread to every corner of the entire ink layer formation region. Here, the surface tension at 23 ° C. in the present invention can be measured by a surface tension meter (Wilhelmi method) (for example, an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.).

Moreover, as said subsolvent, 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 main solvent suitably.
Specific examples of the auxiliary solvent include 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 monopropyl. Polyhydric alcohol ethers such as ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, glycol ethers such as diethylene glycol dimethyl ether, and glycerin ethers such as glycerin 1,3-dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol Glycol esters including glycol ether esters such as propyl monopropyl ether acetate, ethylene glycol monomethoxymethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and glycerin esters such as glycerin 1-monoacetate Polyhydric alcohol 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, methyl lactate, isoamyl propionate, Aliphatic esters such as butyl propionate, butyl butyrate, tributyl citrate, dimethyl oxalate; alkoxy such as ethyl 3-ethoxypropionate Rubonic acid esters; ketocarboxylic acid esters such as methyl acetoacetate; n-amyl alcohol, isoamyl alcohol, 2-ethylbutanol, glycidol, n-hexanol, 2-methylcyclohexanol, 4-methyl-2-pentanol, Monohydric alcohols such as 2-octanol, cyclohexanol, 2-heptanol, 3-heptanol, n-heptanol; ethers such as diisoamyl ether and 1,8-cineol; ethyl-n-butyl ketone, diisobutyl ketone , Ketones such as di-n-propyl ketone, methylcyclohexanone, methyl-n-hexyl ketone, acetylacetone and diacetone alcohol; alkanes such as nonane and decane.

  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. In the case of using esters and ethers as described above, there is an advantage that it is easy to maintain good ink stability even when a highly reactive resin is used for the binder component or the like. 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. .

  Among these co-solvents, 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, 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 From methyl acetoacetate, hexyl formate, cyclohexyl acetate, ethyl lactate, isoamyl propionate, butyl propionate, butyl butyrate, tributyl citrate, dimethyl oxalate, ethyl 3-ethoxypropionate, diisoamyl ether, and 1,8-cineol One or more solvents selected from the group consisting of

  In the inkjet ink for a color filter according to the present invention, the content when such a sub-solvent is used is 5 to 30% by weight, more preferably 5 to 25% by weight, particularly 8 to 20% by weight based on the total amount of the solvent. %, Without impairing the effect of the main solvent, it is excellent in straightness and stability when ejected from the head, and can be dried more efficiently. In addition, it is preferable because it is easy to form good pixels with reduced surface unevenness.

  The ink-jet ink is prepared by using the solvent in a proportion of usually 40 to 95% by weight, preferably 70 to 95% by weight, based on the total amount of the ink-jet ink containing the solvent. When the solvent is less than 40% by weight, the viscosity of the ink-jet ink is high and it becomes difficult to discharge from the ink-jet head. When the solvent exceeds 95% by weight, the ink film deposited on the wettability changing portion before the ink deposit amount (ink deposition amount) with respect to the predetermined wettability changing portion (ink layer forming portion) is not sufficient. Breaks down, protrudes to the surroundings, and further spreads to the adjacent wettability change site (ink layer formation site). In other words, the amount of ink that can be deposited without protruding from the wettability change site (ink layer forming site) to which the ink is to be deposited becomes insufficient, the film thickness after drying is too thin, The light transmission density cannot be obtained.

<Catalyst>
In order to improve the hardness and heat resistance of the cured layer, a catalyst capable of accelerating the thermosetting reaction between acid and epoxy may be added to the inkjet ink for color filter of the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds as described in JP-A-4-218561 can be used. Specifically, (i) compounds obtained by neutralizing halogenocarboxylic acids, sulfonic acids, phosphoric acid mono- and diesters with various amines such as ammonia, monomethylamine, triethylamine, pyridine, ethanolamine, or trialkylphosphine (B) compounds obtained by neutralizing Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the aforementioned Lewis base, (c) methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, etc. Examples include primary alcohols, ester compounds with secondary alcohols, (d) primary alcohols, secondary monoalcohol phosphate monoester compounds, and phosphate diester compounds. Examples of the onium compound include an ammonium compound [R ₃ NR ′] ⁺ X ⁻ , a sulfonium compound [R ₃ SR ′] ⁺ X ⁻ , and an oxonium compound [R ₃ OR ′] ⁺ X ⁻ . Here, R and R ′ are groups such as alkyl, alkenyl, aryl and alkoxy.

The thermal latent catalyst is preferably a halogen-free acidic catalyst from the viewpoint of liquid crystal contamination. Specific examples of the halogen-free acidic catalyst include Nofure LC-1, Nofure LC-2, and Nofure LC-10 (all trade names, manufactured by NOF Corporation).
The heat latent catalyst is usually based on 100 parts by weight of the total of the epoxy group-containing polymer (D1), the epoxy group-containing compound (D2), the dispersion auxiliary resin (C), and the polyvalent carboxylic acid derivative (E). It mix | blends in the ratio of about 0.01-10.0 weight part.

<Other ingredients>
Furthermore, the ink for ink for color filters of this invention can mix | blend 1 type (s) or 2 or more types of other additives as needed. The following can be illustrated as such an additive.
a) Filler: For example, glass, alumina and the like.
b) Adhesion promoter: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
c) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
d) Anti-aggregation agent: for example, sodium polyacrylate.
e) Leveling agents: for example, polyoxyalkylene surfactants, fatty acid ester surfactants, vinyl ether surfactants, and the like.

The color filter inkjet ink of the present invention is preferably produced by the method for producing the color filter inkjet ink according to the present invention.
The method for producing an inkjet ink for a color filter according to the present invention comprises: (F) a dispersion auxiliary resin comprising at least (A) a pigment, (B) a pigment dispersant, and (C) an epoxy resin represented by the following formula (1). Mixing in a solvent and dispersing to prepare a pigment dispersion;

（ただし、Ｒ^ａはｋ個の活性水素を有する有機化合物中の活性水素を除いた残基である。ｎ１、ｎ２・・・ｎｋはそれぞれ０又は１〜１００の整数で、その和が１〜１００である。ｋは１〜１００の整数を表わす。Ａは置換基Ｘを有するオキシノルボルネン骨格または置換基Ｘを有するオキシシクロヘキサン骨格であり、次式で表される。）

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

少なくとも（Ｄ）前記分散補助樹脂（Ｃ）とは異なる、１分子中にエポキシ基を２個以上有するエポキシ化合物、及び（Ｅ）下記式（１１）の構造を有するカルボン酸（ｅ１）がビニルエーテル化合物（ｅ２）により潜在化された多価カルボン酸誘導体を含有するバインダー系を、前記顔料分散液と混合する工程を有する。

At least (D) an epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C), and (E) a carboxylic acid (e1) having a structure of the following formula (11) is a vinyl ether compound A step of mixing the binder dispersion containing the polyvalent carboxylic acid derivative latentized by (e2) with the pigment dispersion.

（式中の６員環は芳香族又は脂環式の炭化水素である。ｍ１は０〜４の整数であり、ｔ１は０〜１の整数であり、ｎは１〜４の整数である。また、ｎが１の場合にはＲ¹は水素原子又は炭素数２〜８の炭化水素基であり、ｎが２〜４の場合にはＲ¹は炭素数２〜８の炭化水素基である。Ｒ²は、炭素数１〜５のアルキル基である。）
本発明のインクの製造方法においては、顔料分散液を調製する際に、分散補助樹脂として上記特定のエポキシ樹脂を用いるので、顔料分散性及び顔料分散経時安定性に優れた顔料分散液を得ることができる。その結果、カラーフィルターに適用したときに輝度やコントラストが向上するインクを調製することができる。

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)
In the method for producing the ink of the present invention, when the pigment dispersion is prepared, the specific epoxy resin is used as the dispersion auxiliary resin, so that a pigment dispersion excellent in pigment dispersibility and pigment dispersion aging stability is obtained. Can do. As a result, it is possible to prepare an ink having improved brightness and contrast when applied to a color filter.

  The pigment dispersion is prepared by mixing the above-described pigment, pigment dispersant, the above-mentioned dispersion auxiliary resin, and other components as necessary, in an organic solvent in an arbitrary order, and kneader, roll mill, attritor, super mill, dissolver, A pigment dispersion can be prepared by dispersing using a known dispersing machine such as a homomixer or a sand mill. When dispersing the pigment, it is preferable to add zirconia beads or the like as appropriate and perform dispersion for several hours using a paint shaker (manufactured by Asada Steel Corporation) or the like. Moreover, it is preferable to filter with a 5.0 micron membrane filter after dispersion.

In addition, as a step of mixing a binder system containing at least the epoxy compound (D) and the polyvalent carboxylic acid derivative (E) and other components as necessary with the pigment dispersion, specifically, the following method may be used. Can be mentioned.
1) The obtained pigment dispersion and at least the binder system are mixed in a newly prepared solvent (F).
2) At least a binder system is dissolved or dispersed in a newly prepared solvent (F) to prepare a binder solution, and then the binder solution and the pigment dispersion are mixed.
3) At least a binder system is dissolved or dispersed in a newly prepared solvent (F) to prepare a binder solution, and then the binder solution, the pigment dispersion, and the solvent (F) are mixed.
Here, the solvent (F) can be used alone or in combination, and the solvent (F) when preparing the pigment dispersion and the solvent (F) when preparing the binder solution may be different. Moreover, the solvent (F) in the case of preparing a pigment dispersion and the solvent (F) in the case of preparing a binder solution may be different from the solvent (F) added last as in the above 3). As in 2) and 3) above, a binder solution is prepared by dissolving or dispersing in a solvent (F) in which a binder system is newly prepared, and then mixed with a pigment dispersion obtained in advance. This is preferable from the viewpoint of maintaining good dispersibility and pigment dispersion aging stability.

  Even when the binder solution is prepared in advance, the blending ratio of the main solvent in the total amount of the ink solvent is finally adjusted to be 60% by weight or more. For this reason, if there is a residual solvent, use a solvent that has a composition obtained by subtracting the solvent used in the preparation of the pigment dispersion or binder solution from the final composition of the entire solvent, and dilute to the final concentration. An inkjet ink may be completed. Alternatively, a high-concentration inkjet ink may be prepared by introducing the pigment dispersion into a relatively small amount of the main solvent. The high-concentration ink-jet ink can be stored as it is and diluted to the final concentration just before use and used in the ink-jet method.

<Physical properties of cured layer>
The cured layer formed using the inkjet ink for a color filter of the present invention is excellent in ITO forming resistance, yellowing resistance, solvent resistance, adhesion, and other properties required for the color filter. For example, a cured layer having the following characteristics can be formed on a transparent substrate using the inkjet ink for a color filter of the present invention.
a) ITO resistance to formation: a color filter provided with a hardened layer is formed at a substrate setting temperature of 200 ° C. and a vacuum of 6 × 10 −3 Torr, and an ITO (indium tin oxide) electrode is formed to a thickness of 120 nm. However, no wrinkles or cracks occur in the ITO film after the heat resistance test at 180 ° C. for 60 minutes.
b) Yellowing resistance: When the cured layer is heated at 240 ° C. for 1 hour and the color difference ΔEab before and after heating is calculated based on the CIE1976 standard, ΔEab <3.
c) Solvent resistance (chemical resistance): ΔEab <1 when the color difference ΔEab before and after immersing the color filter provided with the cured layer in N-methylpyrrolidone at a liquid temperature of 40 ° C. for 1 hour is calculated according to the CIE 1976 standard. It can be.
d) Adhesion: JIS K5600-5-6: 1999 “Coating General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesiveness (Crosscut Method)” on a color filter provided with a cured layer The result of performing can be made 8 points or more.

<Application>
The inkjet ink for a color filter of the present invention is particularly suitably used for forming a film having a predetermined pattern such as a pixel or a black matrix in a color filter. As the color filter, any of a color filter used in an image output device such as a liquid crystal display device or a color filter used in an image input device such as a solid-state imaging device can be suitably used.

2. Manufacturing method of color filter The manufacturing method of the color filter of the present invention is a colored layer forming step of forming a colored layer by selectively attaching the inkjet ink for a color filter of the present invention to a predetermined region on a substrate by an inkjet method. It is characterized by including.
A desired pigment such as R, G, B, or black is blended in the color filter inkjet ink of the present invention, and the color filter inkjet ink is selectively attached to a predetermined region on the substrate of the color filter by an inkjet method. By forming an ink layer and curing the ink layer, a colored layer such as a pixel portion or a light shielding layer can be formed.
In the color filter according to the present invention, the colored layer is a cured layer of the ink formed by curing the inkjet ink for the color filter according to the present invention. Problems with coating film defects such as pattern deformation and poor adhesion do not occur. In addition, since the pattern of the colored layer portion hardly undergoes thermal expansion and contraction, the adjacent layer such as the transparent electrode film is distorted, wrinkles are generated on the surface, and the problem of disconnection does not occur. Therefore, display defects are reduced in the color filter and the display panel formed using the ink-jet ink according to the present invention.

  The method for selectively depositing ink by the ink jet method is not particularly limited as long as it can form a colored layer having a desired thickness in a predetermined region on the substrate. 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 onto a predetermined region on the substrate while moving the inkjet head or the substrate.

(1) Inkjet head The inkjet head 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 below. 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, a general ink jet head such as a discharge type that heats ink jet ink and intermittently discharges using the foaming phenomenon can be used.

(2) Color filter substrate Next, the color filter substrate will be described. In the present invention, the color filter substrate has a base material and a light-shielding portion formed on the base material.
a. Light-shielding part The light-shielding part is formed on a substrate to be described later and has an opening. As the light-shielding portion, one in which openings having the same shape are regularly formed at regular intervals is 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. Usually, a light-shielding part composed of 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 a desired liquid repellency can be exhibited 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 (31) or (32).
General formula (31): Rf-X-Rf '
Formula (32): (Rf-XR) -Y- (R'-X'-Rf ')
In the above formula (31) or (32), 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 a thermal transfer using the above resin composition The law etc. can be mentioned. In addition, an ink-jet ink for color filter according to the present invention, which is prepared by blending light-shielding particles such as a black pigment, is prepared. Alternatively, the light shielding portion may be formed by selectively attaching the ink layer by a method to form an ink layer in a predetermined pattern, curing the ink layer by a method such as ionizing radiation irradiation, and baking as necessary.

  The light-shielding portion is preferably provided to prevent the ink from being mixed when forming a colored layer to be a pixel portion by an inkjet method, and is preferably high to some extent. Considering the overall flatness, the thickness is preferably close to the thickness of the colored layer. The thickness of the light shielding part is appropriately selected and is not particularly limited. Specifically, the thickness is about 1000 to 2000 mm in the case of a metal thin film, and about 0.5 to 2.5 μm in the case of a light shielding resin layer.

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 base material may be a reflective substrate or a white one, but a transparent base material is usually used.
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 given.

(3) Formation of colored layer First, the inkjet ink for a color filter according to the present invention of each color for forming red, green, and blue colored layers as pixels 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 layers are formed by spraying the respective colored layer forming inkjet inks of the corresponding colors by the inkjet method. In this ink spraying step, the ink for a color filter according to the present invention hardly increases in viscosity at the tip of the head 5 and can 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 inkjet ink for color filters of each color can be simultaneously sprayed on a board | substrate using a some head, working efficiency can be improved compared with the case where a colored layer is formed for every color.

  Next, as shown in FIG. 1B, each color ink layer 6R, 6G, 6B is dried, pre-baked as necessary, and then cured by heating. 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 heated, the curable resin contained in the ink-jet ink undergoes a crosslinking reaction, the ink layer is cured, and colored layers (7R, 7G, 7B) are formed.

  The colored layer (pixel) of the color filter formed using the inkjet ink of the present invention is a reaction product of the dispersion auxiliary resin (C) and the epoxy compound (D) and the polyvalent carboxylic acid derivative (E). It is characteristic that it contains things. In this case, the colored layer of the color filter obtained by the present invention is less likely to cause wrinkles and cracks as described above. Moreover, since the inkjet ink of the present invention is excellent in pigment dispersibility and temporal stability of pigment dispersion, the brightness and contrast of the colored layer are improved. In addition, since the dispersion auxiliary resin (C) has an alicyclic skeleton, the yellowing resistance is improved as compared with an acrylic skeleton having a double bond or an aromatic ring skeleton. A colored layer (pixel) with good color purity and improved contrast can be obtained.

Since the colored layer (pixel) of the color filter obtained in the present invention is formed using an ink jet method, the thickness is usually likely to be non-uniform in the region of the colored layer. In other words, when a colored layer is formed by an inkjet method in a region surrounded by the light shielding part on the transparent substrate, the relationship between the ink and the surface of the light shielding part, the height of the light shielding part, the amount of ink to be ejected, etc. The shape of the colored layer in the opening surrounded by the light-shielding part has a portion with a small thickness along the outer edge of the colored layer or in the vicinity thereof, and the center side of the colored layer with respect to the portion with the small thickness. Or a portion having a large thickness along the outer edge of the colored layer or in the vicinity thereof, and on the center side of the colored layer with respect to the thickened portion. Or a surface having a minimum thickness, and the surface tends to be uneven. Here, the outer edge portion of the colored layer is an edge portion that defines the planar shape of the colored layer. Further, the phrase “along the outer edge portion or the vicinity thereof of the colored layer” means that it is only necessary to have a portion having a small thickness along at least a part of the outer edge portion or the vicinity thereof. Further, the thickness of the colored layer refers to the height from the substrate.
Since the colored layer of the color filter according to the present invention is formed using the above-described inkjet ink having good pigment dispersibility according to the present invention, the colored layer has a cross-sectional shape in which, for example, the vicinity of the central portion is raised as described above. Even if it has, it is easy to make it high brightness and high contrast.

  The thickness of the colored layer to be a pixel is usually about 0.5 to 2.5 μm. Further, the thickness of the colored layer of each color may be changed so that the red colored layer is the thinnest, and the green colored layer and the blue colored layer become thicker in this order, and the optimum thickness may be set for each color.

(4) Formation of Protective Layer and Transparent Electrode Film Next, as shown in FIG. 1 (C), the protective layer 8 is formed on the side of the transparent substrate on which the colored layers (7R, 7G, 7B) are formed. To do. The protective layer is provided to flatten the color filter and to prevent components contained in the pixel portion and the like from eluting into the liquid crystal layer of the liquid crystal display device. The thickness of the protective layer can be set in consideration of the light transmittance of the material used, the surface state of the color filter, etc., and can be set in the range of 0.1 to 2.0 μm, for example. The protective layer can be formed using, for example, a known transparent photosensitive resin, two-component curable transparent resin, or the like having a light transmittance required as a transparent protective layer.

In addition, on the protective film, a transparent electrode film is formed using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof, sputtering, vacuum deposition, CVD, etc. It is formed by a general method such as a method (not shown). If necessary, a predetermined pattern can be obtained by etching using a photoresist or using a jig. The thickness of the transparent electrode is about 20 nm to 500 nm, preferably about 100 to 300 nm.
In the method for producing a color filter of the present invention, even if the step of forming the transparent electrode film includes a heating step at a high temperature of 180 ° C. or higher, the inkjet ink for a color filter according to the present invention is used. Therefore, wrinkles and cracks are unlikely to occur in the transparent electrode film. The surface roughness (Ra) of the transparent electrode film obtained in the method for producing a color filter of the present invention is preferably 10 nm or less, and more preferably 8 nm or less. Here, the surface roughness (Ra) refers to the arithmetic average roughness obtained by the following formula.

In the formula, N is the number of divisions with respect to the reference length at the time of measurement, and Rn is a deviation from the average height of the divided sections n when the thickness direction with respect to the surface is height. The surface roughness (Ra) can be measured by an AFM (atomic force microscope).
In others, it can manufacture using the method similar to the method of forming a normal color filter.

(5) Other process The manufacturing method of the color filter of this invention may have another process further. Such other steps can be arbitrarily determined according to the use of the color filter produced according to 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 easier to uniformly spread the ink-jet ink in the opening surrounded by the light-shielding portion in the colored layer forming step, so that no colored layer is formed in the opening. It is because it can prevent that a site | part arises.
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 step used in the present invention, the method of making the light shielding part liquid repellant can make the liquid repellency 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 carried out 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.
Examples of the fluorine compound of the introduced gas used for the plasma irradiation include carbon fluoride (CF ₄ ), fluorine nitride (NF ₃ ), and sulfur fluoride (SF ₆ ).

  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 irradiated plasma electrode 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.

3. Manufacturing method of liquid crystal display device The manufacturing method of the liquid crystal display device of the present invention includes a step of manufacturing a color filter using the manufacturing method of the color filter of the present invention, and the manufactured color filter and the liquid crystal driving side substrate face each other. And assembling.
According to the method for manufacturing a liquid crystal display device of the present invention, the method includes the step of using the method for manufacturing a color filter of the present invention, wherein a color filter with higher performance is obtained using the inkjet ink for the color filter of the present invention. Therefore, a high-quality liquid crystal display device can be obtained.
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 joined by the sealing material, both substrates maintain a cell gap of a predetermined distance. Pasted in state. An active matrix type color liquid crystal display device belonging to the liquid crystal display device manufactured by the manufacturing method of 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 of the present invention is not particularly limited as long as it has the above-described color filter, and may be a known liquid crystal display device. 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.

(Production Example 1: Production of Dispersion Auxiliary Resin 2)
134 g (1 mol) of trimethylolpropane and 3726 g (30 mol) of 4-vinylcyclohexene-1-oxide are mixed at 60 ° C., and the conversion of 4-vinylcyclohexene-1-oxide becomes 98% by gas chromatography analysis. Then, ethyl acetate was added to the resulting reaction solution and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous transparent solution. Further, 573 g of this compound was dissolved in ethyl acetate and charged into the reactor, and 387 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was kept at 40 ° C. After completion of the peracetic acid preparation, the mixture was further aged at 40 ° C. for 4 hours. Ethyl acetate was added to the reaction crude liquid, washed with alkaline water containing 416 g of sodium carbonate, and thoroughly washed with distilled water. The ethyl acetate layer was concentrated to obtain a viscous transparent liquid.

(Production Example 2: Production of Dispersion Auxiliary Resin 3)
In the same manner as in Production Example 1, 25 g (1 mol) of allyl alcohol, 868 g (7 mol) of 4-vinylcyclohexene-1-oxide and 4.7 g of BF3 etherate were reacted to obtain a viscous liquid product. Further, in the same manner as in Production Example 1, 492 g of this compound was reacted with 395 g of peracetic acid to obtain a viscous transparent liquid.

(Production Examples 3 to 5): Synthesis of epoxy group-containing polymer (D1))
A 4-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 44 parts by weight of a solvent not containing a hydroxyl group according to the mixing ratio shown in Table 1, and heated to 115 ° C. while stirring. did. Next, 56.0 parts by weight of a mixture (dropping component) of the above-described solvent BCA containing no monomer, polymerization initiator, and hydroxyl group having the composition described in Table 1 at a temperature of 115 ° C. was added from a dropping funnel over 2 hours. It was dripped quickly. After completion of dropping, the mixture is maintained at 115 ° C. for 2.5 hours, then heated to 125 ° C., and the reaction is terminated when the reaction is completed for 2 hours. was gotten.

* 1) Abbreviations in the table are as follows.
BCA: Diethylene glycol monobutyl ether acetate ECA: Diethylene glycol monoethyl ether acetate GMA: Glycidyl methacrylate CHMA: Cyclohexyl methacrylate MMA: Methyl methacrylate Perhexyl I: tert-hexylperoxyisopropyl monocarbonate (trade name, manufactured by NOF Corporation)
* 2) Property: Appears visually.
* 3) Solid content: Calculated from the heating residue when dried with hot air at 140 ° C. for 60 minutes.
* 4) Epoxy equivalent: An epoxy group was subjected to a ring-opening reaction with an excess of 0.2N · dioxane hydrochloride solution, and then back-titration of unreacted hydrochloric acid with 0.1N · KOH ethanol solution was performed to calculate an epoxy equivalent. .
* 5) Viscosity: measured at 20 ° C. using an E-type viscometer.
* 6) Weight average molecular weight: A value in terms of polystyrene by gel permeation chromatography (GPC).

(Production Examples 6 to 8: Synthesis of polyvalent carboxylic acid derivative (E))
A four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer was charged according to the blending ratio shown in Table 2, heated with stirring and heated to 70 ° C. Next, stirring was continued while maintaining the temperature, and when the acid value of the mixture became 3.0 mgKOH / g or less, the reaction was terminated, and a polyvalent carboxylic acid derivative (E) having the characteristics shown in Table 2 was obtained.

* 1) Acid value of the solution: Calculated by titration with a 0.1 N · KOH ethanol solution. The acid value of the solution is determined according to the method for measuring the acid value of JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. A certain amount of resin was dissolved in a THF) solution, and titration was performed with a KOH / ethanol solution using phenolphthalein as an indicator for measurement.
* 2) Blocking rate: Calculated by converting to solid content from the acid value of the solution.
* 3) Block acid solid content: Ratio of polycarboxylic acid derivative produced by reaction of the charged carboxylic acid with an equivalent amount of vinyl ether compound * 4) Acid equivalent of solution: Blocking agent in water / methanol solution After dissociation, the acid value was measured. The acid value was measured according to the hydrolysis acid value measurement of JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.

(Example B1: Preparation of blue inkjet ink for color filter)
(1) Preparation of Blue Pigment Dispersion (Examples DB1, DB5) A pigment, a pigment dispersant, a pigment dispersion auxiliary resin, and an organic solvent are mixed at a blending ratio shown in Table 3 or Table 4, and zirconia beads having a diameter of 0.5 mm. 300 parts by weight was added and dispersed for 3 hours using a paint shaker (manufactured by Asada Tekko Co., Ltd.). After the dispersion, the mixture was filtered through a 5.0 micron membrane filter to prepare blue inkjet ink pigment dispersions (DB1, DB5).

(2) Preparation of binder composition A Teflon (registered trademark) -covered rotor was placed in a sample bottle and placed on a magnetic stirrer. In this sample bottle, the epoxy group-containing polymer (D1) described in the above production example, the epoxy group-containing compound (D2), the polyvalent carboxylic acid derivative (E) described in the above production example, and a thermal latent catalyst according to the following ratios: The mixture was sufficiently dissolved by stirring at room temperature, and a diluent solvent was added and dissolved by stirring to adjust the viscosity. Then, this was filtered to obtain a binder composition. The acid / epoxy equivalent ratio of the binder composition was 0.9.
[Binder composition ratio]
-Epoxy group-containing polymer (D1) of Production Example 3 (solid content 37.5 wt%): 66.7 parts by weight-Polyvalent carboxylic acid derivative (E) of Production Example 5 (solid content 35.2 wt%) : 49.7 parts by weight-Epoxy group-containing compound (D2) (trade name jER157S70, manufactured by Japan Epoxy Resin Co., Ltd.) (solid content: 27.3% by weight): 54.6 parts by weight-thermal latent catalyst (trade name) LC-1, manufactured by NOF Corporation): 3.6 parts by weight, BCA: 75.4 parts by weight

(3) Preparation of inkjet ink In the mixing ratio shown in Table 5, the blue pigment dispersion (Examples DB1, DB5) and the binder composition prepared above and the binder composition were further mixed with a solvent, and the color of Example B1 was mixed. A blue inkjet ink for filter was obtained.

(Examples B2 to B7: Preparation of blue inkjet ink for color filter)
Similarly to Examples DB1 and DB5, blue pigment dispersions (Examples DB2 to DB8) were prepared at the blending ratios shown in Table 3 or Table 4. Next, in the same manner as in Example B1, the blue pigment dispersion and the binder composition were further mixed with the mixture ratio shown in Table 5 and a solvent was further mixed to obtain a blue inkjet ink for a color filter.

(Comparative Examples B1 to B9: Preparation of blue inkjet ink for color filter)
Similarly to Examples DB1 and DB5, blue pigment dispersions (Comparative Examples DB1 to DB10) were prepared at the blending ratios shown in Table 3 or Table 4. Next, in the same manner as in Example B1, the blue pigment dispersion and the binder composition were further mixed with the mixing ratio shown in Table 6 and a solvent was further mixed to obtain a blue inkjet ink for a color filter.

The abbreviations in Tables 3 to 6 are as follows.
Disperbyk 2000: trade name, Disperbyk 161 manufactured by Big Chemie Japan Co., Ltd .: trade name, dispersion auxiliary resin manufactured by Big Chemie Japan Co., Ltd. 1: trade name EHPE-3150 (1 of 2,2-bis (hydroxymethyl) -1-butanol , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct), average number of epoxy functional groups in the molecule (sum of n1 to nk) 15, epoxy equivalent 179 g / eq, dispersion auxiliary resin 2 manufactured by Daicel Chemical Industries, Ltd .: Production Example 1 (number of epoxy functional groups in the molecule (sum of n1 to nk) average 10, epoxy equivalent 182 g / eq)
Dispersion auxiliary resin 3: Production Example 2 (number of epoxy functional groups in the molecule (sum of n1 to nk) average 7, epoxy equivalent 185 g / eq)
YDPN-638: trade name, phenol novolac type epoxy resin, manufactured by Toto Kasei Co., Ltd., epoxy equivalent of 179 g / eq
SR-16H: trade name, 1,6-hexanediol type epoxy resin, manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent 157 g / eq
EPPN-502H: trade name, trisphenol methane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 168 g / eq
jERYX-4000: trade name, biphenyl type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 180-192 g / eq
BCA: Diethylene glycol monobutyl ether acetate ECA: Diethylene glycol monoethyl ether acetate EEP: Ethyl 3-ethoxypropionate

When the ink compositions shown in Table 5 and Table 6 are shown, only the solid content of the pigment dispersion and the binder component is described. All solvents contained in these components were counted in the solvent column.

Each test method in Tables 3-6 is as follows.
1. Stability of pigment dispersion with time and stability with time of ink Immediately after the preparation of each pigment dispersion, and after storage at 25 ° C. in a sealed container, the viscosity after 1 day, 1 week and the average particle diameter after 1 week were measured. Further, the viscosity and average particle diameter were measured immediately after the ink was prepared and after 1 month of storage in a sealed container at 25 ° C.
<Viscosity>
The viscosity was measured at 23 ° C. with a rotational vibration type viscometer Viscomate VM-1G manufactured by Yamaichi Electronics.
<Average particle size>
The average particle size 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 each pigment dispersion was diluted 100 times with each main solvent. It was measured as 360 seconds. Here, the average particle diameter is a 50% average particle diameter, that is, a volume-based median diameter.

[Create coating film for evaluation]
The coating film for evaluating using each inkjet ink was created.
By spin coating on a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35), the dry film thickness is 1.61 μm for red inkjet ink and 1.65 μm for green and blue inkjet inks. As described above, each of the inkjet inks was applied.
Thereafter, prebaking was performed on a hot plate at 90 ° C. for 10 minutes. Then, in a clean oven, heating was performed at 200 ° C. for 30 minutes to perform post-baking, and heating was further performed at 240 ° C. for 30 minutes to perform post-baking, thereby forming a colored layer.

The substrate on which the coating film for evaluation was formed using ITO-resistant blue inkjet ink was immersed in isopropyl alcohol for 5 minutes, then dried with isopropyl alcohol vapor, washed, and then set at a substrate set temperature of 200 ° C. An ITO (indium tin oxide) electrode was formed to a thickness of 120 nm under a vacuum of 6 × 10 ⁻³ Torr. After the heat resistance test at 180 ° C. for 60 minutes, the evaluation was made according to the following criteria. Further, the surface roughness (Ra) of the formed ITO film was measured by AFM. The AFM used was NanoScope IIIa manufactured by Biko Japan.
[Evaluation criteria for ITO resistance]
A: No abnormality such as wrinkles or cracks was observed on the ITO electrode.
Δ: Several abnormalities such as wrinkles and cracks were observed on the ITO electrode.
X: Abnormalities such as wrinkles and cracks were observed on the entire surface of the ITO electrode.

3. The substrate on which the coating film for evaluation was formed using the yellow-modified blue inkjet ink was heated at 240 ° C. for 1 hour, and the color difference ΔEab before and after heating was calculated based on the CIE 1976 standard and evaluated. The measurement of the color difference ΔEab was performed using a microspectrophotometer OSP200 manufactured by Olympus Optical Co., Ltd.
<Evaluation criteria>
○ ΔEab <3
× 3 ≦ ΔEab

4). Adhesion The substrate on which the coating film for evaluation was formed using the blue ink-jet ink was cut into 11 vertical and horizontal cuts at 1 mm intervals perpendicular to each other with a cutter. Furthermore, the cellophane tape was lightly adhered to the pattern with a finger, the tape was quickly peeled off, the state of the wound was observed, and the determination was made according to the following criteria.
<Evaluation criteria>
8 points: There is slight peeling at the line of cuts, and the area of the defect is less than 5% of the total square area.
6 points: There is peeling at the intersecting line of the cuts, and the area of the missing part is 5% or more and less than 15% of the total square area.
4 points: The width of peeling due to cuts is wide, and the area of the missing part is 15% or more and less than 35% of the total square area.
2 points: The width of peeling due to cuts is wider than 4 points, and the area of the missing part is 35% or more and less than 65% of the total square area.
0 point: The area of peeling is 65% or more of the total square area.

5. Solvent resistance The substrate on which the coating film for evaluation was formed using the blue inkjet ink was immersed in N-methylpyrrolidone having a liquid temperature of 40 ° C. for 1 hour, and the color difference ΔEab before and after immersion was calculated based on the CIE 1976 standard. The measurement was performed using a microspectrophotometer OSP200 manufactured by Olympus Optical Co., Ltd.
<Evaluation criteria>
○ ΔEab <1
△ 1 ≦ ΔEab <3
× 3 ≦ ΔEab

From the results of Tables 3 and 4, Examples DB1 to DB8 in which pigment dispersions were prepared using the dispersion assisting resin according to the present invention were excellent in pigment dispersibility and stability with time of the pigment dispersion. On the other hand, Comparative Examples DB1, DB2, DB4, DB6, DB7, DB9 using a dispersion auxiliary resin different from the present invention, and Comparative Examples DB5 and DB10 using no dispersion auxiliary resin are pigment dispersibility and pigment dispersion. The stability over time was inferior. On the other hand, Comparative Examples DB3 and DB8 were excellent in pigment dispersibility and stability with time of the pigment dispersion.

From the results of Tables 5 and 6, Examples B1 to B8, which are ink jet inks prepared with a pigment dispersion using the dispersion auxiliary resin according to the present invention, are excellent in pigment dispersibility and ink aging stability. It was. Moreover, it was excellent in heat yellowing resistance, excellent in solvent resistance and adhesion of the cured film, and even when the ITO film was formed under ultra-low pressure and high temperature, no wrinkles or cracks were generated in the ITO film, and the film physical properties were good.

On the other hand, Comparative Examples B8 and B9 in which no dispersion auxiliary resin was used were considerably inferior in pigment dispersibility and ink aging stability. In Comparative Examples B8 and B9, wrinkles and cracks were generated in the ITO film when formed under ultra-low pressure and high temperature, the solvent resistance and adhesion of the cured film were poor, and the film properties were poor.

Further, Comparative Examples B1 to B7 using a dispersion auxiliary resin different from the present invention are all of heat-resistant yellowing and / or ITO resistance, adhesion, solvent resistance, pigment dispersibility, and ink aging stability. Either was inferior.

FIG. 2 shows an evaluation coating film surface photograph of Example B1 after ITO resistance evaluation, and FIG. 3 shows an evaluation coating film surface photograph of Comparative Example B2 after ITO resistance evaluation.

(Example R1: Preparation of red inkjet ink for color filter)
(1) Preparation of Red Pigment Dispersion (Examples DR1 to DR3) A pigment, a pigment dispersant, a pigment dispersion auxiliary resin, and an organic solvent are mixed at a blending ratio shown in Table 7, and 300 weight of zirconia beads having a diameter of 0.5 mm are mixed. In addition, dispersion was performed for 3 hours using a paint shaker (manufactured by Asada Tekko Co., Ltd.). After dispersion, the mixture was filtered through a 5.0 micron membrane filter to prepare red inkjet ink pigment dispersions (DR1 to DR3).
(2) Preparation of binder composition The binder composition used was the same as that used in the blue inkjet ink of Example B1.
(3) Preparation of inkjet ink In the mixing ratio shown in Table 8, the prepared red pigment dispersion (Examples DR1 to DR3) and the binder composition were further mixed with a solvent, and the color of Example R1 was mixed. A red inkjet ink for filter was obtained.

(Examples R2 and R3: Preparation of red inkjet ink for color filter)
Similar to Examples DR1 to DR3, red pigment dispersions (Examples DR4 to DR9) were prepared at the blending ratios shown in Table 7. Next, in the same manner as in Example R1, the red pigment dispersion and the binder composition were mixed with the mixing ratio shown in Table 8 and a solvent was further added and mixed well to obtain a red inkjet ink for a color filter.

(Comparative Examples R1 and R2: Preparation of red inkjet ink for color filter)
Similar to Examples DR1 to DR3, red pigment dispersions (Comparative Examples DR1 to DR6) were prepared at the blending ratios shown in Table 7. Next, in the same manner as in Example R1, the red pigment dispersion and the binder composition were mixed with the mixing ratio shown in Table 8 and a solvent was further added and mixed well to obtain a red inkjet ink for a color filter.
The evaluation results are shown in Table 7 and Table 8 together with the amount of each component.

From the results of Table 7, Examples DR1 to DR9, in which pigment dispersions were prepared using the dispersion assisting resin according to the present invention, were excellent in pigment dispersibility and stability over time of the pigment dispersion. On the other hand, Comparative Examples DR1 to DR6 using a dispersion auxiliary resin different from the present invention were inferior in pigment dispersibility and stability with time of the pigment dispersion.

From the results of Table 8, Examples R1 to R3, which are inkjet inks prepared with pigment dispersions using the dispersion assisting resin according to the present invention, were excellent in pigment dispersibility and ink aging stability. Moreover, it was excellent in heat yellowing resistance, excellent in solvent resistance and adhesion of the cured film, and even when the ITO film was formed under ultra-low pressure and high temperature, no wrinkles or cracks were generated in the ITO film, and the film physical properties were good.

On the other hand, Comparative Examples R1 and R2 using a dispersion auxiliary resin different from the present invention are any of heat-resistant yellowing and / or ITO resistance, adhesion, solvent resistance, pigment dispersibility, and ink aging stability. It was inferior.

(Example G1: Preparation of green inkjet ink for color filter)
(1) Preparation of Green Pigment Dispersion (Examples DG1 to DG4) A pigment, a pigment dispersant, a pigment dispersion auxiliary resin, and an organic solvent are mixed at a blending ratio shown in Table 9, and 300 weight of zirconia beads having a diameter of 0.5 mm are mixed. In addition, dispersion was performed for 3 hours using a paint shaker (manufactured by Asada Tekko Co., Ltd.). After dispersion, the mixture was filtered through a 5.0 micron membrane filter to prepare pigment dispersions (DG1 to DG4) for green inkjet ink.
(2) Preparation of binder composition The binder composition used was the same as that used in the blue inkjet ink of Example B1.
(3) Preparation of inkjet ink The green pigment dispersion (Examples DG1 to DG4) and the binder composition prepared above and the binder composition were mixed at the blending ratio shown in Table 11 and further mixed well, and the color of Example G1 A green inkjet ink for filter was obtained.

(Examples G2 and G3: Preparation of green inkjet ink for color filter)
Similarly to Examples DG1 to DG4, green pigment dispersions (Examples DG5 to DG12) were prepared at the blending ratios shown in Table 9. Next, in the same manner as in Example G1, the green pigment dispersion and the binder composition were further mixed with the green pigment dispersion and the binder composition at the blending ratios shown in Table 11 to obtain a green inkjet ink for a color filter.

(Comparative Examples G1 and G2: Preparation of green inkjet ink for color filter)
Similarly to Examples DG1 to DG4, green pigment dispersions (Comparative Examples DG1 to DG8) were prepared at the blending ratios shown in Table 10. Next, in the same manner as in Example G1, the green pigment dispersion and the binder composition were further mixed with the green pigment dispersion and the binder composition at the blending ratios shown in Table 11 to obtain a green inkjet ink for a color filter.
The evaluation results are shown in Table 9 to Table 11 together with the amounts of each component.

From the results of Tables 9 and 10, Examples DG1 to DG12, in which pigment dispersions were prepared using the dispersion assisting resin according to the present invention, were excellent in pigment dispersibility and temporal stability of the pigment dispersion. On the other hand, Comparative Examples DG1 to DG8 using a dispersion auxiliary resin different from the present invention were inferior in pigment dispersibility and stability with time of the pigment dispersion.

From the results of Table 11, Examples G1 to G3, which are inkjet inks prepared with a pigment dispersion using the dispersion assisting resin according to the present invention, were excellent in pigment dispersibility and ink aging stability. Moreover, it was excellent in heat yellowing resistance, excellent in solvent resistance and adhesion of the cured film, and even when the ITO film was formed under ultra-low pressure and high temperature, no wrinkles or cracks were generated in the ITO film, and the film physical properties were good.

On the other hand, Comparative Examples G1 and G2 using a dispersion auxiliary resin different from the present invention are both heat-resistant yellowing and / or ITO resistance, adhesion, solvent resistance, pigment dispersibility, and ink aging stability. Either of them was inferior.

[Evaluation of brightness and contrast of inkjet ink]
The blue inkjet inks of Examples B1, B2 and Comparative Examples B1, B2 obtained above; the red inkjet inks of Examples R1, R2 and Comparative Examples R1, R2; the green colors of Examples G1, G2 and Comparative Examples G1, G2 The inkjet ink was evaluated for brightness and contrast as follows. Table 12 shows the evaluation results.

<Evaluation method>
A coating film for evaluation (colored layer) was prepared in the same manner as described above using each inkjet ink.
(1) It measured using the brightness | luminance microspectroscope (Olympus Co., Ltd. product, OSP-200).
(2) Contrast A polarizing film 43 (NPF-SEG1425DU made by Nitto Denko) was bonded to a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35) 40 to form a polarizing plate 43. As shown in FIG. 4, two polarizing plates 43 are sandwiched so as to be orthogonal or parallel so that the polarizing film 42 side is the outside of the glass substrate 40 on which the colored layer 41 is formed. A measurement sample 44 was obtained. In the configuration of the measurement sample 44, the distance l ₁ between the polarizing plate 43 and the colored layer 41 was 9.3 mm, and the distance l ₂ between the polarizing plate 43 and the glass substrate 40 was 0 mm.
As shown in FIG. 5, luminance measurement was performed in contrast measurement. A backlight 45 was lit on the measurement sample 44, and the luminance was measured. Measurement samples were prepared by setting polarizing plates orthogonally and then in parallel, and the respective luminances were measured. The contrast value was calculated by the luminance when parallel to the luminance when orthogonal (luminance when parallel / luminance when orthogonal). The position where the luminance was measured in the sample was a position where the film thickness was uniform in the color filter layer. As a device 46 for measuring luminance in contrast measurement, a luminance meter (LS-100 manufactured by Konica Minolta Sensing Co., Ltd.) equipped with a close-up lens (No. 153) 47 was used. The viewing angle of the luminance meter was 1 °. The distance L from the close-up lens 47 to the measurement sample 44 was 710 mm.

From the results of Table 12, Examples B1, B2, R1, R2, G1, and G2, which are inkjet inks prepared with a pigment dispersion using the dispersion assisting resin according to the present invention, all have pigment dispersibility and ink properties. Since it was excellent in stability over time and excellent in yellowing resistance, the brightness and contrast during curing were improved. On the other hand, Comparative Examples B1, B2, R1, R2, G1, and G2 using a dispersion auxiliary resin different from the present invention were inferior in brightness and contrast at the time of curing as compared with Examples.

(Example 1: Production of color filter)
By preparing 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, and forming a resin black matrix on this glass substrate by photolithography A color filter substrate was prepared. 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 Example B1 was adhered accurately and uniformly to the blue pixel forming section partitioned by the black matrix of the 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, and 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 all areas of the pixel formation area (1 pixel) every 1 μm using an optical interference type 3D non-contact surface shape measuring device (product name: Micromap557N manufactured by Micromap USA). Is the average.
The substrate on which the RGB pixel pattern is formed is immersed in isopropyl alcohol for 5 minutes, then dried with isopropyl alcohol vapor, washed, and then subjected to ITO (at a substrate set 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 isopropyl alcohol for 5 minutes, steam-washed with isopropyl alcohol, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. A color filter was obtained.

It is explanatory drawing of the method of manufacturing a color filter using the inkjet ink of this invention. It is a photograph which shows the coating-film surface for evaluation of Example B1 after ITO tolerance evaluation. It is a photograph which shows the coating-film surface for evaluation of comparative example B2 after ITO tolerance evaluation. It is a figure explaining the sample in the measurement of contrast in the present invention. It is a figure explaining the measuring method of contrast in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Ink-repellent convex part 4 Pixel part formation area 5 Inkjet head 6 Ink layer 7 Pixel part 8 Protective film 9 Photocatalyst containing layer 10 Photomask 11 Exposure part 12 Light 40 Glass substrate 41 Colored layer 42 Polarizing film 43 polarizing plate 44 measurement sample 45 backlight 46 device for measuring luminance 47 close-up lens 101, 102 ... color filter

Claims (12)

(A) a pigment,
(B) a pigment dispersant,
(C) A dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1):
(D) An epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C),
(E) An inkjet ink for a color filter, comprising a polycarboxylic acid derivative in which a carboxylic acid (e1) having a structure represented by the following formula (11) is latentized by a vinyl ether compound (e2), and (F) a solvent.

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.) (A) a pigment,
(B) a pigment dispersant,
(C) After preparing a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1), and (F) a pigment dispersion containing a solvent, at least (D) different from the dispersion auxiliary resin (C), Addition of an epoxy compound having two or more epoxy groups in one molecule, and (E) a polyvalent carboxylic acid derivative in which a carboxylic acid (e1) having a structure of the following formula (11) is latentized by a vinyl ether compound (e2) An ink-jet ink for color filters.

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)   The inkjet ink for a color filter according to claim 1, wherein the dispersion average particle diameter of the pigment is 100 nm or less.   The inkjet ink for color filters according to any one of claims 1 to 3, wherein a sum of n1 to nk in the epoxy resin represented by the formula (1) is 4 to 30.   The inkjet ink for color filters according to any one of claims 1 to 4, wherein the dispersion auxiliary resin (C) is 5 to 80 parts by weight with respect to 100 parts by weight of the pigment dispersant (B).   The dispersion auxiliary resin (C) is 5 to 70 parts by weight based on 100 parts by weight of the total amount of the epoxy compound (D) and the polyvalent carboxylic acid derivative (E). The inkjet ink for color filters as described in 2.   The solvent contains, as a main solvent, 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 in a proportion of 60% by weight or more based on the total amount of the solvent. The inkjet ink for color filters in any one of 1.   The main solvent is 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, dimethyl succinate, and diethyl succinate. The inkjet ink for a color filter according to claim 7, wherein the ink is one or more selected from the group consisting of: At least (A) a pigment, (B) a pigment dispersant, and (C) a dispersion auxiliary resin composed of an epoxy resin represented by the following formula (1) is mixed with (F) a solvent and dispersed to prepare a pigment dispersion. And a process of

(However, R ^a is a residue obtained by removing active hydrogen in an organic compound having k active hydrogens. N1, n2... Nk are each 0 or an integer of 1 to 100, and the sum is 1 to 1. And k represents an integer of 1 to 100. A is an oxynorbornene skeleton having a substituent X or an oxycyclohexane skeleton having a substituent X, and is represented by the following formula:

At least (D) an epoxy compound having two or more epoxy groups in one molecule, which is different from the dispersion auxiliary resin (C), and (E) a carboxylic acid (e1) having a structure of the following formula (11) is a vinyl ether compound The manufacturing method of the inkjet ink for color filters which has the process of mixing the binder system containing the polyhydric carboxylic acid derivative latentized by (e2) with the said pigment dispersion liquid.

(The six-membered ring in the formula is an aromatic or alicyclic hydrocarbon. M1 is an integer of 0 to 4, t1 is an integer of 0 to 1, and n is an integer of 1 to 4. When n is 1, R ¹ is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R ¹ is a hydrocarbon group having 2 to 8 carbon atoms. R ² is an alkyl group having 1 to 5 carbon atoms.)   Manufacturing of a color filter including a colored layer forming step of forming a colored layer by selectively attaching the inkjet ink for a color filter according to any one of claims 1 to 8 to a predetermined region on a substrate by an inkjet method. Method.   The method for producing a color filter according to claim 10, 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 method for manufacturing a liquid crystal display device, comprising: a step of manufacturing a color filter using the method for manufacturing a color filter according to claim 10 or 11; and a step of assembling the manufactured color filter and a liquid crystal driving side substrate to face each other. .

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