JP2008216802A - Yellow photosensitive composition for color filter, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a yellow photosensitive composition having good coating and ejection properties and suitable for use in the manufacture of a color filter having good contrast, a photosensitive transfer material produced using the yellow photosensitive composition, a color filter with yellow pixels having good contrast, and a liquid crystal display device including the color filter. <P>SOLUTION: The yellow photosensitive composition comprises (A) a yellow pigment, (B) a monomer and (C) a solvent and has a contrast coefficient of 1,000-20,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a yellow photosensitive composition for a color filter, a photosensitive transfer material produced using the same, a color filter, and a liquid crystal display device.

Conventionally, a color filter for a liquid crystal display device is composed of pixels of three colors of RGB. However, in order to realize more realistic color expression, it has been proposed to add a fourth color (yellow pixel) or a fifth color (cyan pixel) (see, for example, Patent Document 1).
However, when a color filter is produced using a commercially available yellow pixel composition for a color filter in order to obtain such a yellow pixel of a multicolor filter, coating defects are likely to occur. Further, when forming a color filter by the ink jet method, the discharge becomes unstable, which is a problem.
JP 2005-523465 A

An object of the present invention is to provide a yellow photosensitive composition suitable for producing a color filter having good coating and ejection characteristics and good contrast.
It is another object of the present invention to provide a photosensitive transfer material produced using the yellow photosensitive composition, a color filter having yellow pixels having good contrast, and a liquid crystal display device including the color filter.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> A yellow photosensitive composition for a color filter containing (A) a yellow pigment, (B) a monomer, and (C) a solvent, wherein the contrast coefficient is 1000 or more and 20000 or less. object.
<2> The yellow photosensitive composition for a color filter according to the above <1>, which has a viscosity at 25 ° C. of 10 mPa · s or more and 20 mPa · s or less and is for inkjet.

<3> The yellow photosensitive composition for a color filter according to <1>, wherein the viscosity at 25 ° C. is 1 mPa · s or more and 5 mPa · s or less, and is used for a slit coater.
<4> A photosensitive transfer material in which a photosensitive layer is provided on the temporary support using the yellow photosensitive composition for a color filter described in any one of the above items <1> to <3>.

<5> A color filter formed using the yellow photosensitive composition for a color filter according to any one of <1> to <3> or the photosensitive transfer material according to <4>.
<6> A liquid crystal display device comprising the color filter according to <5>.

ADVANTAGE OF THE INVENTION According to this invention, the yellow photosensitive composition suitable for manufacture of the color filter which has favorable application | coating and discharge characteristics and has favorable contrast can be provided.
In addition, according to the present invention, there is provided a photosensitive transfer material produced using the yellow photosensitive composition, a color filter having yellow pixels having good contrast, and a liquid crystal display device including the color filter. it can.

  The yellow photosensitive composition for color filters of the present invention (hereinafter also simply referred to as “yellow photosensitive composition”) contains (A) a yellow pigment, (B) a monomer, and (C) a solvent, and has a contrast coefficient. Is 1000 or more and 20000 or less.

(Contrast coefficient)
The yellow photosensitive composition of the present invention is a composition having a contrast coefficient of 1000 or more and 20000 or less. In the present invention, the contrast coefficient is obtained as follows.
A layer made of a photosensitive composition to be measured (hereinafter also simply referred to as “photosensitive layer”) is formed on a glass substrate so as to have a film thickness of 2.0 μm, and a sample glass substrate is manufactured.
The photosensitive layer may be formed by applying and drying the photosensitive composition using a coating machine such as a slit coater, or using a photosensitive transfer material, or an inkjet method. May be formed.
Using a three-wavelength cold-cathode tube light source with a diffusing plate as the backlight unit, the glass substrate prepared above is installed between two polarizing plates, and the light passing through when the polarizing plate is installed in parallel Nicol The contrast value can be obtained by dividing the Y value of chromaticity by the Y value of the chromaticity of light that passes through when installed in crossed Nicols.
For the measurement of chromaticity, a color luminance meter (for example, BM-5 manufactured by Topcon Corporation) is used, and the contrast value of the glass substrate is used as the contrast coefficient in the present invention.

More specifically, the measurement is performed as follows.
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate is heat treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the photosensitive composition to be measured was applied using a spin coater (for example, 1H-DX; manufactured by Mikasa Co., Ltd.) so that the dry film thickness was 2.0 μm. And dried at 100 ° C. for 3 minutes to produce a glass substrate for measurement.
The contrast measurement was performed as follows. That is, using a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) as a backlight unit, between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) Divide the Y value of the chromaticity of the light that passes when the glass substrate prepared above is installed and the polarizing plate is installed in parallel Nicol by the Y value of the chromaticity of the light that passes when installed in crossed Nicol. To find the contrast value. A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. The contrast value of this glass substrate was used as the contrast coefficient of the photosensitive composition.
Two polarizing plates, a glass substrate, and a color luminance meter were installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, and a cylinder 11 mm in diameter and 20 mm in length. Light was irradiated to a measurement sample installed at a position of 65 mm, and the transmitted light was measured with a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm.
The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.

In the present invention, the contrast coefficient of the yellow photosensitive composition is 1000 or more and 20000 or less. Thereby, a color filter having high coating stability or ejection stability and few defects can be produced.
In the present invention, the contrast coefficient in the above range can be achieved by subjecting the above-described pigment in the present invention to the refining treatment described below.

-Refinement treatment-
The pigment refinement treatment in the present invention may be performed simultaneously with the pigment and the dispersant, or may be performed separately without mixing only the pigment with the dispersant. Among these, it is preferable from the viewpoint of production efficiency that the micronization treatment is simultaneously performed in the state where the pigment and the dispersant coexist. In the following, a method for carrying out the micronization process using only the pigment will be described.
~ Pinning-only refinement method ~
As the above-mentioned refinement treatment, (1) a method in which a pigment is mechanically pulverized to make the particle size fine (referred to as a grinding method), and (2) a solution obtained by dissolving a pigment in a good solvent is added to a poor solvent to produce particles. Examples thereof include a method for precipitating a pigment having a small diameter (referred to as a precipitation method), and (3) a method for producing particles having a small particle diameter at the time of synthesis (referred to as a synthetic precipitation method). An appropriate method can be selected depending on the synthesis method and chemical properties of the pigment to be used. You may implement a refinement | miniaturization process combining 2 or more types of methods. Moreover, when performing the refinement | miniaturization process of a pigment and a dispersing agent separately, each refinement | miniaturization process may differ.

  The (1) grinding method is a method in which a pigment and / or a dispersant is ground together with a grinding agent such as salt using a ball mill, a sand mill or a kneader, and then the grinding agent is removed to make the primary particles fine. Thus, relatively uniform pigment particles and / or dispersed particles can be obtained.

The (2) precipitation method is a method in which a pigment and / or a dispersant is dissolved in a suitable good solvent and then mixed with a poor solvent to precipitate fine crystal particles. The size of the primary particles can be controlled by the deposition rate and the like.
Examples of the solvent to be used include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or basic solvents such as liquid ammonia and a dimethylformamide solution of sodium methylate.

  Among the (2) precipitation methods, there is a leuco method as a special precipitation method. When a vat dye, such as a flavantron, perinone, perylene, or indanthrone, is reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. By adding an appropriate oxidizing agent to this aqueous solution and oxidizing it, a fine pigment can be precipitated.

  The (3) synthesis precipitation method is a method in which pigments and / or dispersants are synthesized and simultaneously precipitated as fine crystal particles. However, when the produced fine pigment and / or fine dispersant is taken out from the solvent, filtration, which is a general separation method, becomes difficult unless the particles are aggregated into large secondary particles. It is applied to pigments such as azo-based compounds that are synthesized in an aqueous system where secondary aggregation is likely to occur.

  Any of the above-described methods may be used for the above-mentioned miniaturization treatment. However, since the materials are not relatively limited among these methods, (1) the grinding method is preferable.

(1) The grinding method will be described in detail below.
In this method, a pigment is mechanically kneaded with a water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve the pigment (this process is hereinafter referred to as “salt milling”), and then the inorganic salt and the organic solvent are mixed. Is removed, washed with water, and dried to obtain fine pigments of primary particles. Further, it is preferable to add a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment because the salt milling treatment does not cause crystal growth of the pigment. Although it does not specifically limit as solid resin, The below-mentioned binder (for example, alkali-soluble binder) can be used.

The ratio of the inorganic salt to the pigment is generally 1 to 20 parts by mass, and preferably 2 to 10 parts by mass with respect to 1 part by mass of the pigment. The preferred range is preferable from the viewpoint of improving productivity without decreasing the pigment refining efficiency and without further reducing the amount of pigment processed.
In the salt milling treatment, it is preferable to add a wetting agent so that the pigment and the inorganic salt are uniformly solidified. Usually, depending on the blending ratio of the pigment and the inorganic salt, usually 50% by mass of the pigment. An amount of ~ 300% by weight is used.

More specifically, the above-mentioned salt milling is carried out by adding a small amount of a water-soluble solvent (described later) as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, kneading with a kneader or the like, and then adding the mixture into water. Then, the mixture is stirred with a high speed mixer or the like to form a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment and / or dispersion in which primary particles are refined.
The particle diameter of the refined pigment is preferably 20 nm to 100 nm, more preferably 25 nm to 80 nm, and particularly preferably 30 nm to 70 nm in terms of number average particle diameter.
By setting it as the range of the said number average particle diameter, the yellow photosensitive composition obtained is preferable from a viewpoint from which the application | coating suitability at the time of manufacturing a color filter, or inkjet discharge suitability becomes favorable. By setting the thickness to 20 nm or more, aggregation tends to be difficult, pigment dispersion can be improved, and the dispersion state tends to be kept stable. By setting the thickness to 100 nm or less, the contrast coefficient can be adjusted to a range of 1000 to 20000. This tends to be a trend.
The number average particle diameter of the pigment in the yellow photosensitive composition was measured using 100 FE-SEM (F-900 manufactured by Hitachi, Ltd.) (magnification is 30000 times) in each photographed image. The diameter of a circle equal to this is obtained, and this can be obtained as the particle diameter. The diameters obtained for 100 particles are averaged to obtain the average particle diameter (average diameter) of the particles.
Moreover, it can also measure using Nikkiso Co., Ltd. nano track UPA-EX150.

  The yellow photosensitive composition of the present invention is suitable as an ink for ink jet and also as a coating solution for a coating device (slit coater) having a slit-like nozzle, which will be described later.

(monomer)
The yellow photosensitive composition of the present invention contains at least one monomer. The monomer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, tris (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. In addition, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.
Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers (the monomer or oligomer preferably has a molecular weight of 200 to 1000) may be used alone or in combination of two or more.
As for content of the monomer with respect to the total solid of a yellow photosensitive composition, 5-50 mass% is common, and 10-40 mass% is preferable. Within the preferred range, control of developability does not become difficult, so there is no problem in suitability for production, and the curing power at the time of exposure is not insufficient.

(Yellow pigment)
Examples of yellow pigments include C.I. I. Pigment yellow 11, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 99, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 167, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 199, and the like.
A yellow pigment may be used independently or may be used in mixture of 2 or more types.
As for content of the yellow pigment with respect to the total solid of a yellow photosensitive composition, 5-40 mass% is common, and 10-30 mass% is preferable. If it is within the preferable range, it is not difficult to control the yellow image density, so that there is no problem in suitability for production, and color reproducibility when used in a color filter is not insufficient.

(solvent)
Examples of the solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Also, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, ethyl lactate similar to Solvent described in paragraph number [0054] [0055] of US2005282073 A1 , Methyl lactate, and caprolactam can also be suitably used in the present invention.
Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate (ethylcarbyl Tall acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention.
These organic solvents may be used alone or in combination of two or more.

Moreover, the organic solvent whose boiling point is 180 to 250 degreeC can be used if needed. These high-boiling solvents include diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol diacetate, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol- n-butyl acetate, propylene glycol phenyl ether acetate Over preparative include 1,3-butanediol diacetate.
10-95 mass% is preferable with respect to the photosensitive composition whole quantity, 15-90 mass% is more preferable, and, as for content of a solvent, 20-85 mass% is especially preferable.
By setting it as the range of content of the said solvent, it is preferable at the point which can apply | coat a photosensitive composition stably.

(Alkali-soluble binder)
The yellow photosensitive composition of the present invention preferably contains an alkali-soluble binder in order to enable alkali development.
As the alkali-soluble binder (hereinafter sometimes simply referred to as “binder”) in the present invention, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer.
The binder polymer having these polar groups may be used alone or in a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the yellow photosensitive composition. The amount is generally 20 to 50% by mass, and preferably 25 to 45% by mass.

(Photopolymerization initiator or photopolymerization initiator system)
The yellow photosensitive composition of the present invention preferably contains a photopolymerization initiator or a photopolymerization initiator system.
Examples of the photopolymerization initiator or photopolymerization initiator system include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, An aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 A combination of a triarylimidazole dimer and a p-aminoketone described in the document, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, and described in US Pat. No. 4,239,850 Trihalomethyl-triazine compounds, US Pat. No. 42 And the like trihalomethyl oxadiazole compounds described in 2976 Pat. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

-Surfactant-
Conventionally used color filters have a problem that the color of each pixel becomes dark in order to achieve high color purity, and the film thickness unevenness of the pixel is recognized as color unevenness as it is. For this reason, it has been demanded to improve the film thickness variation during the formation (application) of the photosensitive layer, which directly affects the pixel film thickness.
In the color filter of the present invention or the photosensitive transfer material of the present invention, the colored photosensitive composition can be controlled to have a uniform film thickness and effectively prevent coating unevenness (color unevenness due to film thickness fluctuation). It is preferable to contain an appropriate surfactant therein.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

-Thermal polymerization inhibitor-
The yellow photosensitive composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-Supplementary dyes and pigments-
A known colorant can be added to the yellow photosensitive composition of the present invention, if necessary, in addition to the colorant (pigment) as long as the effects of the present invention are not impaired. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the yellow photosensitive composition. preferable.
Specific examples of the known colorant include color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And pigments described in JP-A-2005-17521 [0080] to [0088] can be preferably used.

-UV absorber-
The yellow photosensitive composition of this invention can contain a ultraviolet absorber as needed. Examples of the UV absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds, etc., in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like.

Moreover, in the yellow photosensitive composition of this invention, the "adhesion adjuvant" described in Unexamined-Japanese-Patent No. 11-133600, other additives, etc. other than the said additive can be contained.
The color filter production method (coating method or transfer method), the constituent material of the transfer material, the component constituting the color filter, and the liquid crystal display device in the present invention are the same as the method and components described in US2005282073 A1, Details will be described below.

<Coating film of yellow photosensitive composition>
The yellow photosensitive composition coating film of the present invention contains at least a yellow pigment, a monomer, and a yellow pigment, and preferably contains an alkali-soluble binder, a photopolymerization initiator, or a photopolymerization initiator system. It is characterized by being a coating film.
The essential components of the yellow pigment, monomer, and solvent and other components are the same as those already described in the section <Yellow photosensitive composition>.

(Slit nozzle)
In addition, although the said coating film can be formed by apply | coating and drying the yellow photosensitive composition of this invention with a well-known coating method, in this invention, it is a slit-like hole in the part which discharges a liquid. It is preferable to apply by a slit-like nozzle having Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Laid-Open Patent Publication No. 2001-310147 and the like are preferably used.
When the yellow photosensitive composition of the present invention is used for a slit coater, the viscosity of the yellow photosensitive composition is 1 mPa · s or more and 5 mPa · s or less at 25 ° C. from the viewpoint of coating fluidity and flatness. It is preferable.
When the viscosity of the composition is 1 mPa · s or more, it tends to show good coating suitability, and when it is 5 mPa · s or less, the flatness of the coating film tends to be improved.
In the present invention, the viscosity is a value obtained by measuring a sample at 25 ° C. for 1 minute using a BL adapter of a B-type viscometer (manufactured by TOKIMEC, trade name: VISCOMETER TV-20).

<Photosensitive transfer material>
Next, the photosensitive transfer material of the present invention will be described.
The photosensitive transfer material of the present invention is preferably formed using a photosensitive transfer material described in JP-A-5-72724, that is, an integral film. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / protective film are laminated in this order.
In the photosensitive transfer material of the present invention, it is essential to provide a photosensitive layer by using the above-described yellow photosensitive composition of the present invention.

(Temporary support)
In the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

(Protective film)
A thin protective film is preferably provided on the photosensitive layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the photosensitive layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

(Method for producing photosensitive transfer material)
The photosensitive transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved on a temporary support, and drying. Subsequently, a solution of an intermediate layer material composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the thermoplastic resin layer, and then the photosensitive layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. can do.
In addition, a sheet provided with a thermoplastic resin layer and an intermediate layer on the temporary support and a sheet provided with a photosensitive layer on a protective film are prepared and pasted together so that the intermediate layer and the photosensitive layer are in contact with each other. In addition, a sheet having a thermoplastic resin layer provided on the temporary support and a sheet having a photosensitive layer and an intermediate layer provided on a protective film are prepared, and the thermoplastic resin layer and the intermediate layer are prepared. It can also be produced by sticking them together so that they are in contact with each other.
In the photosensitive transfer material of the present invention, the thickness of the photosensitive layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. preferable.
Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

  The coating in the above production method can be performed by a known coating apparatus or the like, but in the present invention, the coating using the slit-shaped nozzle already described in the section <Coating film of yellow photosensitive composition>. It is preferable to use an apparatus (slit coater). Preferred specific examples of the slit coater are the same as described above.

<Color filter using coating / transfer method and method for producing color filter>
The color filter of the present invention has a yellow pixel using the yellow photosensitive composition or the photosensitive transfer material, and is formed as a coating film by coating the yellow photosensitive composition on a substrate. It is also a preferred embodiment that the yellow photosensitive composition is applied to a temporary support and formed using a photosensitive transfer material having a photosensitive layer. Details will be described below.

A general color filter is composed of three colors of red, green, and blue (R, G, B), but the color filter of the present invention is preferably composed of four color pixels of YRGB including yellow (Y), and further cyan. It is also preferable that the pixel is composed of YCRGB five-color pixels including (C), and a multicolor filter having more than that may be used.
Among these, the color filter of the present invention is preferably a color filter composed of four color pixels of YRGB in terms of improving color reproducibility.

(Photosensitive layer)
In the color filter of the present invention, each of the red (R), green (G), and blue (B) photosensitive layers other than the yellow photosensitive layer is used as a colorant. I. P. R. 254 and C.I. I. P. R. 177, the photosensitive composition used in combination with 177 or a coating film thereof; I. P. G. 36 and C.I. I. P. Y. 150, or a coating film thereof, which is used in combination with 150; I. P. B. 15: 6 and C.I. I. P. V. It is preferably formed by the photosensitive composition used in combination with No. 23 or a coating film thereof.
The photosensitive composition containing these colorants can be prepared by using the above three colorants of RGB instead of the yellow pigment contained in the yellow photosensitive composition. Moreover, you may use the said coloring agent for the coloring agent of a conventionally well-known photosensitive composition.
By satisfying the above requirements, it has good chromaticity in the F10 light source field of view of 2 degrees, and can achieve high color purity even when used in a liquid crystal display device having a large screen.

  In the color filter of the present invention, the chromaticities of all single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in Table 1 below (hereinafter referred to as the present invention). (Referred to as “target chromaticity”) in the range (ΔE) of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

Here, in the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

The color filter of the present invention can be produced by a known method such as a method in which a photosensitive layer of each color is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
In the above manufacturing method, as a method of forming the photosensitive layer of each color on the substrate, (a) a method of applying the photosensitive composition of each color with a known coating device or the like, and (b) a method of forming each color of the photosensitive layer. Examples thereof include a method of using a photosensitive transfer material and pasting with a laminator.
Hereinafter, although the yellow photosensitive composition is mainly demonstrated about the manufacturing method of a color filter, the photosensitive composition of each other color is also the same.

(A) Application by coating device In the method for producing a color filter of the present invention, a known coating device can be used for coating a colored photosensitive composition. The slit coater described in the section “Film> can be preferably used. The preferred specific example of the slit coater is the same as described above. When the photosensitive layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.0 to 2.0 μm.

(B) Affixing with a laminator The photosensitive layer formed in the form of a film using the photosensitive transfer material of the present invention is heated and / or pressed on a substrate to be described later, with a roller or a flat plate, and pressed or heated. It can be affixed by pressure bonding. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. The preferred film thickness when the photosensitive layer is formed from the photosensitive transfer material of the present invention is the same as the preferred film thickness described in the section <Photosensitive transfer material>.

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, etc. Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive composition or a photosensitive transfer material by performing a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

(Oxygen barrier membrane)
In the color filter of the present invention, when the photosensitive layer is formed by application of a colored photosensitive composition, an oxygen blocking film can be further provided on the photosensitive layer, thereby increasing the exposure sensitivity. Can do. Examples of the oxygen blocking film include those already described in the section of (Intermediate layer) of <Photosensitive transfer material>. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is arranged above the photosensitive layer formed on the substrate, and then exposure is performed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then development with a developer is performed. By repeating the process by the number of colors, the color filter of the present invention can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. The developer is preferably one in which the photosensitive layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable, but is further miscible with water. A small amount of an organic solvent having properties may be added.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used.
Here, the shower development will be described. An uncured portion can be removed by spraying a developer onto the exposed photosensitive layer by a shower. Prior to development, it is preferable to spray an alkaline solution having low solubility of the photosensitive layer with a shower or the like to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In the production of the color filter of the present invention, as described in JP-A Nos. 11-248921 and 3255107, a colored photosensitive composition for forming a color filter is layered to form a base, From the viewpoint of cost reduction, it is preferable to form a spacer by forming a transparent electrode on top of the transparent electrode and further superimposing projections for split orientation.
When the colored photosensitive composition is sequentially applied and stacked, the film thickness becomes thin each time the colored photosensitive composition is stacked due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B, and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
The size of the base is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive layer and maintaining a constant thickness when laminating the transfer material.

<Inkjet color filter and manufacturing method thereof>
The yellow photosensitive composition of the present invention is also preferably used as an inkjet ink for a color filter.
When the yellow photosensitive composition is used as the inkjet ink, the viscosity of the composition is preferably 10 to 20 mPa · s, and more preferably 12 to 18 mPa · s.
When the pressure is 10 mPa · s or more and 20 mPa · s or less, it tends to be able to discharge stably, which is preferable.
The inkjet ink for a color filter has a viscosity of 40 mPa · s or more and 4000 mPa · s at 25 ° C. with a remaining ink obtained by drying for 8 hours under conditions of 5 mmHg (0.67 kPa) and 45 ° C. with an average thickness of 1 mm. It is preferable that it is below s from the viewpoint of the flatness of the color filter.
Here, the average thickness is a thickness obtained by calculation from the container bottom area and the ink volume. Moreover, as a physical property value as ink, the surface tension at 25 ° C. is preferably 10 to 50 mN / m.

(Flowability of ink remaining)
The viscosity at 25 ° C. of the remaining ink is more preferably 50 mPa · s to 3000 mPa · s, further preferably 50 mPa · s to 2000 mPa · s, and more preferably 50 mPa · s to 1000 mPa · s. It is particularly preferred. When the viscosity of the remaining ink is within the above range, a flat pixel portion (colored layer) can be obtained even after the organic solvent is dried.

  The “ink remainder” in the present invention refers to a residue obtained by drying an inkjet ink for a color filter under conditions of 5 mmHg (0.67 kPa) and 45 ° C. for 8 hours with an average thickness of 1 mm. When measuring the viscosity of the remaining ink using a viscoelasticity measuring device, for example, the color filter inkjet ink is placed in an aluminum saucer with an average thickness of 1 mm and vacuum dried at 45 ° C. for 8 hours (0.67 kPa). ), And the resulting residue (ink residue) can be collected from an aluminum dish using a chemical sledge and used as a sample. Viscoelasticity measurement using a viscoelasticity measuring apparatus can be performed by, for example, Jasco International Co. It can be measured under the conditions of a temperature of 25 ° C. and a frequency of 1 Hz using a viscoelasticity measuring device DynAlyser DAS-100 manufactured by Ltd.

  In the method for producing a color filter of the present invention, the yellow photosensitive composition of the present invention (hereinafter referred to as “ink jet ink for color filter”, or simply “ And other ink droplets are formed to form a colored layer. When the ink for color filter is cured / dried by a heating process, the ink mass reduction rate is 5%. The heating step is terminated in a region that is less than / hr.

  The method for producing a color filter of the present invention is a step of forming a colored layer by applying the inkjet ink of the present invention described above to the recess surrounded by the partition wall by an inkjet method (hereinafter referred to as “colored layer forming step”). Preferably, the at least one colored layer formed is cured by irradiation with active energy rays, or is cured by heat after all the colored layers having a desired hue are formed. It has a curing process. In addition, the partition is formed on the substrate in advance before the colored layer forming step, and details of the method for forming the partition will be described below.

(Partition wall)
In the present invention, a colored layer is formed by applying ink-jet ink droplets to a recess surrounded by a partition formed on a substrate by an ink-jet method. The partition may be any type, but is preferably a light-blocking partition having a black matrix function. The partition walls can be produced by the same material and method as those of known black matrixes for color filters. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A No. 2006-10875.
Among the known production methods, it is preferable to use a photosensitive resin transfer material from the viewpoint of cost reduction. The photosensitive resin transfer material is provided with a photosensitive resin layer having at least a light shielding property on a temporary support, and is pressure-bonded to the substrate to transfer the photosensitive resin layer having the light shielding property to the substrate. Can do.

The photosensitive resin transfer material is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film. As an example of the structure of the integral film, a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (in the present invention, the “photosensitive resin layer” refers to a resin layer that can be cured by light irradiation, When it has light-shielding properties, it is also referred to as a “light-shielding resin layer”, and when it is colored in the desired color, it is also referred to as a “colored photosensitive resin layer”.) / A protective film is laminated in this order. It is done.
Regarding the temporary support, the thermoplastic resin layer, the intermediate layer, the protective film, and the production method of the transfer material constituting the photosensitive resin transfer material, paragraphs [0023] to [0066] of JP-A-2005-3861 Those described are preferred.

  The partition wall may be subjected to ink repellent treatment to prevent color mixing of the inkjet ink. As for the ink repellent treatment, for example, (1) a method of kneading an ink repellent substance into a partition wall (for example, see JP-A-2005-36160), and (2) a method of newly providing an ink repellent layer (for example, a special method) (See Kaihei 5-241101), (3) Method of imparting ink repellency by plasma treatment (for example, see JP-A-2002-62420), (4) Method of applying an ink-repellent material to the upper surface of the partition wall (See, for example, Japanese Patent Application Laid-Open No. 10-123500). In particular, (3) a method of performing an ink repellent treatment with plasma on a partition formed on a substrate is preferable.

-Colored layer formation process-
In the colored layer forming step, droplets of inkjet ink are applied to the recesses between the partition walls (dark color separation walls) by an inkjet method to form a colored layer. This colored layer becomes color pixels such as yellow (Y), red (R), green (G), and blue (B) constituting the color filter.
The colored layer is formed by injecting ink-jet ink for forming colored pixels (for example, YRGB four-color pixel pattern) into the recesses surrounded by the partition formed on the substrate as described above. It can be formed to include the plurality of pixels described above.
The shape of the color filter pattern is not particularly limited, and may be a general stripe shape, a lattice shape, or a delta array shape as a black matrix shape.

  As an inkjet method, a method in which charged inkjet ink is continuously ejected and controlled by an electric field, a method in which ink is intermittently ejected using a piezoelectric element, and an ink is heated and intermittently ejected using its foam. Various methods such as a method can be adopted. Details of the inkjet method are described below.

(Ink physical properties)
As the physical properties of the ink, the viscosity at 25 ° C. is 20 to 100 mPa.s. s is preferable, and when discharging with the apparatus, the ink temperature is preferably maintained at a substantially constant temperature in the range of 20 to 90 ° C., and the viscosity at that time is 2 to 20 mPa.s. It is preferable to set to s.
In particular, the yellow inkjet ink preferably has a viscosity described in the above-mentioned section “<Color filter by inkjet method and method for producing the same>”.
Further, the surface tension at 25 ° C. is preferably 10 to 50 mN / m, and when ejected by the apparatus, the ink temperature is preferably maintained at a substantially constant temperature in the range of 20 to 90 ° C., and the surface tension at that time is 20 It is preferable to set it to -30mN / m. In order to keep the ink temperature constant with a predetermined accuracy, it is preferable to have an ink temperature detecting means, an ink heating or cooling means, and a control means for controlling the heating or cooling according to the detected ink temperature. In addition, it is also preferable to have means for reducing the influence on the change in ink physical properties by controlling the energy applied to the means for ejecting ink according to the ink temperature.

  In addition, in order to keep the ink spreading properly after landing on the substrate, it is preferable to keep the ink physical properties after landing on the substrate at a predetermined level. For this purpose, the substrate or its vicinity is held within a predetermined temperature range. It is preferable to do. Alternatively, it is also effective to reduce the influence of the temperature change by increasing the heat capacity of the table that supports the substrate.

(System configuration)
An example of a system configuration for creating a color filter using the ink is shown in FIG.
Reference numeral 100 denotes a head portion, the details of which are shown in FIG. The head unit 100 includes four inkjet heads 101, 102, 103, and 104, and each ejects three colors of ink onto the substrate. The ejection of the head unit 100 is controlled by the control unit 200, and the ejected ink lands on the substrate 300 to form each pixel of YRGB. Here, the substrate 300 is placed on the substrate table 400, and the substrate table 400 is provided with a motor (not shown) for moving the substrate 300 and the substrate table 400 in the XY2 directions orthogonal to each other with respect to the head. The operation of the motor is controlled by the control unit 200, and pixels are formed in synchronization with ink ejection. The head maintenance station 500 has a mechanism for maintaining the ejection performance of the head unit 100 well.

(head)
Each of the four heads shown in FIG. 2 is supplied with Y, R, G, and B4 inks from an ink supply unit (not shown). Reference numeral 110 denotes a microscope camera, which captures an image of a partition (black matrix, BM) pattern, a positioning dedicated pattern, or ink landing on the substrate, and processes the captured image to place the ink in a desired position. The operation of the substrate base 400 is controlled so as to land.
The four ink heads 101, 102, 103, and 104 may be heads having the same configuration or may be heads having different configurations. As a configuration of the head, for example, as disclosed in Japanese Patent Laid-Open No. 5-193140, it has a portion for imparting ejection energy to ink and a nozzle portion for ejecting ink.

(Head drive system)
As a method for applying ejection energy to ink, a so-called continuous method as disclosed in Japanese Patent Laid-Open No. 7-81090 is used, and ink droplets are ejected continuously depending on whether or not they are landed. The method may be a method in which the ink is deflected and selectively controlled, or a so-called on-demand method, in which ink droplets are ejected only at necessary portions. As disclosed in JP-A-5-16349, the on-demand system may be a system that generates and discharges ink pressure by deformation of a structure using a piezoelectric element or the like. As disclosed in Japanese Patent No. 234255, a method of discharging at a pressure generated by expansion accompanying vaporization by thermal energy may be used. Further, as disclosed in Japanese Patent Laid-Open No. 2001-277466, a method of controlling ejection to a medium by an electric field may be used.

(Speeding up)
At this time, in order to eject a plurality of colors of ink, a plurality of inkjet heads 101, 102, 103, and 104 are configured integrally as described in Japanese Patent Laid-Open No. 6-71904, thereby achieving a small size and a high speed. In addition, it is possible to form a color image, and it is possible to further increase the speed by arranging a plurality of head units having a plurality of nozzle rows.
Further, by arranging the nozzles of the respective colors by a width equal to or larger than the width of the image as described in JP-A-63-160849, so-called line heads can be formed, and an image can be formed more compactly and at high speed. It becomes possible.

(nozzle)
The material of the nozzle may be a metal such as nickel or stainless steel, for example, silicon or resin. The surface of the nozzle is subjected to a surface treatment as disclosed in, for example, Japanese Patent Application Laid-Open No. 5-116327, so that the formation of ejected ink droplets can be stably maintained, and ink droplets can be prevented from adhering to the nozzle surface. It becomes possible. The process may be a process that makes the ink easily wet or a process that makes the ink difficult to wet. When the ink is easily wetted, the nozzle surface is covered with ink, so that there are advantages such as uniform ink physical properties around the nozzle portion and smooth supply of ink during high-speed ejection. On the other hand, when the treatment that makes the ink difficult to wet is performed, the adhesion of the ink to the nozzle plate is reduced, so that the problem that the adhered ink on the nozzle plate becomes an obstacle to ejection can be reduced.

(Movement control)
Regarding the relative movement of the head and the substrate, the head unit may be stationary and the substrate table may be moved as described above, or the substrate table may be stationary and the head may be moved. The relative movement of the head and the substrate is as follows. The substrate is moved in the X direction orthogonal to the nozzle row shown in FIG. 1 and discharged from the start end to the end, and then the substrate is moved by a predetermined amount in the Y direction. It may be discharged in the reverse direction from the end to the start end, or after discharging from the start end to the end, the substrate is moved from the end to the start end in the X direction without discharging ink from the head. You may make it move, discharging from the start end toward the end. Here, the discharge conditions when discharging from the start to the end, such as the relative positional relationship between the head and the substrate, the discharge timing, and the distribution of the amount of ink discharged in the pixel, are discharged in the reverse direction from the end to the start. The discharge conditions may be the same, or when the landing state is different in the opposite direction, the discharge conditions may be set differently to reduce this.
In addition, one substrate 300 may be divided into a plurality of regions and discharged while performing the movement control in each region, or one substrate may be discharged as one region.

(Substrate replacement)
After the discharge onto one substrate 300 is completed, the substrate on which ink has landed is discharged from the substrate table 400 by a mechanism (not shown), and the substrate on which ink has not landed is newly placed on the substrate table 400. Repeat the same control.
Here, it is not necessary to eject ink from the head while discharging and placing the substrate. However, if the ejection is not stopped, the ink on the nozzle surface of the head is dried during this period, and the nozzle portion An increase in the viscosity of the ink can be prevented. As a result, when starting to discharge onto a new substrate, the amount of ink at the initial stage of discharge is reduced or the discharge speed is reduced, so that the delay time until the ink is discharged after the head is driven increases. It is possible to prevent the landing positions of the ink droplets from deviating by the moving distance between the head and the substrate. Also, the behavior of the meniscus when discharging after a pause changes with changes in physical properties, and it is prevented that air is sucked into the head from outside the nozzle by excessively retreating to the inside of the nozzle, and this becomes an obstacle to subsequent discharge. Can do.

(Flushing)
Specifically, the flushing performs ink ejection that does not contribute to pixel formation when the head is located outside the pixel portion on the substrate, as disclosed in JP-A-11-157102, during the pause, Fresh ink is supplied to the nozzle surface to prevent adverse effects due to changes in viscosity and the like, and to maintain a stable meniscus. This ejection may be performed on the substrate, or the head unit 100 may be moved to the head maintenance station 500 shown in FIG. Here, the amount of ink to be ejected is preferably a small amount within a range in which the ink physical properties are recovered to the same level as the initial state, in order to reduce waste of ink.
As the means for ejecting ink, it is possible to eject by ejecting ejection energy applying means for forming pixels, or by applying pressure to the ink in the head from the ink supply side. Is possible.

(Capping)
During the pause, as disclosed in JP-A-11-138830, the nozzle surface is substantially sealed with a cap to reduce the vapor pressure of the low boiling point component of the ink and delay drying. This can reduce the above-mentioned adverse effects. Alternatively, in the head maintenance station 500, the change in physical properties due to drying can be reduced by immersing the nozzle surface in an ink reservoir (not shown).
It is more effective to use a combination of such ink discharge and substantially sealing or dipping in ink.

(Wiping)
The above-described treatment on the nozzle surface can reduce the adhesion of the ink to the nozzle surface. However, if the ink is deposited for a long time or a large amount of ejection within a short time, the ink may adhere. As disclosed in JP-A-6-71904 in the station 500, it is preferable to perform appropriate wiping with a blade.

(Non-discharge detection)
Further, in the head maintenance station 500, whether or not discharge is properly performed from each nozzle is inspected by means disclosed in, for example, Japanese Patent Laid-Open No. 2000-343686, and there is a nozzle that does not discharge. It is effective to take action.
In addition to cleaning with the blade, as a measure for the nozzle that does not discharge, as disclosed in JP-A-6-71904, ink is sucked from the outside of the nozzle plate, and ink near the meniscus whose ink properties have changed, and It is effective to discharge bubbles in the head.
As a cause of the generation of bubbles in the head, in addition to the case of sucking outside air due to insufficient meniscus formation as described above, the gas contained in the ink, particularly air, is caused by the pressure fluctuation of the ink in the head. , May grow into bubbles. As means for preventing this, it is effective to contain a defoaming agent as disclosed in, for example, JP-A-8-34943 in the ink.
It is also effective to supply the ink after defoaming as disclosed in JP-A-2000-251689 and JP-A-2002-45608. As the defoaming means, as disclosed in JP-A-9-286743, means for applying ultrasonic waves, means for vacuum defoaming, and means for using these in combination are preferable. Further, as disclosed in JP-A-8-506540, it is more effective to provide means for sucking and degassing the gas dissolved in the ink in the ink flow path near the head.

(Ink holding means)
As a means for holding the ink, a method of maintaining the ink surface at a predetermined height with respect to the nozzle surface while communicating with the atmosphere or a method of filling a known ink cartridge is preferable. It is also possible to store in a deformable container and form a tank. Further, by providing a sub-tank as disclosed in JP-A-5-16382, the supply of ink to the head is further stabilized. Further, as disclosed in JP-A-8-174860, it is also possible to use a cartridge that supplies ink by moving a valve when the pressure in the ink supply chamber decreases.

(Ink supply path)
As a method of supplying ink from these ink holding means to the head, a method of directly connecting the holding means to the head unit or a method of connecting by a flow path such as a tube may be used. The ink holding means and the flow path are preferably made of a material having good wettability with respect to the ink or subjected to a surface treatment. When the wettability is not good, a portion that does not get wet with ink occurs in the tube, and the ink supply to the head is slowed down, or bubbles easily adhere to the inner wall of the tube.

(filter)
During ink storage, if the color material dispersed in the ink agglomerates and grows large, or if dust is mixed, large solids in the ink will inhibit ejection inside the head, especially near the nozzles. To do. In order to prevent this, it is preferable to install a filter for trapping solid matter in the flow path from the ink holding portion to the head, and the pore diameter of the filter is preferably 0.1 to 20 μm. .

(Negative pressure)
Here, in order to properly maintain the meniscus shape due to the surface tension of the ink at the nozzle, it is necessary to maintain the ink pressure negative in the range of −1 to −3000 Pa.
As a method of applying a negative pressure to the ink by these ink holding means, a method of managing the height of the ink holding means, that is, a method based on a water head pressure difference, a method based on a capillary force of a filter provided in the ink flow path, or A method of controlling the pressure with a pump or the like, and a method of holding the ink on the ink absorber and applying a negative pressure by this capillary force as disclosed in Japanese Patent Application Laid-Open No. 50-74341 can be applied.

(Discharge condition)
The higher the ink ejection from the head unit 100, the more ink can be ejected per unit time, and the productivity of the color filter can be improved. Here, in order to stably discharge ink at a high frequency, the supply of ink is stable, the shape of the meniscus is stable, the discharge shape of the ink droplets from the nozzle, and the discharge amount are stable. is required.
In order to stabilize the supply of ink, it is effective to improve the wettability of the supply path to ink as described above and to reduce the flow path resistance of the supply path. Further, in order for the meniscus shape, the ink droplet discharge shape, and the discharge amount to be stable, it is necessary to optimize the driving conditions of the head at the driving frequency.

To determine the optimal drive conditions, follow the procedure below.
Hereinafter, an example of an on-demand method using a piezo will be described, but the same method can be applied regardless of whether it is a thermal drive method or an electrostatic method.
The stability of the meniscus shape and the ejection shape determines the driving conditions for observing the shape of the flying droplet and obtaining a stable shape. FIG. 3 shows the simplest voltage waveform for driving the piezo element. V _p is the piezo voltage, t _p is the driving time duration, t _f, t _r is the rise of each driving waveform, a fall time, may control the four each, and simplified manner V _p it may control two of _{t p} or _t r + _{t p.} While changing these parameters, observe the shape of the flying droplets and evaluate the stability. Here, a simple trapezoidal drive waveform is shown. However, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 10-235859 and 2003-34148, the discharge amount and the like can be controlled better by further changing the waveform shape. Is also possible.
The shape of the flying droplet can be observed with the configuration shown in FIG. The timing controller 600 generates a piezo drive waveform according to the input ejection frequency f604 and the piezo voltage Vp602 piezo drive time width tp603, and the head 640 is driven by the piezo waveform generator circuit 610.

Ink droplets are ejected from the head, but the portion where the ink flies is illuminated by the LED 650. Here, the timing at which the LED is turned on is determined by the delay amount 621 input to the variable delay circuit 620 after the piezo waveform is generated. Since the LED 650 is turned on by the LED lighting circuit 630 after a predetermined time is delayed from the piezo drive waveform according to the delay amount, the shape of the ink droplet ejected from the nozzle and flying is photographed by the CCD camera 661 equipped with the microscope lens 660. Can be observed with a monitor 670. It is possible to determine Vp and tp while observing the monitor so that the droplet shape thus observed is stable even at a high frequency. Here, “stable as a droplet shape” means a state in which images when a plurality of droplets are sequentially imaged on a monitor are stable without shaking, and no minute droplets of ink called satellites are generated. Furthermore, the closer the shape after the time to reach the substrate after ejection is closer to a sphere, the closer the landing shape on the substrate is to a circle, and the better the ink amount distribution in the pixel can be controlled.
Next, in order to confirm that the discharge amount is stable, the discharge amount is measured by the following method. In the configuration of FIG. 4, ink is ejected from a predetermined nozzle of the head 640 for a predetermined time, and the discharged ink is supplemented and the weight is measured. By dividing this by ejection time × frequency × number of nozzles, the amount of ink ejected at one time from one nozzle can be determined. It is determined whether or not the ejection ink amount thus obtained is within a specified range.
Here, in the case of a head having a plurality of nozzles and the discharge amount for each nozzle is not uniform, the energy of the discharge energy driving means can be individually controlled to make the discharge amount uniform for each nozzle. preferable.

(Head substrate gap)
Even if the shape of the ink discharged from the head unit 100 is stable and the discharge amount is stable, good pixels cannot be formed unless the accuracy of the landing position on the substrate is high. In order to maintain the landing position accuracy satisfactorily, it is important that the minute scattered droplets are not generated and that the ejection direction from the nozzle is stable. The accuracy of the ejection direction from the nozzle is dominated by the accuracy of the work of the nozzle shape, the ink physical property stability of the meniscus portion, and the nozzle surface being soiled. In order to maintain the ink properties of the meniscus stably, it is effective to purge the ink whose viscosity has been increased as described above and replace it with fresh ink, and cleaning with a blade or the like is effective to clean the nozzle surface. It is.
Further, when the error in the ink ejection direction is a predetermined amount, the landing position accuracy on the substrate can be increased by reducing the distance between the head unit 100 and the substrate 300.

The distance between the head and the substrate can be reduced as the flatness of the nozzle surface of the head, the flatness of the substrate 300 and the substrate table 400 on which the substrate 300 is placed, and the linearity of the substrate table moving mechanism (not shown) are improved. In general, the distance between the nozzle surface and the substrate surface is preferably 200 to 2000 μm from these mechanical precisions.
Here, when the unevenness of the substrate is gentle, the head unit 100 is provided with means for detecting the distance from the substrate, such as a laser length meter (not shown), and drives the head unit height control means (not shown). Therefore, it is possible to further reduce the height by controlling the height in order to keep the distance between the substrate and the head at a predetermined amount according to the unevenness during the movement of the substrate, and the distance detection means and the height control means When the follow-up speed is sufficiently high, it can be made 100 μm or less.

(Nozzle diameter / interval, pixel shape)
The ink landing diameter on the substrate 300 is preferably between 10 and 500 μm, and the landing diameter is determined by the size of the ink droplet and the wettability of the ink to the substrate. The contact angle of the ink droplet to the substrate is preferably 0 to 80 degrees, and the diameter of the flying ink droplet is preferably 5 to 250 μm, and the nozzle diameter at this time is preferably 15 to 100 μm. Here, the contact angle of the ink droplets with respect to the substrate was determined by dropping about 2 μl of ink onto the glass surface subjected to plasma treatment on which no BM was formed using a DropMaster 700 manufactured by Kyowa Interface Science, and a droplet shape image after 500 msec. Can be measured by the θ / 2 method.
When the period of the pixels in the nozzle row direction and the interval between the nozzles are an integer multiple, it is possible to form the pixels by making the nozzle row direction of the head and the substrate moving direction orthogonal to each other. Is not an integral multiple, the nozzle row direction is set to an angle other than 90 degrees with respect to the substrate movement direction as disclosed in Japanese Patent Laid-Open No. 9-300664, and apparently in the substrate movement direction. It is possible to land on the pixels by changing the nozzle row interval. At this time, the discharge control from each nozzle needs to correct the discharge timing corresponding to the angle. In addition, as disclosed in Japanese Patent Laid-Open No. 2000-89020, it is possible to reduce the variation in the discharge amount between nozzles by ejecting droplets using different nozzles.

(Ink amount)
The shape of the pixel formed by the partition wall on the substrate is not limited, but if the longitudinal direction of the pixel is the X direction in which the substrate is scanned at high speed, ink ejection can be continued in the longitudinal direction. Therefore, it is preferable.
The amount of ink to be landed on the substrate is determined from the concentration of the colorant contained in the ink and the amount of colorant necessary to ensure the performance of the color filter. Usually, the colorant concentration in the ink solids (the ink remainder) is about 20 to 70% by mass, and the color material amount required on the filter is about 0.5 to 5.0 g / m ^2. The ink landing amount in the pixel is preferably 1 to 30 g / m ² .

  If the amount of landing fluctuation for each pixel is small, uneven density is unlikely to occur, and it is possible to prevent a decrease in transmission density in a portion where the amount of landing is small due to fluctuation in the amount of landing within the pixel, thereby preventing a reduction in filter performance. . In addition, if the amount of ink in the pixel is uniform, it is difficult to cause a failure in a subsequent process. Therefore, the uniformity of the height in the pixel after the ink is landed and heat-treated is preferably 50% or less. .

(Landing position)
In order to make the landing amount uniform within the pixel, it is preferable that the amount of ink uniformly spreads to the end of the pixel and that the distribution of the ink amount after the wet spreading is uniform. For this purpose, it is preferable to land a large number of small droplets uniformly within a pixel, but the size of a small droplet that can be realized is about 1.5 ng / droplet, and it is necessary to land a large number of droplets at high speed. The discharge frequency is preferably about 20 KHz. In order to make a large number of droplets uniformly land within a pixel, if the landing position accuracy is particularly good at the periphery of the pixel, there are obstacles such as ink landing on the partition wall and further flowing into adjacent pixels. Is less likely to occur. For this reason, it is effective to increase the landing position accuracy by reducing the distance between the nozzle and the substrate as described above.
In addition, when sequentially landing while moving the substrate, as shown in FIG. 5, the surface area of the combined ink is reduced by the surface tension when the previously landed ink and the ink droplet landed later are merged. A force is applied, and a phenomenon occurs in which an ink droplet ejected later is drawn closer to the preceding landing ink side than the position where the ink droplet should land. It is preferable to set the landing position appropriately in consideration of this phenomenon.
On the other hand, when the wettability of the ink on the substrate is good, that is, when the contact angle of the ink to the substrate is small, the necessary ink amount may be concentrated and landed near the center of the pixel.

  The color filter in the present invention is preferably in the form of a group consisting of at least three colored layers by spraying at least three colors of ink such as RGB.

In the present invention, after droplet ejection, the solvent contained in the droplet is removed to form an ink residue, and then the ink residue is heated to cure the ink residue to form a colored layer (so-called baking treatment). This heating process can be performed in one stage or in multiple stages.
The heating in one stage is by heating at a predetermined temperature that completely cures the ink from the beginning after removing the solvent, and the heating in the multi-stage is started at a relatively low temperature at first, and the heating temperature is sequentially increased. Is heated at a predetermined temperature to finally cure the ink completely. Examples of the heating method include, but are not limited to, heating with a hot plate, an electric furnace, a dryer, or the like, or heating by irradiating infrared rays.
Before the heating step, a step of irradiating the remaining ink with active energy rays to cure the ink may be performed.

  The heating temperature and heating time in the heating step depend on the composition of the inkjet ink and the thickness of the colored layer, but generally from about 120 ° C. to about 250 ° C. from the viewpoint of ensuring sufficient pixel strength, solvent resistance, alkali resistance, and the like. It is preferable to heat at about 10 minutes to about 120 minutes.

The method for producing a color filter of the present invention is to end the heating step in a region where the ink mass reduction rate is 5% / hr or less when the inkjet ink for color filter is cured / dried by the heating step. It is preferable to end the heating step in a region that is 3% / hr or less, and it is most preferable to end the heating step in a region that is 2% / hr or less. The ink mass reduction rate at the end of the heating process is ideally 0% / hr.
When the ink mass reduction rate at the end of the heating step is within this range, the flatness within the pixel is good.

  Here, the ink mass reduction rate is a measurement of a change in mass of ink used for manufacturing a color filter at a set temperature in a heating process using a TG (thermogravimetric analyzer). It can be determined as a mass reduction rate (%) per unit time (h). For example, when the heating process is 230 ° C. for 2 hours, the mass change when the temperature is set to 230 ° C. by TG is measured, and the mass decrease at the end of the heating process is obtained with the differential value of the mass decrease after 2 hours. Rate (% / hr). Even when the temperature condition is changed on the way, it is possible to obtain the mass reduction rate at the end of the heating process by measuring the mass change by TG under the same temperature condition as the heating process.

  In the method for producing a color filter of the present invention, the colored layer forming step to the heating step is preferably performed within 24 hours, more preferably within 12 hours, and even more preferably within 6 hours. . After the colored layer is formed, it is preferable not to leave for a long time until the final curing step (heating step), because it is less likely to cause aggregation of pigments and precipitation of various binders in the ink, and the surface state of the pixel is less likely to deteriorate. .

  After forming the color filter by forming the colored region (colored pixel) and the partition as described above, an overcoat layer can be formed to cover the entire surface of the colored region and the partition for the purpose of improving the durability. .

The overcoat layer can protect the colored regions such as R, G, and B and the partition walls and can flatten the surface. However, it is preferable not to provide from the point which the number of processes increases.
An overcoat layer can be comprised using resin (OC agent), and acrylic resin composition, an epoxy resin composition, a polyimide resin composition etc. are mentioned as resin (OC agent). Among them, the acrylic resin composition is desirable because it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin and has excellent adhesion. . Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and commercially available overcoat agents such as Optomer SS6699G manufactured by JSR.

  The color filter of the present invention is produced by the above-described method for producing the color filter of the present invention, and includes, for example, a portable terminal such as a television, a personal computer, a liquid crystal projector, a game machine, a mobile phone, a digital camera, and a car navigation system. It can be suitably applied to applications such as without particular limitation. In the color filter of the present invention, at least one of color pixels such as red (R), green (G), blue (B), white (W), and purple (V) is formed by the method for producing a color filter of the present invention. It only has to be done.

<Liquid crystal display device>
The liquid crystal display device of the present invention is characterized by using the color filter of the present invention having good chromaticity in an F10 light source field of view of 2 degrees, thereby realizing high color purity and coating unevenness (due to film thickness variation). Color unevenness) can be effectively prevented, and it can be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor.

  The present invention will be described below in more detail based on examples, but the present invention is not limited thereto. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the mass average molecular weight.

[Example 1] Pixel formation using a slit coater (Preparation of salt milled yellow pigment)
Oven kneader (manufactured by Moriyama Seisakusho, trade name S1-1) containing 500 g of sodium chloride, 5 g of hydrogenated rosin ester (trade name: Ester Gum HP, manufactured by Arakawa Chemical Co., Ltd.), 50 g of yellow pigment described in Table 4, and 300 g of polyethylene glycol. Kneaded for the time described in Table 4 (time described in the column of salt milling). The kneaded product was poured into 2 liters of warm water and stirred vigorously at about 70 ° C. with a dissolver for 2 hours. Thereafter, the obtained dispersion is filtered, and the residue on the filter is washed with water to remove sodium chloride and polyethylene glycol, followed by drying in a dry oven at about 40 ° C. for 2 days to obtain a salt milled yellow pigment. It was.

(Preparation of yellow pigment dispersion composition by bead dispersion treatment)
Next, the components in Table 2 below were dispersed with a motor mill M-50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 2 hours to prepare a yellow pigment dispersion composition.

(Preparation of yellow photosensitive composition: slit coater coating solution)
A yellow photosensitive composition was prepared by mixing the formulations shown in Table 3 below.

(Examples 2-6, Comparative Examples 1-3)
In Example 1, a yellow photosensitive composition was prepared in the same manner as in Example 1 except that the yellow pigment species and the salt milling treatment time were changed as shown in Table 4 below.

[Evaluation]
<Measurement of coating solution viscosity>
The viscosity was measured for 1 minute using a BL adapter using a B-type viscometer (manufactured by TOKIMEC, trade name: VISCOMETER TV-20), and the value was determined.

<Measurement of contrast coefficient>
A non-alkali glass substrate having a size of 550 × 650 mm was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a yellow pixel produced in Examples and Comparative Examples using a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) equipped with a slit nozzle. The forming composition was applied so that the dry film thickness was 2.0 μm, and dried at 100 ° C. for 3 minutes to produce a contrast coefficient measuring glass substrate on which a photosensitive layer having a thickness of 2 μm was formed. Thus, the contrast coefficient was measured.
Using a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) as a backlight unit and using a diffusion plate, a contrast coefficient between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) Contrast by dividing the Y value of the chromaticity of light that passes when the glass substrate for evaluation is installed and the polarizing plate is installed in parallel Nicol by the Y value of the chromaticity of light that passes when installed in crossed Nicols Asked. A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity.
Two polarizing plates, a glass substrate, and a color luminance meter were installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, and a cylinder 11 mm in diameter and 20 mm in length. Light was irradiated to a measurement sample installed at a position of 65 mm, and the transmitted light was measured with a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed. The results are shown in Table 4.

<Measurement of number average particle diameter of yellow pigment in yellow photosensitive composition>
The number average particle diameter of the pigment in the yellow photosensitive composition was measured using 100 FE-SEM (F-900 manufactured by Hitachi, Ltd.) (magnification is 30000 times) in each photographed image. The salt diameter equal to this was determined, and this was determined as the particle diameter. The diameters obtained for 100 particles were averaged to obtain the average particle diameter (average diameter) of the particles.

<Evaluation of coating stability>
As an index of manufacturing stability, the number of sheets that can be applied without cleaning the slit nozzle was measured and evaluated according to the following criteria.
Note that the number of sheets that can be applied is the number of sheets that can be applied without application failure such as streaks or running out of liquid.
(Evaluation criteria)
A: 4 or more B: 2-3 sheets C: Less than 2 sheets

(Example 7)
(Preparation of yellow pigment dispersion)
In Example 1, a yellow pigment dispersion was produced in the same manner as in Example 1 except that the yellow pigment type and the salt milling treatment time were changed as shown in Table 6.

(Yellow photosensitive composition: inkjet ink)
Next, a yellow photosensitive composition (inkjet ink (hereinafter simply referred to as “yellow ink”)) having the formulation shown in Table 5 below was prepared.

(Examples 8-12, Comparative Examples 4-6)
In Example 7, a yellow photosensitive composition was produced in the same manner as in Example 7 except that the yellow pigment type and the salt milling treatment time were changed as shown in Table 6. The number average particle diameter of the yellow pigment in the ink was measured by the same method as in Example 1.

[Evaluation]
The coating solution viscosity and the contrast coefficient were measured by the same method as in Example 1, and the discharge stability was measured by the following method and evaluated. The results are shown in Table 6.

<Evaluation of ejection stability>
As an index of production stability, ink ejection stability was performed according to the following criteria.
The ejection was performed continuously for 10 minutes, and the ink was ejected onto plain paper of 150 mm × 200 mm at the beginning and 10 minutes after the ejection, thereby confirming the stable ejection visually.
(Evaluation criteria)
A No nozzle discharge failure from beginning to end.
B: Disturbance occurred in the droplet ejection position with either nozzle.
C Discharge failure due to clogging occurred in any nozzle.

-Yellow pixel formation for evaluation by inkjet method-
The yellow photosensitive composition obtained above was used below as an inkjet ink.
The head unit 100 shown in FIG. 1 includes a Dimatix SX-3 as an inkjet head, and the ejection control device 200 uses a dedicated piezo drive circuit and a stage control dedicated circuit. SX-3 is an on-demand type piezo-drive head, and 128 nozzles are arranged in one head at intervals of 508 μm.
When driving the piezo, the central value of the voltage is 50 V, the pulse width is 8 microseconds, and the nozzles are set so that the difference in the discharge amount from each nozzle is within 2% by the above-mentioned flight shape observation and discharge amount measurement. Each voltage was adjusted.
The central value of the discharge amount was 8 ng / droplet.

The substrate table 400 on which the plain paper is placed is an aluminum plate placed on a dedicated automatic two-dimensional moving stage, and is fixed to the moving stage.
The distance between the head and the plain paper was adjusted to 500 μm, and the time from when the piezo of the head was driven until ink droplets were formed and landed on the plain paper was about 63 μsec.
The driving frequency of the piezo for continuous droplet ejection was set to 10 KHz, and the substrate was moved at a constant speed of 1 m / second to continuously deposit droplets on the plain paper.

(Example 13)
(Production of color filters and liquid crystal display devices)
A KRGB colored photosensitive composition was prepared in the same manner as Example 3 described in [0125] to [0164] of US2005282073 A1.
Next, except that the yellow photosensitive composition prepared in Examples 1 to 6 was added, the color filter 1 to 4 including YRGB four-color pixels and a black matrix was used in the same manner as the color filter manufacturing method of the publication. 6 was produced.

An ITO (Indium Tin Oxide) transparent electrode was further formed by sputtering on the Y pixel, R pixel, G pixel, B pixel, and black matrix of the color filters 1 to 6 obtained above. Separately, a glass substrate was prepared as a counter substrate, and an ITO transparent electrode was similarly formed by sputtering. Then, a photo spacer was provided in a portion corresponding to the upper part of the black matrix on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, the liquid crystal display devices 1 to 6 of Examples were configured by disposing a backlight of a cold cathode tube on the side to be the back surface of the liquid crystal cell provided with the polarizing plate.

(Example 14)
(Preparation of color filter by ink jet method and preparation of liquid crystal display device)
[Preparation of dark color composition for barrier rib formation]
In the dark color composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 7 are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. However, the amounts of methyl ethyl ketone, cyclohexanone, binder 1, phenothiazine, DPHA solution, 2,4-bis (trichloromethyl) -6- [4′-N, N-bis (ethoxycarbonylmethyl) amino- described in Table 7 3′-Bromophenyl] -s-triazine and Surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Obtained by. In addition, the quantity of Table 7 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (compound 1) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The above structure 1 30%
・ Methyl ethyl ketone 70%

(Formation of partition walls)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a dark color prepared as described above with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum dryer, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer. A composition layer K1 was obtained.

With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and dark color The distance between the composition layers K1 was set to 200 μm, and pattern exposure was performed in a nitrogen atmosphere with an exposure amount of 100 mJ / cm ² to a partition wall width of 20 μm and a space width of 100 μm.

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color composition layer K1, and then a KOH developer (containing a nonionic surfactant, trade names: CDK-1, Fuji Film). Electronics Materials Co., Ltd. 100-fold diluted) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post-exposure was performed from above at an exposure amount of 2500 mJ / cm ^{2 in} the atmosphere. After heating at 240 ° C. for 50 minutes, a stripe-shaped partition wall having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm was obtained.

[Ink repellent plasma treatment]
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
(conditions)
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

-Preparation of pigment dispersion-
Brominated phthalocyanine green (CI Pigment Green 36, trade name: Rionol Green 6YK, manufactured by Toyo Ink Manufacturing Co., Ltd.) with a dispersant (the above compound 1) and a solvent (1,3-butanediol diacetate) “1,3-BGDA” was abbreviated as shown in Table 8 below and premixed. Then, using a motor mill M-50 (manufactured by Eiger Japan), zirconia beads having a diameter of 0.65 mm were used at a filling rate of 80%, and dispersed at a peripheral speed of 9 m / s for 25 hours, and a pigment dispersion for G (G1) Was prepared.
In the G pigment dispersion (G1), the G pigment dispersion (G2) and R were used in the same manner as the G pigment dispersion (G1) except that the pigment and other components were blended as shown in Table 8. Pigment dispersions (R1), (R2), and pigment dispersions for B (B1), (B2) were prepared.
The number average particle size of the pigment dispersion was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

-Preparation of monomer solution and inkjet ink-
Next, as shown in the following Table 9, the solvent, the monomer and the surfactant component were mixed and stirred at 25 ° C. for 30 minutes. After confirming that there was no insoluble matter, a monomer solution was prepared.
Next, while stirring the pigment dispersion liquid for G (G1) and the pigment dispersion liquid for G (G2), the monomer liquid is slowly added and stirred at 25 ° C. for 30 minutes. 1) was prepared.
In the same manner as described above, each color ink was prepared for the inkjet ink for R (ink R-1) and the inkjet ink for B (ink B-1).

Details of the materials used are shown.
・ C. I. P. R. 254 (Brand name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ C. I. P. R. 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ C. I. P. Y. 150 (Brand name: Bayplast Yellow 5GN 01, manufactured by Bayer Corporation)
・ C. I. P. B. 15: 6 (trade name: Rionol Blue ES, manufactured by Toyo Ink Manufacturing Co., Ltd.)
・ C. I. P. V. 23 (Product name: Hostaperm Violet RL-NF, manufactured by Clariant Japan Co., Ltd.)
1,3-BGDA (1,3-butanediol diacetate; boiling point 232 ° C.)
・ DPHA (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA),
Surfactant: Structure 1 shown in the above-mentioned surfactant 1 column

(Formation of pixel part by inkjet method)
Using the ink sets R-1, G-1, and B-1 prepared above and the yellow photosensitive compositions (Y-1 to Y-6) prepared in Examples 7 to 12, ink ejection was performed as follows. It was done in the form of
The head unit 100 shown in FIG. 1 includes four SX-3s manufactured by Dimatix as four-color inkjet heads, and the ejection control device 200 uses a dedicated piezo drive circuit and a dedicated stage control circuit. SX-3 is an on-demand type piezo-drive head, and 128 nozzles are arranged in one head at intervals of 508 μm. When driving the piezo, the central value of the voltage is 50 V, the pulse width is 8 microseconds, and the nozzles are set so that the difference in the discharge amount from each nozzle is within 2% by the above-mentioned flight shape observation and discharge amount measurement. Each voltage was adjusted.
The central value of the discharge amount was 8 ng / droplet.

A substrate table 400 on which a substrate manufactured in the above process (a substrate on which a partition wall that has been subjected to ink-repellent plasma treatment) is placed is an aluminum plate placed on a dedicated automatic two-dimensional moving stage, and is a moving stage. It is fixed to.
The distance between the head and the substrate was adjusted to 500 μm, and the time from when the piezo of the head was driven until ink droplets were formed and landed on the substrate was about 63 μs.
The size of the pixel on the substrate is 300 μm in the X direction and 100 μm in the Y direction. By tilting the head 53.8 degrees with respect to the X direction, the apparent nozzle interval in the Y direction becomes 300 μm. Adjusted.
The driving frequency for continuous ejection of the piezo was set to 10 KHz, and the substrate was moved at a constant speed of 8.2 cm / second to eject 264 ng of 33 droplets within a section of 270 μm in the X direction of the pixel.

  Curing was performed by heating and drying on a hot plate at 100 ° C. for 2 minutes, followed by baking in an oven at 230 ° C. for 90 minutes to completely cure both the partition walls and the pixels, thereby producing color filters 7 to 12.

(Production of display device)
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the Y pixel, R pixel, G pixel, B pixel and partition walls of the color filter (substrate) obtained above. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.
A photo spacer was provided in a portion corresponding to the upper part of the partition wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
Then, a UV curable resin sealant is applied to the position corresponding to the outer wall of the partition wall surrounding the pixel group of the color filter by a dispenser method, and the PVA mode liquid crystal is dropped and bonded to the counter substrate. Thereafter, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealing agent. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, liquid crystal display devices 7 to 12 of Examples, each having a cold cathode tube backlight arranged on the back side of the liquid crystal cell provided with the polarizing plate, were obtained.

  The liquid crystal display devices 1 to 12 all showed good display characteristics.

It is a figure which shows an example of the system configuration | structure which produces a color filter. It is a figure which shows the detail of a head part. It is a figure which shows the simplest voltage waveform which drives a piezoelectric element. It is a figure which shows the structure for observing the shape of the flying droplet. It is a figure which shows the shape of an ink drop when an ink drop is made to land one by one.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Head part 200 Control part 300 Substrate 400 Substrate stand 500 Head maintenance station

Claims (6)

A yellow photosensitive composition for a color filter, comprising (A) a yellow pigment, (B) a monomer, and (C) a solvent, wherein the contrast coefficient is 1000 or more and 20000 or less. 2. The yellow photosensitive composition for a color filter according to claim 1, having a viscosity at 25 ° C. of 10 mPa · s to 20 mPa · s and for inkjet. 2. The yellow photosensitive composition for a color filter according to claim 1, which has a viscosity of 1 to 5 mPa · s at 25 ° C. and is used for a slit coater. The photosensitive transfer material which provided the photosensitive layer on the temporary support body using the yellow photosensitive composition for color filters of any one of Claims 1-3. The color filter formed using the yellow photosensitive composition for color filters of any one of Claims 1-3, or the photosensitive transfer material of Claim 4. A liquid crystal display device comprising the color filter according to claim 5.

Images