KR20120112154A - Process for forming pixel pattern, color filter and display device - Google Patents

Abstract

PURPOSE: A method for forming a pixel pattern, a color filter, and a display device are provided to sufficiently make superior chromaticity of a dye and a lake pigment when the dye or the lake pigment is used as a coloring agent. CONSTITUTION: A conductive film of a colored radiation-sensitive composition of at least one type is formed on a substrate. The one type is selected from a group made of a dye or a lake pigment. A radiation is irradiated to at least one portion of the conductive film. The spectral distribution of the radiation has peaks whose ranges are 350nm to 450nm. The maximum strength under a 350nm radiation is under 50% of the maximum peak strength from 350nm to 450nm. [Reference numerals] (AA) Light relative intensity(%); (BB) Wavelength(nm)

Description

Formation method of pixel pattern, color filter and display element {PROCESS FOR FORMING PIXEL PATTERN, COLOR FILTER AND DISPLAY DEVICE}

The present invention relates to a method of forming a pixel pattern, a color filter manufactured by the method, and a display element comprising the color filter.

The color filter transmits light of a specific wavelength region in the visible light, thereby producing colored transmitted light. The liquid crystal display element using the liquid crystal cannot itself develop color, but can function as a color liquid crystal display element by using a color filter. The color filter is also used for color display such as an organic EL (Electro Luminescence) device using an white light emitting layer or an electronic paper. In addition, the color filter enables color imaging of solid-state imaging devices such as CCD image sensors and CMOS image sensors.

The following are known as a manufacturing method of a color filter. For example, a coloring radiation sensitive composition is apply | coated as a coloring composition which responds to a suitable irradiation line on the transparent substrate or the transparent substrate in which the light shielding layer of the desired pattern was formed. Subsequently, after drying a coating film, radiation is irradiated to a dry coating film through a mask (henceforth "exposure"), and a developing process is performed. Thereby, it is the method of obtaining the pixel of each color (for example, refer patent document 1 and 2.). Moreover, the method etc. which obtain the pixel of each color by the inkjet system using a colored curable resin composition are also known (for example, refer patent document 3).

By the way, in order to implement | achieve high brightness of a display element, high color purity, or high definition of a solid-state image sensor, it is known that it is effective to use dye and a lake pigment as a coloring agent (for example, refer patent document 4 and 5).

Japanese Patent Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Laid-Open No. 2000-310706 Japanese Patent Laid-Open No. 2008-304766 Japanese Patent Laid-Open No. 2001-081348

However, the colored radiation-sensitive composition containing a dye or a lake pigment is significantly inferior in process stability to chromaticity characteristics as compared to the colored radiation-sensitive composition containing only a pigment. For this reason, even if dye or a lake pigment is used as a coloring agent, there exists a problem that the color filter which has an advantage in chromaticity characteristic with respect to a pigment is hard to be obtained eventually.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a method of forming a pixel pattern, a color filter formed by the method, and the color filter in order to sufficiently express the excellent chromaticity characteristics of the dye or the lake pigment when a dye or a lake pigment is used as the colorant. It is an object to provide a display element excellent in chromaticity characteristics.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, it discovered that the said subject can be solved by using specific ultraviolet-ray as exposure radiation when forming a pixel pattern.

That is, this invention is a process of (1) forming the coating film of the colored radiation-sensitive composition containing at least 1 sort (s) chosen from the group which consists of a dye and a rake pigment on a board | substrate, and (2) at least one part of the said coating film Irradiating the radiation, wherein the spectral distribution of the radiation has a plurality of peaks in the range of 350 nm to 450 nm, and the maximum intensity at less than 350 nm of the radiation is the maximum peak intensity at 350 nm to 450 nm. It is to provide a method for forming a pixel pattern, characterized in that 50% or less. In addition, hereinafter, "the radiation having a spectral distribution having a plurality of peaks in the range of 350 nm to 450 nm, and the maximum intensity at less than 350 nm is 50% or less of the maximum peak intensity at 350 nm to 450 nm" is referred to as "specific radiation. Also called.

Moreover, this invention provides the color filter which comprises the pixel pattern formed by the said method, and the display element provided with the said color filter.

According to the present invention, when a dye or a lake pigment is used as a colorant, a color filter can be produced in which the excellent chromaticity characteristics of the dye and the lake pigment are sufficiently exhibited.

1 is a diagram showing a representative spectral distribution of radiation emitted from an ultrahigh pressure mercury lamp.
FIG. 2 is a diagram showing a spectral distribution of radiation obtained by interposing an ultraviolet cut filter 1 to radiation emitted from an ultra-high pressure mercury lamp.
FIG. 3 is a diagram showing a spectral distribution of radiation obtained by interposing a UV cut filter 2 to radiation emitted from an ultra-high pressure mercury lamp.
FIG. 4 is a diagram showing the spectral distribution of radiation obtained by interposing an ultraviolet cut filter 3 to radiation emitted from an ultra-high pressure mercury lamp.

Hereinafter, this embodiment is described in detail.

<Formation method and color filter of pixel pattern>

The method of forming a pixel pattern of the present invention includes at least the steps (1) and (2) below.

(1) Process of forming the coating film of the colored radiation-sensitive composition containing at least 1 sort (s) chosen from the group which consists of a dye and a lake pigment on a board | substrate (henceforth a "coating film formation process").

(2) Process of exposing specific radiation to at least a part of said coating film (hereinafter also called "exposure process")

Hereinafter, each process of (1) and (2) is explained in full detail, giving a specific example.

(1) Coating film formation process

First, prepare a substrate. As a board | substrate, transparent glass substrates, such as borosilicate glass, alumino borosilicate glass, an alkali free glass, quartz glass, synthetic quartz glass, soda-lime glass, white sapphire, can be used, for example. Moreover, acryl, such as polymethyl methacrylate, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, Polyether ether ketone, fluororesin, polyether nitrile, polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene-based resin, polysulfone, polyether sulfone, polyarylate, polyamideimide, polyether You may use transparent resin films, such as a mid or thermoplastic polyimide. In particular, alkali-free glass is a material having a low coefficient of thermal expansion, and is preferably used because it is excellent in dimensional stability and high temperature heat treatment.

These substrates may be subjected to a suitable pretreatment such as film formation of a silicon dioxide film by ion plating, sputtering, vapor phase reaction or vacuum deposition, in addition to chemical treatment or plasma treatment with a silane coupling agent or the like as necessary.

Next, a light shielding layer (black matrix) is formed on a board | substrate so that the part which forms a pixel may be divided. For example, a metal thin film such as chromium formed by sputtering or vapor deposition is processed into a desired pattern using a photolithography method. Or the radiation sensitive composition containing a black coloring agent can be apply | coated on a board | substrate, and a desired pattern can be formed by the photolithographic method. It is preferable that the film thickness of the light shielding layer containing a metal thin film shall be 0.1 micrometer-0.2 micrometer normally. On the other hand, it is preferable that the film thickness of the light shielding film formed using the black radiation sensitive composition shall be around 1 micrometer.

In addition, a light shielding layer may be unnecessary, and in that case, the process of forming a light shielding layer can be skipped.

Next, the negative type blue radiation sensitive composition containing a blue dye or a lake pigment is apply | coated on the said board | substrate, for example. Next, prebaking is performed to evaporate the solvent to form a coating film.

When apply | coating colored radiation-sensitive composition to a board | substrate, the spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, etc. can be selected suitably. It is preferable to employ | adopt the spin coating method or the slit die coating method from the point which the coating film of uniform film thickness is obtained.

Prebaking is normally performed combining pressure reduction drying and heat drying. Drying under reduced pressure is usually performed until it reaches 50 Pa-200 Pa. In addition, the conditions of heat drying are about 1 to 10 minutes at the temperature of 70 degreeC-110 degreeC normally using a hotplate. In addition, the thickness of the coating film apply | coated is 0.6 micrometer-8 micrometers normally as film thickness after drying, Preferably they are 1.2 micrometers-5 micrometers.

Moreover, as another example of forming the coating film of a coloring radiation sensitive composition on a board | substrate, the method by the inkjet system currently disclosed by Unexamined-Japanese-Patent No. 7-318723, Unexamined-Japanese-Patent No. 2000-310706, etc. is also Can be mentioned. In this method, the partition which also has a light shielding function is first formed on the surface of a board | substrate. Subsequently, a colored radiation-sensitive composition containing, for example, a blue dye or a lake pigment is discharged into the partition by an inkjet apparatus. Thereafter, prebaking is performed to evaporate the solvent. The method and conditions of the prebaking are the same as in the first example described above.

In addition, the partition wall mentioned above functions not only the light shielding function but the color-sensitive radiation-sensitive composition of each color discharged in the division not to be mixed. For this reason, a film thickness is thick compared with the light shielding layer (black matrix) used by said 1st example. A partition is normally formed using a black radiation sensitive composition.

Moreover, the dry film method currently disclosed by Unexamined-Japanese-Patent No. 9-5991 etc. is mentioned as an additional example of forming the coating film of a colored radiation-sensitive composition on a board | substrate. In this method, a colored radiation-sensitive composition is formed on a support by applying a colored radiation-sensitive composition containing, for example, a blue dye or a lake pigment, onto the film-like support and prebaking to evaporate the organic solvent. A layered dry film is prepared. And the support body in which this colored radiation-sensitive composition layer was formed is laminated on the board | substrate for color filter formation using a laminator. Thereafter, the colored radiation-sensitive composition layer is transferred to the substrate by peeling the colored radiation-sensitive composition layer from the support. The method of apply | coating a coloring radiation sensitive composition on a support body, the method and conditions of prebaking are the same as that of the said 1st example.

(2) exposure process

After a coating film formation process, at least one part of the formed coating film is exposed through the photomask which has a predetermined pattern normally. The present invention is characterized in that the exposure radiation used at this time exhibits specific spectral characteristics. Usually, the radiation irradiated from the ultrahigh pressure mercury lamp used when manufacturing the color filter for color liquid crystal display shows the spectral characteristics like FIG. In Fig. 1, the peak at 436 nm is g-line, the peak at 405 nm is h-line, and the peak at 365 nm is i-line. Radiation emitted from an ultra-high pressure mercury lamp usually has several peaks below 350 nm. Contains deep ultraviolet light. The present inventors have found that the stability of dyes and lake pigments is increased by reducing the light intensity below 350 nm for exposure radiation exhibiting these spectroscopic properties.

In specific radiation, although the maximum intensity below 350 nm is 50% or less of the maximum peak intensity in 350 nm-450 nm, in order to raise a desired effect, it is preferable that it is 45% or less, and it is more preferable that it is 30% or less.

Although specific radiation can be obtained using the lamp which shows the above-mentioned spectral characteristics as a light source, it can also obtain through the ultraviolet-ray filter through the radiation radiated | emitted from an ultrahigh pressure mercury lamp. The ultraviolet blocking filter is not particularly limited as long as the light intensity of less than 350 nm can be reduced to the above conditions, but for example, the ultraviolet blocking filter UV-35, UV-33, UV-31 (manufactured by Toshiba Glass Co., Ltd.), etc. Can be.

Although the exposure amount of specific radiation is 10-100,000 J / m <2> normally, in order to raise a desired effect, it is preferable that it is 50-5,000 J / m <2>, and it is more preferable that it is 100-2,000 J / m <2>.

After the exposure process, a process (hereinafter, also referred to as a "development process") of developing the coating film after exposure (3) and / or (4) the process of post-baking the coating film is performed as needed.

(3) developing process

By developing with a developing solution after the exposure step, the unexposed part of the coating film is dissolved and removed. As the developer, an alkaline developer is preferable, and for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, Aqueous solutions, such as 5-diazabicyclo- [4.3.0] -5-nonene, are used. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline developing solution. In addition, after an alkali image development process, water washing is normally performed.

As the developing treatment method, for example, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid buildup) developing method, or the like can be applied. The developing conditions can be, for example, 5 seconds to 300 seconds at room temperature.

In addition, when the coating film of a colored radiation-sensitive composition is formed by the said inkjet system, the image development process is unnecessary and is abbreviate | omitted.

(4) post-baking the coating film

After the development process or after forming a coating film by the said inkjet method and passing through an exposure process, post-baking a patterned coating film is preferable at the point which improves sclerosis | hardenability. The conditions of post-baking can be made into about 20 to 40 minutes at 150 degreeC-250 degreeC, for example, when using a warm air heating furnace.

In this way, a pixel array in which blue pixel patterns containing blue dyes or lake pigments are arranged in a predetermined arrangement can be formed. Next, a green pixel pattern is formed on the same substrate by repeating the above process using a negative green radiation-sensitive composition, and further, by repeating the above process using a negative red radiation-sensitive composition, red By forming a pixel pattern of on the same substrate, a pixel array in which three primary color pixel patterns of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, in this embodiment, the order of forming the pixel pattern of each color on a board | substrate is not limited to the example mentioned above. The formation order of each color can be changed suitably.

The film thickness of the pixel pattern formed as mentioned above is 0.5 micrometer-5 micrometers normally, Preferably they are 1.0 micrometer-3 micrometers.

In the present invention, the pixel pattern constituting the color filter is not limited to red, green, and blue, and may be a pixel pattern having three primary colors of yellow, magenta, and cyan. In addition to the coloring pattern corresponding to the pixel of the three primary colors, the fourth or fifth coloring pattern may be formed. For example, as disclosed in Japanese Patent Laid-Open No. 2005-523465 or the like, a fourth pixel (yellow pixel) for widening the color gamut in addition to the coloring pattern corresponding to the pixels of the three primary colors of red, green, and blue. The fifth pixel (cyan pixel) can be disposed.

By providing a protective film further on the pixel pattern formed in this way, the display characteristic of a display element can be improved. As a protective film, the organic film or organic-inorganic hybrid film formed from curable composition, or inorganic films, such as a SiNx film and a SiOx film, are mentioned. In this embodiment, it is preferable to form a protective film using a curable composition.

As a method of forming a protective film using curable resin composition, the method disclosed by Unexamined-Japanese-Patent No. 4-53879, Unexamined-Japanese-Patent No. 6-192389, etc. can be employ | adopted, for example. .

As curable resin composition used for formation of a protective film, the thermosetting resin composition disclosed by Unexamined-Japanese-Patent No. 3-188153, Unexamined-Japanese-Patent No. 4-53879, etc. Disclosed in the radiation-sensitive resin composition disclosed in Japanese Patent Application Laid-Open No. 6-192389 or Japanese Patent Application Laid-Open No. Hei 8-183819, Japanese Patent Application Laid-Open No. 2006-195420 or Japanese Patent Application Laid-Open No. 2008-208342 The curable composition containing the polyorganosiloxane which has become is mentioned.

According to the method for forming a pixel pattern of the present invention, a pixel pattern is obtained in which the excellent chromaticity characteristics of the dye and the lake pigment are not lost, that is, the color difference ΔE * ab before and after exposure is small. Therefore, it becomes possible to obtain the color filter excellent in chromaticity characteristic by using the formation method of the pixel pattern of this invention. The method of forming the pixel pattern of the present invention includes various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It is preferable for manufacture, and it is especially suitable for manufacture of the color filter for color liquid crystal display elements using a large substrate.

Next, the coloring radiation sensitive composition used in the formation method of the pixel pattern of this invention is demonstrated. The colored radiation-sensitive composition contains at least one colorant, a binder resin, a crosslinking agent and a photopolymerization initiator containing at least one selected from the group consisting of dyes and lake pigments. A colored radiation-sensitive composition is mix | blended with a solvent normally and is used as a liquid composition.

Hereinafter, each component is demonstrated.

The colored radiation-sensitive composition used in the method of forming a pixel pattern of the present invention contains at least one selected from the group consisting of dyes and lake pigments as colorants. Although it does not specifically limit as dye, For example, azo dye, anthraquinone dye, xanthene dye, triaryl methane dye, phthalocyanine dye, quinone imine dye, quinoline dye, nitro dye, methine type Dyes; and the like. Specifically, what is attached to the following color index (C.I.) names is mentioned.

C.I. Acid yellow 11, C.I. Acid orange 7, C.I. Acid red 37, C.I. Acid red 180, C.I. Acid blue 29, C.I. Solvent Red 89, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive red 17, C.I. Reactive Red 120, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant red 7, C.I. Azo dyes, such as maltant yellow 5;

C.I. Bat Blue 4, C.I. Acid blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Anthraquinone dyes such as Disperse Blue 60;

C.I. Basic Red 1, C.I. Basic Red 1: 1, C.I. Basic Violet 10, C.I. Xanthene dyes such as solvent red 49;

C.I. Basic Blue 7, C.I. Triarylmethane dyes such as basic blue 11;

C.I. Phthalocyanine-based dyes such as pad blue 5;

C.I. Basic Blue 3, C.I. Quinone imine dyes such as basic blue 9;

C.I. Solvent Yellow 33, C.I. Acid yellow 3, C.I. Quinoline dyes such as Disperse Yellow 64;

C.I. Acid yellow 1, C.I. Acid orange 3, C.I. Nitro dyes such as Disperse Yellow 42;

C.I. Methine-based dyes such as solvent yellow 179.

In addition, claim 3 or claim 4 of Unexamined-Japanese-Patent No. 2010-168531, Unexamined-Japanese-Patent No. 2010-170073, Unexamined-Japanese-Patent No. 2010-170074, Unexamined-Japanese-Patent No. 2010-275531, Japan Patent Azo dyes disclosed in Japanese Patent Application Laid-Open No. 2010-275533, triaryl methane dyes described in Japanese Patent Application Laid-Open No. 14-503477, and Japanese Patent Publication No. 2007-503477 Xanthene type dye etc. which were described in Claim 3, Unexamined-Japanese-Patent No. 2010-244027, Unexamined-Japanese-Patent No. 2010-254964, etc. are mentioned.

Of these dyes, azo dyes, triarylmethane dyes, xanthene dyes, and methine dyes are preferable in that the effect that is particularly excellent in the method of forming the pixel pattern of the present invention is obtained.

In this invention, dye can be used individually or in mixture of 2 or more types.

In addition, a rake pigment is what makes soluble dye the insoluble pigment by the precipitant. As the precipitating agent, for example, barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, catanol, tamole, isopoly acid, heteropoly acid (e.g., phosphotungstic acid, phosphomolybdic acid , Phosphotungsten molybdate, silico tungsten molybdate, silico tungstic acid, silicomolybdic acid) and the like. Among these, isopoly acid and heteropoly acid are preferable as a precipitating agent.

Examples of such lake pigments include those having the following color index (C.I.) names.

C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 24, C.I. Pigment Blue 24: 1, C.I. Pigment Blue 56, C.I. Pigment Blue 61, C.I. Pigment blue 62,

C.I. Pigment Violet 1, C.I. Pigment violet 2, C.I. Pigment violet 3, C.I. Pigment violet 3: 1, C.I. Pigment violet 3: 3, C.I. Pigment Violet 27, C.I. Pigment violet 39,

C.I. Pigment Green 1, C.I. Pigment green 4,

C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 48: 5, C.I. Pigment Red 49, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 49: 3, C.I. Pigment Red 52: 1, C.I. Pigment Red 52: 2, C.I. Pigment Red 53: 1, C.I. Pigment Red 54, C.I. Pigment Red 57: 1, C.I. Pigment Red 58, C.I. Pigment Red 58: 1, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 3, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 63: 3, C.I. Pigment Red 64: 1, C.I. Pigment Red 68, C.I. Pigment Red 81, C.I. Pigment Red 81: 1, C.I. Pigment Red 200, C.I. Pigment Red 237, C.I. Pigment Red 239, C.I. Pigment Red 247,

C.I. Pigment Yellow 61, C.I. Pigment Yellow 61: 1, C.I. Pigment Yellow 62, C.I. Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment Yellow 133, C.I. Pigment Yellow 168, C.I. Pigment Yellow 169, C.I. Pigment Yellow 183, C.I. Pigment Yellow 191, C.I. Pigment Yellow 191: 1, C.I. Pigment Yellow 206, C.I. Pigment Yellow 209, C.I. Pigment Yellow 209: 1 and C.I. Pigment Yellow 212.

Among these lake pigments, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 62, C.I. Pigment Violet 1, C.I. Pigment violet 2, C.I. Pigment violet 3, C.I. Pigment Violet 27, C.I. Triarylmethane type lake pigments, such as pigment violet 39, are preferable at the point which the especially excellent effect is acquired in the formation method of the pixel pattern of this invention. Triaryl methane lake pigments having isopoly acid or heteropoly acid as a precipitating agent are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-150195, Japanese Patent Application Laid-Open No. 2011-186043, and the like.

Lake pigments in the present invention can be used alone or in combination of two or more.

In the present invention, other colorants may be used together with the dye and the lake pigment as the colorant. It does not specifically limit as another coloring agent, A color and a material can be selected suitably according to the use of a color filter. Specifically, organic pigments, inorganic pigments and natural pigments can all be used as colorants, but organic pigments are preferably used because high color purity, brightness and contrast are required.

As a specific example of the organic pigment, the color index (C.I.) name, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 1, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Pigment violet 23, and the like.

Since the content rate of a coloring agent forms the pixel which is high in luminance and excellent in color purity, it is 5-70 mass% normally in solid content of a colored radiation-sensitive composition, Preferably it is 5-60 mass%. Solid content here is components other than the solvent mentioned later.

In addition, the sum total content ratio of at least 1 sort (s) chosen from the group which consists of a dye and a lake pigment becomes like this. Preferably it is 5 mass% or more, Especially preferably, it is 10 mass% or more in all the coloring agents.

Although it does not specifically limit as binder resin in colored radiation-sensitive composition, It is preferable to contain the polymer which has an acidic functional group. As an acidic functional group, a carboxyl group, a phenolic hydroxyl group, an imid acid group, a sulfo group, a sulfino group, or a sulfeno group etc. are mentioned, for example. Of these, carboxyl groups are preferably used.

As a polymer which has a carboxyl group, For example, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-140654, Japanese Patent Laid-Open ( Japanese Patent Application Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 09-325494, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144 Japanese Patent Laid-Open No. 11-174224 Japanese Patent Laid-Open No. 11-231523 Japanese Patent Laid-Open Polymers disclosed in 258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2002-296778, Japanese Patent Laid-Open No. 2004-101728, and Japanese Patent Laid-Open No. 2008-181095. Can be.

The acid value of the binder resin is preferably 10 to 200 KOH / mg, more preferably 30 to 270 KOH / mg, still more preferably 50 to 250 KOH / mg. The "acid value" herein refers to the number of mg of KOH necessary to neutralize 1 g of the solid content of the binder resin. In this invention, binder resin can be used individually or in mixture of 2 or more types.

The crosslinking agent in the colored radiation-sensitive composition is not particularly limited as long as it is a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, or an N-alkoxy methylamino group etc. are mentioned, for example.

As the crosslinking agent in the present invention, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferably used.

As a particularly preferable crosslinking agent, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and succinic anhydride are reacted. Compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, and caprolactone modified in paragraphs [0015] to [0018] of JP-A-11-44955 Functional (meth) acrylate, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine or N, N, N ', N'-tetra (alkoxymethyl) benzoguanamine Can be mentioned.

In this invention, a crosslinking agent can be used individually or in mixture of 2 or more types.

The photoinitiator in a colored radiation-sensitive composition is a compound which can generate | occur | produce the active species which can start the hardening reaction of the crosslinking agent mentioned above by exposure of specific radiation.

As a preferable photoinitiator, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, O-acyl oxime type compound, an onium salt type compound, a benzoin type compound, a benzophenone type compound, α-diketone compounds, polynuclear quinone compounds, diazo compounds or imidesulfonate compounds.

In this invention, a photoinitiator can be used together with a well-known sensitizer and a hydrogen donor. In addition, a photoinitiator can be used individually or in mixture of 2 or more types.

The solvent in the colored radiation-sensitive composition can be appropriately selected and used as long as it disperses or dissolves the components constituting the colored radiation-sensitive composition and does not react with these components and has suitable volatility.

Preferred solvents in the present invention include propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate and diethylene glycol dimethyl ether. , Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, propionic acid n -Butyl, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. are mentioned.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

The colored radiation-sensitive composition may further contain other components. As other components, for example, a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, a polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, a polyester type Dispersants such as dispersants and acrylic dispersants; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryl Adhesion promoters, such as a loyloxypropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

<Display element>

The display element of this invention is equipped with the color filter manufactured by the method mentioned above. As a specific example of a display element, a color liquid crystal display element, an organic electroluminescence display element, an electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter manufactured by the method of this invention is a drive board | substrate with which the thin film transistor (TFT) was arrange | positioned, for example, and the other board | substrate with which the color filter of this embodiment was provided. It can be set as the structure which opposes through this liquid crystal layer. Or a color liquid crystal display element forms the board | substrate with which the color filter of this embodiment was formed on the surface of the drive board | substrate with which the thin-film transistor (TFT) was arrange | positioned, and the indium tin oxide (ITO) electrode which is doped with tin. It is also possible to have a structure in which one substrate opposes through the liquid crystal layer. The latter structure can remarkably improve the aperture ratio, and has the advantage that a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display element includes a backlight unit. As the backlight unit, for example, a structure in which a fluorescent tube such as a Cold Cathode Fluorescent Lamp (CCFL) and a scattering plate are combined may be used. It is also possible to use a backlight unit having a white LED as a light source. As a white LED, for example, a white LED which combines a red LED, a green LED, and a blue LED to obtain white light by mixing, and a white LED and a blue LED which combines a blue LED, a red LED and a green phosphor to obtain white light by mixing White LED that obtains white light by mixing by combining red light emitting phosphor and green light emitting phosphor, white LED which obtains white light by mixing of blue LED and YAG fluorescent material, and blue LED, orange light emitting phosphor and green light emitting phosphor in combination The white LED which obtains white light, the ultraviolet-ray LED, the red light emitting fluorescent substance, the green light emitting fluorescent substance, and the blue light emitting fluorescent substance are combined, and the white LED etc. which obtain white light by mixing are mentioned.

The color liquid crystal display device including the color filter manufactured by the method of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching switching (IPS) type, a vertical alignment (VA) type, Appropriate liquid crystal modes such as OCB (Optically Compensated Birefringence) type can be applied.

The organic EL display element having the color filter manufactured by the method of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Laid-Open No. 11-307242.

The electronic paper having the color filter manufactured by the method of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

As mentioned above, although this embodiment was described, this invention is not limited to the said embodiment, It can variously deform and implement in the range which does not deviate from the summary.

[Example]

Hereinafter, an Example is given and this invention is demonstrated further more concretely. However, the present invention is not limited to the following examples.

[Production of pigment dye mixture liquids]

Production Example 1

As a colorant, C.I. Pigment Green 58 / C.I. 15 parts by mass of solvent yellow 179 = 60/40 (mass ratio) mixture, 10 parts by mass of BYK-LPN21116 (BYK Co., Ltd.) as a dispersant (non-volatile components = 40 mass%), and propylene glycol monomethyl ether acetate as a solvent. 75 mass parts was mixed and dispersed for 12 hours using a bead mill to prepare a pigment dye mixed solution (A1).

Production Example 2

As a colorant, C.I. Pigment Blue 15: 6 / C.I. 15 parts by mass of a basic blue 7 = 60/40 (mass ratio) mixture, 10 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (nonvolatile components = 40 mass%), and a propylene glycol monomethyl ether acetate as a solvent. 75 mass parts was mixed and dispersed for 12 hours using a bead mill to prepare a pigment dye mixture (A2).

Production Example 3

As a colorant, C.I. Pigment Green 58/15 parts by mass of a yellow dye (barbituric acid azo dye) represented by the following formula: 70 parts by mass / 30 (mass ratio) mixture, 10 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant Non-volatile component = 40 mass%) and 75 mass parts of propylene glycol monomethyl ether acetates as a solvent were mixed and dispersed for 12 hours using a bead mill to prepare a pigment dye mixture (A3).

Production Example 4

As a colorant, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 = 60/40 (mass ratio) 15 parts by mass of a mixture, 10 parts by mass of BYK-LPN21116 (manufactured by BYK Co., Ltd.) as a dispersant (non-volatile component = 40% by mass), and propylene glycol monomethyl ether as a solvent. 75 parts by mass of acetate was mixed and dispersed for 12 hours using a bead mill to prepare a pigment dispersion (A4).

Production Example 5

As a colorant, C.I. Pigment Blue 15: 6 / Xanthene-based dyes C.I. Rhodamine 6G = 60/40 (mass ratio) 15 parts by mass of a mixture, 10 parts by mass of BYK-LPN21116 (by Chemie Co., Ltd.) as a dispersant (non-volatile components = 40 mass%), and propylene glycol monomethyl ether acetate as a solvent 75 mass parts was mixed and dispersed for 12 hours with a bead mill to prepare a pigment dye mixture (A5).

Production Example 6

As a colorant, C.I. Pigment Blue 15: 6 / triarylmethane-based lake pigment represented by the following formula (wherein, x = 1 to 2) = 60/40 (mass ratio) 15 parts by mass of the mixture, BYK-LPN21116 (Bikke (BYK Corporation) 10 mass parts (non-volatile component = 40 mass%) and 75 mass parts of propylene glycol monomethyl ether acetates as a solvent were mixed and dispersed for 12 hours with the bead mill, and the pigment dispersion (A6) was produced.

Synthesis of Binder Resin

Synthesis Example 1

2 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by mass of methacrylic acid and N-phenylmaleimide. 3 masses of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Nippon Yushi Co., Ltd., trade name: Nova MSD) as 20 parts by mass, 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and a molecular weight regulator. Part was added and nitrogen-substituted. Thereafter, the mixture was stirred gently, the temperature of the reaction solution was raised to 80 ° C, and the temperature was maintained for 5 hours to polymerize, thereby obtaining a resin solution (solid content concentration = 33 mass%). Obtained resin was Mw = 16,000 and Mn = 7,000. This resin solution is referred to as "binder resin solution (B1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 44 parts by mass of p-vinyl benzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide, and 16 parts by mass of benzyl methacrylate were dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate, Further, 8 parts by mass of 2,2'-azobisisobutyronitrile and 8 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were added and nitrogen-substituted. Thereafter, with gentle stirring, the reaction solution was heated to 80 ° C with nitrogen bubbling, and maintained at this temperature to polymerize for 5 hours.

Subsequently, 17 mass parts of methacrylic acid, 0.5 mass part of p-methoxyphenol, and 4.4 mass parts of tetrabutylammonium bromide were added to this reaction solution, and reaction was performed at the temperature of 120 degreeC for 9 hours. Further, 18.5 parts by mass of succinic anhydride was added, the reaction was carried out at a temperature of 100 ° C. for 6 hours, followed by washing with water twice while maintaining the reaction solution temperature at 85 ° C., followed by concentration under reduced pressure, to obtain a binder resin solution (solid content concentration). = 33 mass%). Obtained binder resin was Mw = 7,800 and Mn = 5,000. This binder resin solution is referred to as "binder resin solution (B2)".

Example 1

[Production of colored radiation-sensitive composition]

100 parts by mass of the pigment dye mixture (A1), 18 parts by mass of the binder resin solution (B1) as a binder resin (solid content concentration = 33% by mass), and Nippon Kayaku Co., Ltd. (KAYARAD) MAX-3510 (D 8 parts by mass of a mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) and 4 parts by mass of kayarrad DPCA-60 (caprolactone-modified dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. 1 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H as an initiator -Carbazol-3-yl]-, 1- (O-acetyl oxime) 3 parts by mass, propylene glycol monomethyl ether acetate as 0.2 parts by mass of Megapack F-554 manufactured by DIC Corporation Mixing to prepare a green radiation-sensitive composition having a solid content concentration of 15% by mass The.

[Formation of pixel pattern and evaluation of color stability]

After apply | coating the obtained green radiation sensitive composition on a glass substrate using the slit die coater, it prebaked for 4 minutes with the 90 degreeC hotplate, and formed the coating film of 2 micrometers in film thicknesses.

Subsequently, after cooling the board | substrate with a coating film to room temperature, using the radiation which shows the spectral characteristic of FIG. The coating film was exposed by the exposure amount of 2,000 J / m <2> through the stripe-shaped photomask. Then, shower development was performed for 1 minute by discharging the developing solution containing the 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with the developing pressure of 1 kgf / cm <2> (nozzle diameter 1mm) with respect to the obtained board | substrate. Thereafter, the substrate was washed with ultrapure water and air dried to form a green striped pixel pattern on the substrate.

About the coating film and the formed pixel pattern before exposure, the spectral characteristic was measured using the color analyzer (MCPD2000 by Otsuka Denshi Co., Ltd.), and color difference ((DELTA) E * ab) was calculated | required. The evaluation results are shown in Table 1 below.

Examples 2 to 11, Comparative Examples 1 to 5 and Reference Examples 1 to 2

In Example 1, each colored radiation sensitive composition was produced like Example 1 except having changed the kind and content of each component as shown in Table 1. Subsequently, using the obtained colored radiation-sensitive composition, a pixel pattern was formed in the same manner as in Example 1 except that the exposure radiation was selected as shown in Table 1, and color stability was evaluated. The evaluation results are shown in Table 1. In addition, the radiation which shows the spectral characteristic of FIG. 3 is obtained through the ultraviolet-ray filter 2 (UV-33 (made by Toshiba Glass Co., Ltd.)) to the radiation radiated | emitted from an ultrahigh pressure mercury lamp, The radiation which shows the spectral characteristic of FIG. It is obtained through the ultraviolet-ray filter 3 (UV-35 (made by Toshiba Glass Co., Ltd.)) through the radiation radiated | emitted from the radiation.

In Table 1, each component is as follows.

C1: caprolactone modified dipentaerythritol hexaacrylate (made by Nippon Kayaku Co., Ltd., brand name Kayarrad DPCA-60)

C2: A mixture of dipentaerythritol pentaacrylate and succinic acid monoester, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Toago Kosei Co., Ltd., trade name TO-1382)

C3: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name Kayarard MAX-3510)

C4: ethylene oxide oligomer-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., brand name Kayarade DPEA-12)

D1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, product name Irgacure 369)

D2: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals, product name Irga Cure OXE02)

D3: 2-mercaptobenzothiazole

D4: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- 1,2'-biimidazole (made by Hodogaya Chemical Co., Ltd. make, brand name B- CIM)

D5: 2,4-diethyl thioxanthone (made by Nippon Kayaku Co., Ltd., brand name CAYACURE DETX-S)

D6: 4,4'-bis (diethylamino) benzophenone

D7: Made by Adeka (brand name NCI930)

Claims (3)

(1) forming a coating film of a colored radiation-sensitive composition containing at least one member selected from the group consisting of dyes and lake pigments on a substrate, and (2) irradiating radiation to at least a portion of the coating film. Including,
Wherein the spectral distribution of the radiation has a plurality of peaks in the range of 350 nm to 450 nm, and the maximum intensity at less than 350 nm of the radiation is 50% or less of the maximum peak intensity at 350 nm to 450 nm. How to form a pattern. The color filter provided with the pixel pattern formed by the method of Claim 1. The display element provided with the color filter of Claim 2.

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