JP2012189994A - Formation method of pixel pattern, color filter, display element and colored radiation-sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a formation method of pixel pattern by which, if a dye or a lake pigment is used as a colorant, the excellent chromaticity characteristic of the dye is sufficiently exhibited.SOLUTION: A formation method of pixel pattern includes steps of: (1) forming a coating film of a colored radiation-sensitive composition containing at least one type selected from the group consisting of a dye and a lake pigment, on a substrate and (2) exposing at least part of the coating film with ultraviolet LED.

Description

  The present invention relates to a method for forming a pixel pattern, a color filter provided with the pixel pattern formed by this method, a display element including the color filter, and a colored radiation-sensitive composition.

  The color filter transmits light in a specific wavelength region of visible light to generate colored transmitted light. A liquid crystal display element using liquid crystal cannot develop color by itself, but can function as a color liquid crystal display element by using a color filter. The color filter is also used for color display of an organic EL (Electro Luminescence) element using a white light emitting layer, electronic paper, or the like. Furthermore, if a color filter is used, color imaging of a solid-state imaging device such as a CCD image sensor or a CMOS image sensor becomes possible.

  The following is known as a manufacturing method of a color filter. For example, a colored radiation-sensitive composition is applied as a coloring composition sensitive to appropriate radiation on a transparent substrate or a transparent substrate on which a light-shielding layer having a desired pattern is formed. Next, after the coating film is dried, the dried coating film is irradiated with radiation (hereinafter referred to as “exposure”) through a mask and subjected to a development treatment. This is a method for obtaining pixels of each color (see, for example, Patent Documents 1 and 2). Moreover, the method of obtaining the pixel of each color by the inkjet system using a colored curable resin composition is also known (for example, refer patent document 3).

  By the way, it is known that it is effective to use a dye or a lake pigment as a colorant in order to realize high brightness and high color purity of a display element or high definition of a solid-state imaging element (for example, And Patent Documents 4 and 5).

JP-A-2-144502 JP-A-3-53201 JP 2000-310706 A JP 2008-304766 A JP 2001-081348 A

  However, a colored radiation-sensitive composition containing a dye or a lake pigment is significantly inferior in process stability of chromaticity characteristics as compared with a colored radiation-sensitive composition containing only a pigment. Therefore, there is a problem that even if a dye or a lake pigment is used as the colorant, it is difficult to obtain a color filter having superior chromaticity characteristics over the pigment.

  The present invention has been made in view of the above problems. That is, the object of the present invention is to provide a pixel pattern forming method and a chromaticity characteristic to fully express the excellent chromaticity characteristic of the dye when a dye or a lake pigment is used as a colorant. It is to provide a display element.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using an ultraviolet LED as an exposure light source when forming a pixel pattern.

  That is, the present invention includes (1) a step of forming a coating film of a colored radiation-sensitive composition containing at least one selected from the group consisting of a dye and a lake pigment on a substrate, and (2) the coating film The present invention provides a method for forming a pixel pattern including a step of exposing at least a part using an ultraviolet LED.

  Further, the present invention provides a color filter comprising a pixel pattern formed by the above method, a display element comprising the color filter, and (A) a color containing at least one selected from the group consisting of a dye and a lake pigment. A colored radiation-sensitive composition for forming a pixel pattern by ultraviolet LED exposure, containing an agent, (B) a binder resin, (C) a crosslinking agent, and (D) a photopolymerization initiator.

  According to the present invention, when a dye or a lake pigment is used as a colorant, a color filter that can fully exhibit the excellent chromaticity characteristics of the dye or the lake pigment can be produced.

  Hereinafter, this embodiment will be described in detail.

<Pixel pattern forming method and color filter>
The pixel pattern forming method of the present invention includes at least the following steps (1) and (2).
(1) The process of forming the coating film of the coloring radiation sensitive composition containing dye on a board | substrate (henceforth "the coating film formation process").
(2) A step of exposing at least a part of the coating film using an ultraviolet LED (hereinafter also referred to as an “exposure step”).

  Below, each process of (1) and (2) is demonstrated in detail, giving a specific example.

(1) Coating film forming step First, a substrate is prepared. As the substrate, for example, a transparent glass substrate such as borosilicate glass, aluminoborosilicate glass, alkali-free glass, quartz glass, synthetic quartz glass, soda lime glass, and white sapphire can be used. Also, acrylic such as polymethyl methacrylate, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, polyether ether ketone, fluororesin, poly A transparent resin film such as ether nitrile, polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene resin, polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, or thermoplastic polyimide can also be used. In particular, alkali-free glass is a material having a small coefficient of thermal expansion, and is preferably used from the viewpoint of excellent dimensional stability and characteristics in high-temperature heat treatment.

  Moreover, on these substrates, if desired, in addition to chemical treatment and plasma treatment with a silane coupling agent, etc., a silicon dioxide film is formed by ion plating, sputtering, gas phase reaction or vacuum deposition, etc. Appropriate pretreatment can be applied.

Next, a light-shielding layer (black matrix) is formed on the substrate so as to partition a portion where a pixel is to be formed. For example, a metal thin film such as chromium formed by sputtering or vapor deposition is processed into a desired pattern by using a photolithography method. Or you may apply | coat the radiation sensitive composition containing a black coloring agent on a board | substrate, and may form a desired pattern with the photolithographic method. The thickness of the light shielding layer made of a metal thin film is usually preferably 0.1 μm to 0.2 μm. On the other hand, the thickness of the light-shielding film formed using the black radiation-sensitive composition is preferably about 1 μm.
In some cases, the light shielding layer is unnecessary, and in this case, the process of forming the light shielding layer can be omitted.

  Next, a negative blue radiation-sensitive composition containing, for example, a blue dye is applied onto the substrate. Next, pre-baking is performed to evaporate the solvent, thereby forming a coating film.

  When the colored radiation-sensitive composition is applied to the substrate, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be appropriately selected. In view of obtaining a coating film having a uniform film thickness, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 Pa to 200 Pa. Moreover, the conditions of heat drying are normally about 1 minute-10 minutes under the temperature of 70 to 110 degreeC using a hotplate. Moreover, the thickness of the coating film to be applied is usually 0.6 μm to 8.0 μm, preferably 1.2 μm to 5.0 μm, as the film thickness after drying.

  In addition, as another example of forming a coating film of a colored radiation-sensitive composition on a substrate, there is a method using an inkjet method disclosed in JP-A-7-318723, JP-A-2000-310706, and the like. It is done. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, a colored radiation-sensitive composition containing, for example, a blue dye is discharged into the partition wall by an inkjet device. Thereafter, pre-baking is performed to evaporate the solvent. The prebaking method and conditions are the same as in the first example.

In addition, the above-mentioned partition fulfill | performs not only the light-shielding function but the function for the coloring radiation sensitive composition of each color discharged in the division not to be mixed. Therefore, the film thickness is thicker than the light shielding layer (black matrix) used in the first example. A partition is normally formed using a black radiation sensitive composition.
Further, as a further example of forming a coating film of a colored radiation-sensitive composition on a substrate, there is a dry film method disclosed in JP-A-9-5991. In this method, for example, a colored radiation-sensitive composition containing a blue dye is applied onto a film-like support, and pre-baking is performed to evaporate the organic solvent. A dry film formed with a conductive composition is produced. 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 for applying the colored radiation-sensitive composition on the support and the prebaking method and conditions are the same as those in the first example.

(2) Exposure step After the coating film forming step, at least a part of the formed coating film is usually exposed through a photomask having a predetermined pattern. The present invention is characterized in that the exposure light source used at this time is an ultraviolet LED. The ultraviolet LED is a light emitting diode that emits ultraviolet light. The ultraviolet LED that can be used is not particularly limited as long as the photopolymerization initiator described later emits ultraviolet light that is sensitized, but in order to obtain a color filter having extremely excellent chromaticity characteristics, a peak wavelength is required. Is preferably an ultraviolet LED that emits ultraviolet light having a wavelength of 300 nm or more, particularly 350 nm to 400 nm. In this invention, it is guessed that decomposition | disassembly of the dye in an exposure process is suppressed by using ultraviolet LED which has this light emission characteristic as an exposure light source. Here, the “peak wavelength” means a wavelength at which the emission intensity is maximum in the emission spectrum, and can be measured using a commercially available spectrophotometer.

The exposure amount in the pixel pattern forming method of the present invention is usually 10 to 10,000 J / m ² . The illuminance is usually 10 mW / cm ² or more. As an ultraviolet LED irradiation device, for example, it is commercially available from Panasonic Electric Works Co., Ltd.

  After the exposure step, a step of (3) developing the coated film after exposure (hereinafter also referred to as “developing step”) and / or (4) a step of post-baking the coated film is performed as necessary.

(3) Development step After the exposure step, the unexposed portion of the coating film is dissolved and removed by developing with a developer. The developer is preferably an alkali developer, such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 1,5-diazabicyclo- [4.3.0] -5-nonene is used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. Incidentally, after the alkali development treatment, washing with water is usually performed.

As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, or a paddle (liquid accumulation) development method can be applied. The development 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 abbreviate | omitted.

(4) Step of post-baking the coating film After the development step or after forming the coating film by the ink jet method and passing through the exposure step, it is preferable to post-bake the patterned coating film from the viewpoint of improving curability. . The conditions for the post-baking can be, for example, 150 ° C. to 250 ° C. for about 20 minutes to 40 minutes when a hot air heating furnace is used.

  In this manner, a pixel array containing a blue dye and having a blue pixel pattern arranged in a predetermined arrangement can be formed. Next, by using the negative type green radiation sensitive composition, by repeating the above process, a green image color pattern is formed on the same substrate, and further using the negative type red radiation sensitive composition, By repeating the above steps, a red pixel pattern is formed on the same substrate, whereby a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged in a predetermined arrangement can be manufactured. However, in this embodiment, the order in which the pixel patterns of the respective colors are formed on the substrate is not limited to the above example. The order of forming each color can be changed as appropriate.

  The film thickness of the pixel pattern formed as described above is usually 0.5 μm to 5.0 μm, preferably 1.0 μm to 3.0 μm.

  In the present invention, the pixel pattern constituting the color filter is not limited to red, green, and blue, but may be a pixel pattern having three primary colors of yellow, magenta, and cyan. In addition to the coloring patterns corresponding to the pixels of the three primary colors, the fourth and fifth coloring patterns can also be formed. For example, as disclosed in JP-T-2005-523465, etc., a fourth pixel (yellow pixel) for expanding the color specification range in addition to the coloring patterns corresponding to the three primary color pixels of red, green and blue And a fifth pixel (cyan pixel) can be arranged.

  By providing a protective film on the pixel pattern thus formed, the display characteristics of the display element can be improved. Examples of the protective film include organic films or organic-inorganic hybrid films formed from curable compositions, or inorganic films such as SiNx films and SiOx films. In this Embodiment, it is preferable to form a protective film using a curable composition.

  As a method for forming a protective film using the curable resin composition, for example, a method disclosed in JP-A-4-53879 or JP-A-6-192389 can be employed.

  Examples of the curable resin composition used for forming the protective film include a thermosetting resin composition disclosed in JP-A-3-188153 or JP-A-4-53879, and JP-A-6-192389. And a polyorganosiloxane disclosed in Japanese Patent Application Laid-Open No. 2006-195420 and Japanese Patent Application Laid-Open No. 2008-208342. A curable composition etc. can be mentioned.

  According to the pixel pattern forming method of the present invention, the excellent chromaticity characteristics of dyes and lake pigments are exhibited without loss, that is, the color purity and brightness stimulus value (Y) in the CIE color system. A high color filter can be obtained. Therefore, by using the pixel pattern forming method of the present invention, a color filter having excellent chromaticity characteristics can be obtained. The pixel pattern forming method of the present invention includes various colors such as a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image sensor, a color filter for an organic EL display element, and a color filter for electronic paper. It is suitable for manufacturing a filter, and particularly suitable for manufacturing a color filter for a color liquid crystal display element using a large substrate.

<Colored radiation-sensitive composition>
In the method for forming a pixel pattern of the present invention, a colored radiation-sensitive composition containing at least one selected from the group consisting of dyes and lake pigments is used. The colored radiation-sensitive composition contains at least one colorant selected from the group consisting of (A) a dye and a lake pigment, (B) a binder resin, (C) a crosslinking agent, and (D) a photopolymerization initiator. Containing. Hereinafter, each component will be described.

-(A) Colorant-
The colored radiation-sensitive composition used in the method for forming a pixel pattern of the present invention contains (A) at least one selected from the group consisting of a dye and a lake pigment as a colorant. The dye is not particularly limited. For example, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, methine And dyes. Specific examples include those with the following color index (CI) names.

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

C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;
C. I. Basic Red 1, C.I. I. Basic Red 1: 1, C.I. I. Basic Violet 10, C.I. I. Xanthene dyes such as Solvent Red 49;
C. I. Basic Blue 7, C.I. I. Triarylmethane dyes such as Basic Blue 11;
C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42;
C. I. Methine dyes such as Solvent Yellow 179.

  In addition, Claim 3 or Claim 4 of JP 2010-168531, JP 2010-170073, JP 2010-170074, JP 2010-275531, JP 2010-275533, etc. Azo dyes described in JP-A No. 2007-503477, claim 14 of Japanese Patent Publication No. 2007-503477, triarylmethane dyes described in International Publication No. 10/123071, pamphlet, etc. Examples thereof include xanthene dyes described in JP2010-244027A and JP2010-254964A.

Of these dyes, azo dyes, triarylmethane dyes, xanthene dyes, and methine dyes are preferable in that a particularly excellent effect can be obtained in the method for producing a color filter of the present invention.
In this invention, dye can be used individually or in mixture of 2 or more types.

  The lake pigment is a pigment that is insoluble with a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, katanol, tamol, isopolyacid, heteropolyacid (for example, phosphotungstic acid, phosphomolybdic acid, phosphorous acid). Phosphotungstic molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid) and the like. Among these, as the precipitant, isopolyacid and heteropolyacid are preferable.

Examples of such lake pigments include those having the following color index (CI) names.
C. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 56, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62,
C. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 27, C.I. I. Pigment violet 39,
C. I. Pigment green 1, C.I. I. Pigment Green 4,
C. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 54, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 200, C.I. I. Pigment red 237, C.I. I. Pigment red 239, C.I. I. Pigment red 247,
C. I. Pigment yellow 61, C.I. I. Pigment yellow 61: 1, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 133, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 169, C.I. I. Pigment yellow 183, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 191: 1, C.I. I. Pigment yellow 206, C.I. I. Pigment yellow 209, C.I. I. Pigment yellow 209: 1, and C.I. I. Pigment yellow 212.

Of these lake pigments, C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 62, C.I. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 27, C.I. I. A triarylmethane lake pigment such as CI Pigment Violet 39 is preferable in that a particularly excellent effect can be obtained in the pixel pattern forming method of the present invention. Triarylmethane-based lake pigments having an isopolyacid or heteropolyacid as a precipitating agent are also disclosed in, for example, JP2011-150195A, JP2011-186043A, and the like.
In the present invention, the lake pigments can be used alone or in admixture of two or more.

  In the present invention, other colorants can be used as the colorant together with the dye and the lake pigment. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the use of the color filter. Specifically, any of organic pigments, inorganic pigments, and natural pigments can be used as a colorant, but organic pigments are preferably used because high color purity, luminance, and contrast are required.

  Preferable specific examples of the organic pigment include a color index (CI) name, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 1, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Pigment orange 38, C.I. I. And CI Pigment Violet 23.

(A) The content of the colorant is usually 5 to 70% by mass, preferably 5 to 60% by mass in the solid content of the colored radiation-sensitive composition, from the viewpoint of forming a pixel having high luminance and excellent color purity. It is. Solid content here is components other than the solvent mentioned later.
The content ratio of at least one selected from the group consisting of dyes and lake pigments is preferably 5% by mass or more, particularly preferably 10% by mass or more, based on the total colorant.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, or a sulfo group. In order to enhance the desired effect of the present invention, it is preferable that the polymer having an acidic functional group and a polymerizable unsaturated group is contained in an amount of 10% by mass or more, further 30% by mass or more in the total binder resin. The upper limit of the content of such a polymer is preferably 90% by mass and particularly preferably 80% by mass in the total binder resin from the viewpoint of the storage stability of the colored radiation-sensitive composition.

Examples of the acidic functional group include a carboxyl group, a phenolic hydroxyl group, and a sulfo group, and a carboxyl group is preferable from the viewpoint of alkali solubility and storage stability of the resulting colored radiation-sensitive composition.
Examples of the polymerizable unsaturated group include a vinylaryl group, a (meth) acryloyl group, an allyl group, and the like, and a (meth) acryloyl group is preferable from the viewpoint of enhancing a desired effect. Moreover, it is preferable that the polymer which has an acidic functional group and a polymerizable unsaturated group has a polymerizable unsaturated group in the side chain.

  The polymer having an acidic functional group and a polymerizable unsaturated group is not particularly limited as long as the above requirements are satisfied. For example, (b-1) a polymer of a polymerizable unsaturated compound having a carboxyl group is used. A polymer obtained by reacting a carboxyl group with a polymerizable unsaturated compound having an oxiranyl group (hereinafter also referred to as “binder resin (b-1)”), (b-2) a polymerizable unsaturated group having a hydroxyl group. A polymer obtained by reacting a polymerizable unsaturated compound having an isocyanato group with a hydroxyl group of a copolymer of a compound and a polymerizable unsaturated compound having an acidic functional group (hereinafter referred to as “binder resin (b-2)”) (B-3) a polymerizable unsaturated compound having a carboxyl group is reacted with an oxiranyl group of a polymer of a polymerizable unsaturated compound having an oxiranyl group, A polymer obtained by reacting an acid anhydride with the hydroxyl group (hereinafter also referred to as “binder resin (b-3)”), (b-4) a polymerizable non-polymerizable group having a carboxyl group in the epoxy group of the epoxy resin. A polymer obtained by reacting a saturated compound and further reacting an acid anhydride with a hydroxyl group produced by the reaction (hereinafter also referred to as “binder resin (b-4)”), (b-5) styrene or Examples thereof include a polymer obtained by reacting a copolymer of the derivative with maleic anhydride or an ester thereof and a polymerizable unsaturated compound having a hydroxyl group (hereinafter also referred to as “binder resin (b-5)”). It is done.

The polymer of the polymerizable unsaturated compound having a carboxyl group used for the production of the binder resin (b-1) is not particularly limited as long as it has a carboxyl group, and the polymerizable unsaturated compound having a carboxyl group is polymerized. Is obtained.
Examples of the polymerizable unsaturated compound having a carboxyl group include (meth) acrylic acid and maleic acid, unsaturated compounds obtained by adding lactones to (meth) acrylic acid; hydroxyalkyl (meth) acrylate and succinic acid , Unsaturated acid compounds to which dibasic acids such as maleic acid, phthalic acid, or their anhydrides or anhydrides are added. A plurality of these may be used.
Among these, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and ω-carboxypolycaprolactone mono (meth) acrylate are preferable, and (meth) acrylic acid is more preferable.

Examples of the polymerizable unsaturated compound having an oxiranyl group used in the production of the binder resin (b-1) include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso ) Unsaturated compounds having a glycidyl group such as crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, p-vinylbenzyl glycidyl ether; 2 An alicyclic epoxy group such as a 1,3-epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, a 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] group, and (meth) Having a polymerizable unsaturated group such as an acryloyl group Saturated compounds. A plurality of these may be used.
Examples of the polymerizable unsaturated compound having a hydroxyl group used in the production of the binder resin (b-2) include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono In addition to hydroxyalkyl (meth) acrylates such as (meth) acrylate, N-methylolacrylamide, allyl alcohol and the like can be mentioned. Moreover, as a polymerizable unsaturated compound which has an acidic functional group used for manufacture of binder resin (b-2), the polymerizable unsaturated compound which has the carboxyl group quoted in the said binder resin (b-1), etc. are mentioned. It is done. A plurality of these may be used.

  Examples of the polymerizable unsaturated compound having an isocyanato group used in the production of the binder resin (b-2) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, Examples include 1,1- (bisacryloyloxymethyl) ethyl isocyanate. A plurality of these may be used.

  The polymer of the polymerizable unsaturated compound having an oxiranyl group used for the production of the binder resin (b-3) may be any polymer having an oxiranyl group, but a poly (meth) acrylic acid ester having an oxiranyl group. Examples thereof include a copolymer and a polystyrene copolymer having an oxiranyl group. The poly (meth) acrylic acid ester-based copolymer having an oxiranyl group is a copolymer of a (meth) acrylic acid ester having an oxiranyl group and another polymerizable unsaturated compound. Examples of the (meth) acrylic acid ester having an oxiranyl group include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) ) Acrylate glycidyl ether and the like. A plurality of these may be used.

  Examples of styrenes having an oxiranyl group constituting a styrenic copolymer having an oxiranyl group include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 2,4-diglycidyloxy. Examples thereof include styrenes having 1 to 3 glycidyl groups such as methylstyrene and 3,4,5-triglycidylmethylstyrene. A plurality of these may be used.

Examples of the polymerizable unsaturated compound having a carboxyl group used in the production of the binder resin (b-3) include (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and 2- (meth) acryloylethylsuccinate. An acid etc. can be mentioned. A plurality of these may be used.
Examples of the acid anhydride used for the production of the binder resin (b-3) include malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, and diglycol anhydride. Examples thereof include polybasic acid anhydrides such as acid, phthalic anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and diphenic acid anhydride. A plurality of these may be used.

  In addition, the polymer of the polymerizable unsaturated compound which has a carboxyl group used for manufacture of binder resin (b-1), the polymerizable unsaturated compound which has a hydroxyl group used for manufacture of binder resin (b-2), and an acidic function In the copolymer of the polymerizable unsaturated compound having a group and the polymer of the polymerizable unsaturated compound having an oxiranyl group used for the production of the binder resin (b-3), copolymerization with each polymerizable unsaturated compound Other possible polymerizable unsaturated compounds can be copolymerized.

Examples of such other polymerizable unsaturated compounds include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; and fragrances such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, and acenaphthylene. Group vinyl compound; methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2. ^1.02,6 ] (Meth) such as decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Acrylic acid Ester, and the like. Moreover, the polymer of the polymerizable unsaturated compound which has a carboxyl group used for manufacture of a polymer (b-1), and the weight of the polymerizable unsaturated compound which has an oxiranyl group used for manufacture of a polymer (b-3). In the coalescence, a polymerizable unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate can be copolymerized. A plurality of these may be used.

  Epoxy resins used in the production of the binder resin (b-4) include bisphenol A type epoxy resins, epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A type epoxy resins and epichlorohydrin, bisphenol F type epoxy resins, bisphenol F. Type epoxy resin obtained by reaction of alcoholic hydroxyl group with epichlorohydrin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, fluorene epoxy resin, alicyclic epoxy Examples thereof include resins and dicyclopentadiene type epoxy resins. A copolymer type epoxy resin can also be used.

  Examples of the polymerizable unsaturated compound having a carboxyl group and the acid anhydride used in the production of the binder resin (b-4) include the same compounds as those used in the production of the binder resin (b-3).

  Examples of the copolymer of styrene or a derivative thereof and maleic anhydride used in the production of the binder resin (b-5) include styrene, m-methoxystyrene, p-methoxystyrene, maleic anhydride, or maleic acid. Maleic acid such as monomethyl acid, monoethyl maleate, mono-n-propyl maleate, mono-iso-propyl maleate, mono-n-butyl maleate, mono-iso-butyl maleate, mono-tert-butyl maleate And a copolymer with a mono-lower alkyl ester.

  Examples of the polymerizable unsaturated compound having a hydroxyl group used in the production of the binder resin (b-5) include hydroxyalkyl (meth) acrylate, N-methylolacrylamide, and allyl alcohol.

  In the present invention, as the binder resin, a polymer having an acidic functional group but having no polymerizable unsaturated group can be used alone, and the polymer can be used as an acidic functional group and a polymerizable unsaturated group. It can also be used with a polymer having Specific examples of the polymer having an acidic functional group but not having a polymerizable unsaturated group include, for example, JP-A-7-140654, JP-A-9-31144, JP-A-10-31308, It is disclosed in Kaihei 10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2002-296778, JP-A-2004-101728, etc. Can be mentioned.

  The acid value of the binder resin in the present invention is preferably 10 to 300 KOH / mg, more preferably 30 to 270 KOH / mg, and still more preferably 50 to 250 KOH / mg. Here, the “acid value” represents the number of mg of KOH required to neutralize 1 g of the solid content of the binder resin.

  The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is 1,000 to 100,000, and further 3,000. ~ 50,000 is preferred. In this case, if Mw is too small, the remaining film rate of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, There is a possibility that the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

  Further, the ratio (Mw / Mn) between the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is , Preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method. Further, the above-mentioned polymer having an acidic functional group and a polymerizable unsaturated group can be prepared by a known method, for example, JP-A-5-19467, JP-A-5-61196, JP-A-6-230212, It can be produced by the methods disclosed in Kaihei 7-207211 and JP-A-2008-181095.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In the present invention, the content of the binder resin is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the binder resin is too small, for example, alkali developability may be reduced, or residues or background stains may be generated on the substrate in the unexposed area or on the light shielding layer. Since the concentration of the colorant is relatively lowered, it may be difficult to achieve the target color density as a thin film.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethanes ( (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N′— Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (B) binder resin. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the colored radiation-sensitive composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and the ground on the unexposed portion of the substrate or the light shielding layer. Dirt, film residue, etc. tend to occur easily.

-(D) Photopolymerization initiator-
In the present invention, the (D) photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of the (C) crosslinking agent by exposure with the ultraviolet LED.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. Examples of commercially available O-acyloxime compounds include NCI-831 and NCI-930 (manufactured by ADEKA Corporation).

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-Solvent-
The colored radiation-sensitive composition of the present invention contains the above-mentioned components (A) to (D) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent. Is done. As said solvent, (A)-(D) component and other components which comprise a colored radiation sensitive composition are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. As long as it can be appropriately selected and used.

In the present invention, preferred solvents include, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 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, formic acid n- Mill, acetic i- amyl, n- butyl propionate, ethyl butyrate, i- propyl, and butyric acid n- butyl or ethyl pyruvate and the like.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

-Other ingredients-
The colored radiation-sensitive composition of the present invention can further contain other components. Other components include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants such as polyester dispersants and acrylic dispersants; surfactants such as fluorine surfactants and silicon surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane And adhesion promoters such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Kill.

<Display element>
The display element of this invention comprises the color filter manufactured by the method mentioned above. Specific examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

  A color liquid crystal display element including a color filter manufactured by the method of the present invention includes, for example, a driving substrate on which a thin film transistor (TFT) is disposed, and a color filter according to the present embodiment. The substrate can be structured to face the liquid crystal layer. Alternatively, the color liquid crystal display element includes a substrate in which the color filter of this embodiment is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (Indium Tin Oxide) electrode. It is also possible to adopt a structure in which the substrate on which the film is formed faces the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be 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 can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, and a white light that is obtained by mixing a blue LED, a red LED, and a green phosphor to emit white light. A white LED that obtains white light by mixing white LEDs, a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED that obtains white light by mixing colors with a YAG phosphor, A combination of a blue LED, an orange light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED, an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor And white LEDs that obtain white light by color mixing.

  The color liquid crystal display device including the color filter manufactured by the method of the present invention includes a TN (Twisted Nematic) type, a STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, and a VA (Vertical Alignment) type. An appropriate liquid crystal mode such as an OCB (Optically Compensated Birefringence) type can be applied.

  An organic EL display element having a color filter manufactured by the method of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  An electronic paper having a 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 Application Laid-Open No. 2007-41169.

  Although the present embodiment has been described above, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Preparation of pigment dye mixture, etc.]
Preparation Example 1
As a coloring agent, C.I. I. Pigment green 58 / C.I. I. Solvent Yellow 179 = 15 parts by mass of 60/40 (mass ratio) mixture, BYK-LPN21116 (by BYK) as a dispersant, 10 parts by mass (nonvolatile component = 40% by mass), and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixed solution (A1).

Preparation Example 2
As a coloring agent, C.I. I. Pigment green 58 / C.I. I. Solvent yellow 179 = 80 parts by weight (mass ratio) 15 parts by weight of mixture, BYK-LPN21116 (made by BYK) as a dispersant, 10 parts by weight (non-volatile component = 40% by weight), propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A2).

Preparation Example 3
As a coloring agent, C.I. I. Pigment Blue 15: 6 / C.I. I. 15 parts by weight of Basic Blue 7 = 60/40 (mass ratio) mixture, 10 parts by weight (non-volatile component = 40% by weight) of BYK-LPN21116 (produced by BYK) as a dispersant, and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A3).

Preparation Example 4
As a coloring agent, C.I. I. Pigment Blue 15: 6 / C.I. I. 15 parts by weight of Basic Blue 7 = 80/20 (mass ratio) mixture, 10 parts by weight (non-volatile component = 40% by weight) of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A4).

Preparation Example 5
As a coloring agent, C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 150 = 60/40 (mass ratio) 15 parts by mass of a mixture, BYK-LPN21116 (manufactured by BYK) as a dispersant, 10 parts by mass (nonvolatile component = 40% by mass), and propylene glycol monomethyl ether acetate 75 as a solvent Mass parts were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A5).

Preparation Example 6
As a coloring agent, C.I. I. Pigment Blue 15: 6 / C. I. Rhodamine 6G = 60/40 (mass ratio) 15 parts by mass of mixture, BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, 10 parts by mass (non-volatile component = 40% by mass), and 75 mass of propylene glycol monomethyl ether acetate as a solvent A portion was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dye mixture (A6).

Preparation Example 7
As a coloring agent, C.I. 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 (BIC Chemie ( BYK)) 10 parts by mass (nonvolatile component = 40% by mass) and 75 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A7).

[Synthesis of binder resin]
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and 20 parts by mass of N-phenylmaleimide. , 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) as a molecular weight regulator, nitrogen Replaced. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution (solid content concentration = 33% by mass). The 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 condenser and a stirrer, 44 parts by mass of p-vinylbenzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide, and 16 parts by mass of benzyl methacrylate are dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate. 8 parts by mass of '-azobisisobutyronitrile and 8 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were charged and purged with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring and nitrogen bubbling, and polymerization was carried out for 5 hours while maintaining this temperature.
Next, 17 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol and 4.4 parts by mass of tetrabutylammonium bromide were added to the reaction solution, and the reaction was performed at a temperature of 120 ° C. for 9 hours. Furthermore, after adding 18.5 parts by mass of succinic anhydride and reacting at a temperature of 100 ° C. for 6 hours, the reaction solution temperature was maintained at 85 ° C. and washed twice with water, followed by concentration under reduced pressure to obtain a binder. A resin solution (solid content concentration = 33 mass%) was obtained. The obtained binder resin was Mw = 7,800 and Mn = 5,000. This binder resin solution is referred to as “binder resin solution (B2)”.

Synthesis example 3
In a flask equipped with a condenser and a stirrer, 25 parts by weight of 3-methacryloyloxymethyl-3-ethyloxetane, 18 parts by weight of methacrylic acid, 9 parts by weight of mono-2-acryloxyethyl succinate, 10 parts by weight of N-phenylmaleimide, 24 parts by mass of benzyl methacrylate and 14 parts by mass of hydroxyethyl methacrylate are dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate, and further 6 parts by mass of 2,2′-azobisisobutyronitrile and 2,4-diphenyl-4-methyl. -1-Pentene (6 parts by mass) was charged and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.
To 200 parts by mass of the obtained copolymer solution, 13.4 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.2 part by mass of 4-methoxyphenol as a polymerization inhibitor were added and reacted at 90 ° C. for 2 hours. The reaction solution was washed twice with ion-exchanged water and concentrated under reduced pressure to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 5,800. This binder resin solution is referred to as “binder resin solution (B3)”.

Synthesis example 4
In a flask equipped with a condenser and a stirrer, 30 parts by mass of N-phenylmaleimide, 20 parts by mass of methacrylic acid, 20 parts by mass of styrene and 30 parts by mass of benzyl methacrylate are dissolved in 200 parts by mass of cyclohexanone, and 2,2′-azo Bisbutyronitrile (3 parts by mass) and 2,4-diphenyl-4-methyl-1-pentene (2 parts by mass) were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. and polymerized for 3 hours with stirring and nitrogen bubbling.
To 60 parts by mass of the obtained copolymer solution, 0.2 part by mass of 4-methoxyphenol, 0.2 part by mass of tetraethylammonium chloride and 40 parts by mass of cyclohexanone are added, and 3,4-epoxycyclohexylmethyl acrylate is further added. 1 part by mass was added and reacted at 90 ° C. for 30 hours. The reaction solution was washed with water twice while maintaining the solution temperature at 80 ° C., and concentrated under reduced pressure to obtain a binder resin solution (solid content concentration = 33 mass%). The obtained binder resin was Mw = 16,200 and Mn = 6,500. This binder resin solution is referred to as “binder resin solution (B4)”.

Example 1
(Preparation of colored radiation-sensitive composition)
100 parts by mass of pigment dye mixture (A1), 18 parts by mass of binder resin solution (B1) as a binder resin (solid content concentration = 33% by mass), KAYARAD MAX-3510 (dipentaerythritol manufactured by Nippon Kayaku Co., Ltd.) as a crosslinking agent 6 parts by mass of a mixture of hexaacrylate and dipentaerythritol pentaacrylate) and 6 parts by mass of KAYARAD DPCA-60 (caprolactone-modified dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., 2-benzyl-2-dimethyl as a photopolymerization initiator 1 part by weight of amino-1- (4-morpholinophenyl) butan-1-one and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) 3 parts by mass as a fluorosurfactant The DIC Corporation Megafac F-554 as a mixture of propylene glycol monomethyl ether acetate as a 0.2 parts by mass of a solvent, to prepare a green radiation-sensitive composition with a solid content of 15% by mass.

[Formation of pixel pattern and evaluation of color stability]
The obtained green radiation-sensitive composition was applied on a glass substrate using a slit die coater and then pre-baked on a 90 ° C. hot plate for 4 minutes to form a coating film having a thickness of 2 μm.
Next, after the substrate on which the coating film was formed was cooled to room temperature, the coating film was exposed at an exposure amount of 2,000 J / m ² through a striped photomask using an ultraviolet LED having a peak wavelength of 365 nm. Thereafter, a developer consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) on the obtained substrate, and shower development was performed for 1 minute. . Thereafter, this substrate was washed with ultrapure water and air-dried to form a green stripe pixel pattern on the substrate.
About the coating film before exposure and the formed pixel pattern, spectral characteristics were measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), and a color difference (ΔE * ab) was obtained. The evaluation results are shown in Table 1.

Examples 2-13
In Example 1, each colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type and content of each component were changed as shown in Table 1. Subsequently, using the obtained colored radiation-sensitive composition, a pixel pattern was formed and color stability was evaluated in the same manner as in Example 1 except that the exposure conditions were set as shown in Table 1. . The evaluation results are shown in Table 1.

Comparative Examples 1-6 and Reference Examples 1-2
Each colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type and content of each component were changed as shown in Table 2 in Example 1. Next, a pixel pattern was formed and the color stability was evaluated in the same manner as in Example 1 except that the exposure conditions were set as shown in Table 2 using the obtained colored radiation-sensitive composition. . The evaluation results are shown in Table 2.

In Tables 1 and 2, each component is as follows.
C1: caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPCA-60)
C2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and a mixture of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd., trade name TO-1382)
C3: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD MAX-3510)
C4: ethylene oxide oligomer-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPEA-12)
D1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
D2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name, manufactured by Ciba Specialty Chemicals) Irgacure OXE02)
D3: 2-mercaptobenzothiazole D4: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (Hodogaya Chemical Co., Ltd., product) Name B-CIM)
D5: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name CAYACURE DETX-S)
D6: 4,4′-bis (diethylamino) benzophenone D7: ADEKA Corporation, trade name NCI-930

Claims (4)

(1) forming a coating film of a colored radiation-sensitive composition containing at least one selected from the group consisting of a dye and a lake pigment on a substrate; and (2) an ultraviolet LED on at least a part of the coating film. A method of forming a pixel pattern, which includes a step of exposing using light.   A color filter comprising a pixel pattern formed by the method according to claim 1.   A display element comprising the color filter according to claim 2. (A) a colorant comprising at least one selected from the group consisting of dyes and lake pigments,
(B) binder resin,
A colored radiation-sensitive composition for forming a pixel pattern by ultraviolet LED exposure, comprising (C) a crosslinking agent, and (D) a photopolymerization initiator.