KR20050014725A - Color filter for lcd - Google Patents

Abstract

PURPOSE: A color filter for an LCD(Liquid Crystal Display) is provided to make it possible to reproduce a natural color by including a cyan color as a coloring agent which has a specific CIE(Commission International de I Eclairage) standard value. CONSTITUTION: A plurality of pixels with a plurality of colors are formed on a substrate. The pixels with the colors are comprised of pixels having a red color(R), a green color(G), a blue color(B) and a cyan color(C). CIE standard values in CIE chromaticity of the pixels are included in ranges of red color(R)(x=0.50-0.70,y=0.28-0.36), green color(G)(x=0.20-0.33,y=0.50-0.73), blue color(B)(x=0.13-0.17,y=0.04-0.11), and cyan color(C)(x=0.08-0.20,y=0.25-0.70).

Description

Color filter for LCD {COLOR FILTER FOR LCD}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to color filters, and more particularly to color filters having excellent color reproducibility used in liquid crystal display devices (LCDs).

The color filter is an essential component of a liquid crystal display (hereinafter also referred to as "liquid crystal display device" or "LCD"). This liquid crystal display is very compact, and in terms of performance, is equal to or larger than the CRT display so far, and has been changed from a CRT display to a liquid crystal display as a television screen, a personal computer screen, and other display devices.

In the formation of a color image of a liquid crystal display (LCD), the light passing through the color filter is colored as it is in the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. At present, a color image is formed by pixels of three colors of RGB. In other words, in the CIE chromaticity diagram, the ratio of three colors of RGB is changed to reproduce colors in the range of RGB triangles. Therefore, the color of the outside of the triangle represented by the three colors of this RGB cannot be reproduced.

In recent years, with the spread of liquid crystal display devices, their use has also been expanded to various monitors and TVs, and further improvements in color reproducibility have been required. In order to meet this demand, it is desired to provide a color filter having a wide color reproduction area. In particular, the expansion of the color reproduction area is demanded in TV use more conventionally.

In order to realize a bright and good color reproduction area, a method of specifying the CIE marker values of x, y, and Y of each RGB color, and realizing the pigment selection ratio, the mixing ratio, the particle size, and the mixing ratio of the pigment in the resist is disclosed. (For example, Japanese Patent Application Laid-open No. Hei 10-186124).

Also disclosed is a method of obtaining a color filter having a wide color reproduction region and high transmittance by the inkjet method by containing a water-soluble dye having x and y values in a specific range and a water-soluble dye having specific spectral characteristics in the CIE chromaticity diagram. (For example, Japanese Patent Laid-Open No. 11-158431).

In addition, a method is disclosed in which a fluorine-based compound having a hexafluoropropene structure is used as a surfactant, and a CIE chromaticity diagram of RGB is used to form a coating film having good color purity and good storage stability (for example, Japanese Patent Laid-Open No. 2001-139848.

An attempt to enlarge the color reproducibility of a reproduced image is, for example, as a photosensitive layer for a negative film of a color photographic film, in addition to the cyan layer, the magenta layer, and the yellow layer, a fourth layer is further formed to directly observe the subject. It is intended to improve the color reproduction by making the color tone close to the color tone or by multicolor printing of 6 to 7 colors with an inkjet printer.

As described above, in any of the above methods, there is a need for an LCD color filter that is insufficient as a color reproduction area of a color filter for a TV LCD and has excellent color reproducibility.

As described above, it is a reality that LCD color filters which can exhibit sufficient color reproducibility that can be preferably applied to TV applications have not yet been provided.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a color filter for LCDs having a wide color reproduction area capable of reproducing natural colors.

Fig. 1 is a hexagon surrounded by four points of four CIE marker values (x, y) on a CIE 1931 standard indicator chromaticity diagram of a cyan (C-5) unexposed state film obtained in Example 1; The chromaticity diagram which shows.

Fig. 2 is a chromaticity diagram showing a triangle surrounded by three points of CIE marker values (x, y) on the CIE 1931 standard display chromaticity diagram of each of the colors R, G, and B of the color filter of the comparative example.

As a result of examining various colorants with respect to color reproducibility, in particular, the color reproducibility is obtained by adding cyan (C) color having a specific CIE marking value (hereinafter also referred to as "chromaticity") in the CIE chromaticity diagram as a colorant. The present invention has been found to be noticeably enlarged in the region.

<1> A color filter for an LCD comprising a plurality of pixels formed on a substrate, wherein the plurality of pixels comprise red (R), green (G), blue (B), and cyan (C) pixels. And the CIE marking value in the CIE chromaticity diagram of the pixel is in the following range.

Red (R): x = 0.60-0.69, y = 0.30-0.35

Green (G): x = 0.20 to 0.32, y = 0.50 to 0.73

Blue (B): x = 0.13 to 0.17, y = 0.04 to 0.11

Cyan (C): x = 0.08-0.20, y = 0.30-0.65

<2> The color filter for LCD according to <1>, wherein the cyan (C) pixel contains at least one of the following colorants.

Colorant (i): C.I. Pigment Green 7 (PG7),

Colorant (ii): C.I. Pigment Green 7 (PG7) and C.I. Pigment Yellow 150 (PY150) mixture,

Colorant (iii): C.I. Pigment Blue 15: 3 (PB15: 3) and C.I. Pigment Yellow 150 (PY150) mixture,

Colorant (iv): aluminum phthalocyanine and C.I. Pigment Yellow 150 (PY150) mixture,

Colorant (v): C.I. Pigment Green 7 (PG7) and C.I. Pigment blue 15: 6 (PB15: 6) mixture,

Colorant (vi): C.I. Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. Mixture of Pigment Yellow 150 (PY150)

<3> The color filter for LCD as described in <1> or <2> whose mixing ratio of PG7 and PY150 in the said coloring agent (ii) is 100/5-100/100 (mass ratio).

The mixing ratio of PB15: 3 and PY150 in said coloring agent (iii) is 100/5-100/400 (mass ratio) in any one of <4> <1>-<3>. Color filter.

Aluminum phthalocyanine and C.I. in any one of <5> <1>-<4> in the said coloring agent (iv). Pigment Yellow 150 (PY150) The mixing ratio of the color filter for LCD, characterized in that 100/5 to 100/100 (mass ratio).

C.I. in any one of <6> <1>-<5> in the said coloring agent (v). Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) The mixing ratio of the color filter for LCD, characterized in that 100/10 to 100/50 (mass ratio).

C.I. in any one of <7> <1>-<6> in the said coloring agent (vi). Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. Pigment Yellow 150 (PY150) The mixing ratio of the color filter for LCD, characterized in that 100/5/5 to 100/50/50 (mass ratio).

Hereinafter, the color filter for LCDs of this invention is demonstrated in detail.

<< color filter for LCD >>

In the color filter for LCD of the present invention, a pixel of a plurality of colors formed on a substrate is composed of pixels of red (R), green (G), blue (B) and cyan (C), and the CIE 1931 XYZ color system of the pixel. The CIE marking value in the chromaticity diagram (hereinafter referred to as "CIE chromaticity diagram") is characterized by the following range.

Red (R): x = 0.50 to 0.70, y = 0.28 to 0.36

Green (G): x = 0.20 to 0.33, y = 0.50 to 0.73

Blue (B): x = 0.13 to 0.17, y = 0.04 to 0.11

Cyan (C): x = 0.08 to 0.20, y = 0.25 to 0.70

In addition, in the present invention, CIE marking values of pixels of red (R), green (G), blue (B), and cyan (C) should be in the above ranges, and x and y of preferred cyan (C) are preferred. The value is x = 0.08-0.20, y = 0.25-0.70, More preferably, it is x = 0.09-0.18, y = 0.30-0.65, Especially preferably, it is X = 0.10-0.17 and y = 0.32-0.63. . By setting the CIE marking values of RGB and cyan (C) within the above ranges, the CIE marking values are significantly improved compared with the conventional one, and the color reproduction area can be increased by 30%.

The color filter for LCD of this invention is formed by what is called photocurable coloring composition for LCD which consists of four types of pixel regarding the chromaticity of red (R), green (G), blue (B), and cyan (C). It is composed of pixels of color. Hereinafter, the component of the photocurable coloring composition for LCD (henceforth a "coloring composition") is demonstrated.

(Photocurable coloring composition for LCD)

As a photocurable coloring composition for LCD in the color filter of this invention, coloring agents, such as an alkali-soluble resin and a pigment component, a photosensitive polymerization component, and a photoinitiator are made into components, and it is a thing for improving the hardening | curing degree of a thermal polymerization inhibitor and a film | membrane. It can contain and contain a crosslinking agent and another component. Generally, it contains a solvent (henceforth an organic solvent). The said photocurable coloring composition for LCD can be comprised in negative form by containing the said photosensitive polymerization component and a photoinitiator.

In addition, the color filter of this invention has the same structure as a well-known color filter, and can be manufactured using a well-known manufacturing method.

Each component of the said photocurable coloring composition for LCDs in this invention is demonstrated.

-coloring agent-

As a coloring agent which implements the cyan (C) color of the photocurable coloring composition for LCD, any well-known pigment and dye can be used as long as it satisfy | fills the said CIE marking value (henceforth "CIE chromaticity").

As cyan pigment, specifically, C.I. Pigment Blue 15: 1 (PB15: 1), C.I. Pigment Blue 15: 2 (PB15: 2), C.I. Pigment Blue 15: 3 (PB15: 3), C.I. Pigment Blue 15: 4 (PB15: 4), C.I. Pigment Blue 15: 6 (PB15: 6), C.I. Pigment Green 7 (PG7), C.I. Pigment Green 36 (PG36) and an aluminum phthalocyanine pigment are used preferably.

By using these pigments, even when a thin film is used, high chromaticity and color concentration can be obtained, high color purity and good color reproducibility can be obtained.

As said aluminum phthalocyanine pigment, the compound represented by the following structural formula (I) is preferable. Moreover, the dimer which two molecules of this compound couple | bonded may be sufficient.

In said structural formula (I), X represents OH, Cl, or Br. R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same as or different from each other. Y represents the integer of 0-4.

Among the aluminum phthalocyanine pigments represented by the above structural formula (I), the compound represented by the following structural formula (II) is particularly preferable. Also preferred are dimers in which two molecules of this compound are bonded via an oxygen atom of an OH group.

Moreover, as cyan dye, if it is a thing of the said CIE label value, there will be no restriction | limiting in particular, Any dye can be used as long as it does not interfere with the objective. As said dye, the well-known dye mentioned later for a conventional color filter is also mentioned.

Especially, from a viewpoint of chromaticity and light resistance, it is preferable that a phthalocyanine type dye, for example, a center metal is Cu, Ni, Co Zn, Al, and copper phthalocyanine dye and aluminum phthalocyanine dye are especially preferable. For example, a -SO ₃ M and -COOM (M is an alkali metal) substituent is bonded to the four aromatic rings of the outermost nucleus of the formula (II).

As phthalocyanine-based dyes, Japanese Patent Laid-Open No. 60-249102, Japanese Patent Laid-Open No. 63-280083, Japanese Patent Laid-Open No. 2-19803, Japanese Patent Laid-Open No. 2-108004 and Japanese Patent Publication What is disclosed in Unexamined-Japanese-Patent No. 7-49412 etc. is mentioned.

The cyan pigment and dye can be used in combination with a yellow pigment.

As said yellow pigment, it can select suitably from the conventionally well-known inorganic or organic yellow pigment, For example, a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, an iso indolin yellow pigment, etc. Can be mentioned. Specifically, C.I. Pigment Yellow (PY) 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199, etc. are preferable. And CI Pigment Yellow 83, 93, 109, 110, 138, 139, 150, 154, 180, or 185 is preferred, and Pigment Yellow 138, 150, 180 or 185 is preferred, and PY150 and PY180 are most preferred. Do. These yellow pigments may use not only 1 type but 2 types or more together.

Among the cyan colorants, the colorant (i): C.I. Pigment green 7 (PG7), colorant (ii): C.I. Pigment Green 7 (PG7) and C.I. Pigment Yellow 150 (PY150) mixture, colorant (iii): C.I. Pigment Blue 15: 3 (PB15: 3) and C.I. Pigment Yellow 150 (PY150) mixture, colorant (iv): aluminum phthalocyanine (AL-PC) and C.I. Pigment Yellow 150 (PY150) mixture, colorant (v): C.I. Pigment Green 7 (PG7) and C.I. Pigment blue 15: 6 (PB15: 6) mixture, colorant (vi): C.I. Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. It is preferable to contain at least one of the colorants of the mixture of Pigment Yellow 150 (PY150).

C.I. which is the coloring agent (ii). Pigment Green 7 (PG7) and C.I. As the mixing ratio (mass ratio) in the mixture of pigment yellow 150 (PY150) (hereinafter also referred to as "PG7 / PY150") from the point of chromaticity, it is 100/5- It is preferable that it is 100/100, Furthermore, 100/10-100/80 are preferable, and 100/15-100/60 are especially preferable.

C.I., which is the colorant (iii). Pigment Blue 15: 3 (PB15: 3) and C.I. As a mixing ratio (mass ratio) in the pigment yellow 150 (PY150) mixture (henceforth "PB15: 3 / PY150"), it is preferable that it is 100 / 5-100 / 400 from a chromaticity point, 100/10-100/300 are preferable and 100/15-100/200 are especially preferable.

The aluminum phthalocyanine pigment (AL-PC) which is the said coloring agent (iv) is preferable also in the case of using together alone or in combination with other pigments, such as PY150, as mentioned above, Especially when using together, mixture with PY150 is preferable. Do.

AL-PC and C.I. As a mixing ratio (mass ratio) in the pigment yellow 150 (PY150) mixture (henceforth "AL-PC / PY150"), it is preferable that it is 100/5-100/100 from a chromaticity point, 100 / 8-100 / 90 is preferable and 100 / 10-100 / 85 is especially preferable.

C.I., which is the colorant (v). Pigment Green 7 (PG7) and C.I. As a mixing ratio (mass ratio) in Pigment Blue 15: 6 (PB15: 6) mixture (henceforth "PG7 // PB15: 6"), it is 100/10-100/50 from a chromaticity point. It is preferable, and 100/15-100/40 are preferable and 100/20-100/35 are especially preferable.

C.I. in said coloring agent (vi). Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. As a mixing ratio (mass ratio) in pigment yellow 150 (PY150) mixture (henceforth "PG7 / PB15: 6 / PY150"), it is 100/5/5-100/50/50 from a chromaticity point. It is preferable that it is more, and 100/10/10-100/40/40 is preferable, and 100/20/20-100/35/35 is especially preferable.

As said green (G) pigment in this invention, conventionally well-known green pigments other than the said aluminum phthalocyanine pigment can also be used, Either an inorganic or an organic pigment may be sufficient, For example, CI pigment green 7, 7 And halogenated phthalocyanine-based pigments such as 37 and the like. These may use not only 1 type but 2 types or more together.

As the blue (B) colorant in the present invention, conventionally known inorganic or organic colorants can be used, and include triphenylmethane, phthalocyanine, anthraquinone, triarylmethane, disazo and indigoide. Organic or inorganic pigments are preferred, and among these, phthalocyanine pigments are more preferable.

Specifically, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment blue 15: 6, and the like.

Moreover, as dyes other than the pigment and dye used for the said coloring agent, if it exists in the range of the said CIE labeling value, there will be no restriction | limiting in particular and it is known dye for conventional color filters, for example, Unexamined-Japanese-Patent No. 64-90403. Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. Hei 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, US Patent No. 4,808,501, US Patent No. 5,667,920 JP-A-5,059,500, JP-A 5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. Pigment | dye. Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine and pyrrolopyrazole azo. And dyes such as methine.

As a total amount of the coloring agent of cyan (C) in the photocurable cyan composition for LCDs in this invention, 5-60 mass% is especially preferable with respect to the total solid (mass) of the said composition, and chromaticity of a color filter 10-50 mass% is more preferable from a viewpoint of the balance of a film thickness and 15-45 mass% is especially preferable.

As a total amount of the coloring agent of red (R) in the photocurable red composition for LCDs in this invention, 5-60 mass% is especially preferable with respect to the total solid (mass) of the said composition, and chromaticity of a color filter 10-50 mass% is more preferable from a viewpoint of the balance of a film thickness and 15-45 mass% is especially preferable.

As a total amount of the coloring agent of green (G) in the photocurable green composition for LCDs in this invention, 5-60 mass% is especially preferable with respect to the total solid (mass) of the said composition, and chromaticity of a color filter 10-50 mass% is more preferable from a viewpoint of the balance of a film thickness and 15-45 mass% is especially preferable.

As a total amount of the coloring agent of blue (B) in the photocurable blue composition for LCDs in this invention, 5-60 mass% is especially preferable with respect to the total solid (mass) of the said composition, and chromaticity of a color filter 10-50 mass% is more preferable from a viewpoint of the balance of a film thickness and 15-45 mass% is especially preferable.

The ratio between the colors in the color filter of the present invention, that is, the colorant, can be appropriately selected for the purpose such as color.

By selecting the colorant as described above, the CIE marker value on the CIE chromaticity diagram by the C light source of the pixels of red (R), green (G), blue (B) and cyan (C) is red (R): x = 0.50 to 0.70, y = 0.28 to 0.36, green (G): x = 0.20 to 0.33, y = 0.50 to 0.73, blue (B): x = 0.13 to 0.17, y = 0.04 to 0.11, cyan (C): x Color filters for LCDs satisfying = 0.08 to 0.20 and y = 0.25 to 0.70 can be easily obtained, thereby greatly widening the color reproduction region. In Example 1 of the present specification, the color reproduction area of 30% could be enlarged.

The color reproduction region of the color filter refers to a range of triangles surrounded by three CIE marker values (x, y) on the CIE chromaticity diagram of red (R), green (G), and blue (B), that is, This is the range in which color reproduction is possible. Therefore, it becomes an area | region which color reproduction is impossible except the range of the said triangle.

By adding new cyan (C) here, one point of new CIE mark values (x, y) is added in addition to the conventional CIE mark values (x, y). That is, a new color reproducible area is generated in addition to the conventional triangular range, and as a result, a color filter suitable for an LCD (liquid crystal display device) requiring natural color reproduction can be obtained.

In addition, as a measuring method of the CIE marker value (chromatic point) on the CIE chromaticity diagram by the C light source of a color filter, (1) a colorimeter (made by Otsuka Denshi Co., Ltd.) etc. with respect to the coating film of each color on a transparent board | substrate. Method of measuring CIE marker value (x value, y value) using (2) measuring each pixel formed on the transparent substrate using a microspectral photometer, or (3) a size of about 3cm × 3cm The method which produced a pixel and measured with a normal ultraviolet visible spectrophotometer etc. is used, and measured in this invention using the method of (1).

The pigment used as said coloring agent can make dispersibility and dispersion stability favorable by using it as a powdery process colorant undispersed in acrylic resin, maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc. .

Next, the processing method of a pigment is demonstrated.

In this invention, it is preferable to process a pigment with various resin previously. That is, the pigment is generally dried after synthesis, and dried in various ways. Usually, the pigment is dried from a water medium and supplied as a powder. However, a large amount of latent heat of evaporation is required for drying the water, and a large thermal energy is required for drying the powder. Gives. Therefore, it is common for the pigments to form aggregates (secondary particles) in which primary particles are aggregated, and it is not easy to disperse the pigments forming such aggregates in the fine particles, so that it is easy to disperse the resins in advance. desirable. As resin here, alkali-soluble resin mentioned later is mentioned.

As the method of the dispersion treatment, there is a flashing treatment, a kneading method using a kneader, an extruder, a ball mill, two or three roll mills, or the like. Among them, a flashing treatment or a kneading method using two or three roll mills is preferable for atomization.

The flashing treatment is a method of mixing a water dispersion of a pigment and a resin solution dissolved in a solvent which is incompatible with water, extracting the pigment from the water medium into the organic medium, and treating the pigment with a resin. According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion becomes easy. In addition, in the kneading by the two or three roll mills, after mixing the pigment and the solution of the resin or the resin, the pigment is coated by coating the pigment surface by kneading the pigment and the resin while applying a high shear force. That's how to handle it. Pigment particles aggregated in this process are dispersed from lower aggregates to primary particles.

Moreover, it can also be used as a processing pigment previously processed with acrylic resin, a vinyl chloride-vinyl acetate resin, maleic acid resin, an ethyl cellulose resin, a nitrocellulose resin. As a form of this process pigment, the powder, paste form, and pellet form in which resin and a pigment are disperse | distributed uniformly is preferable. In addition, it is not preferable that the resin is a gelled nonuniform mass.

In order to improve the dispersibility of the said pigment, a conventionally well-known pigment dispersant and surfactant can be used together. Examples of the pigment dispersant and the surfactant include various kinds of compounds, but examples thereof include phthalocyanine derivatives (EFKA-745 from Efca Co.) and Solsper 5000 (Geneca Co.); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushikagaku Kogyo Co., Ltd.), W001 ( Cationic surfactants such as those produced by Yutaka Shoji; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yutaka Shoji); EFKA-46, EFKA-47, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, Morishitasan Co., Ltd.), Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Disperse Ade Polymer dispersants such as 9100 (manufactured by Sanofucco), etc .: Various solvent dispersants such as Solsper 3000, Copper 5000, Copper 9000, Copper 12000, Copper 13240, Copper 13940, Copper 17000, Copper 24000, Copper 26000, Copper 28000, etc. Four products); Adeka Pluronic L31, East F38, East L42, East L44, East L61, East L64, East L68, East L72, East P95, F77, East P84, East F87, East P94, East L101, East P103, East F108 And L121, P-123 (manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.).

Alkali Soluble Resin

It is preferable that the said photocurable coloring composition for LCD in this invention contains at least 1 sort (s) of alkali-soluble resin. It does not specifically limit as alkali-soluble resin, It is a linear organic polymer polymer, It is preferable to be soluble in an organic solvent, and to develop with weak alkaline aqueous solution.

As such linear organic polymer, a polymer having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, as described in the respective publications of 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 And maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are likewise mentioned. In addition to the above, those in which an acid anhydride is added to a polymer having a hydroxyl group are also useful.

Among these, in particular, a multipart copolymer composed of a benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomers is preferable. In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful as a water-soluble polymer. Moreover, in order to raise the intensity | strength of a cured film, alcohol-soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl)-propane, epichlorohydrin, etc. are also useful. These polymers can be mixed and used in arbitrary quantities.

In addition, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropylacryl acrylate described in JP-A-7-140654 Rate / Polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

Preferred alkali-soluble resin in this invention has a carboxyl group in a side chain especially. Moreover, it is preferable that acid values are 30-200 from a viewpoint which maintains developability and applicability | paintability after exposure favorably.

As mentioned above, alkali-soluble resin is generally the acryl-type copolymer which mostly used unsaturated carboxylic acid for the copolymerizable monomer. Especially, the acrylic copolymer which has a polyalkylene oxide chain | strand in a side chain improves the liquid characteristic at the time of preparing the photocurable coloring composition for LCD in coating liquid form, and there is little problem of the residual liquid in a coating piping, It is preferable at the point which becomes a thin film and the coating film of uniform thickness becomes easy to obtain. In particular, a favorable coating film with a high yield can be obtained with respect to the slit coating suitable for application | coating to the board | substrate of wide width and a large area.

As total amount in the photocurable coloring composition for LCD of the said alkali-soluble resin, 5-80 mass% is preferable with respect to a total solid component (mass), More preferably, it is 20-60 mass%. When the total amount is less than 5% by mass, the film strength may be lowered. When the total amount is more than 80% by mass, the acid component increases, so that the solubility is difficult to control, or the amount of pigment is relatively low, so that sufficient image concentration cannot be obtained. There is a thing.

Moreover, in order to improve the crosslinking efficiency of the photocurable coloring composition for LCDs in this invention, you may have a polymeric group in the side chain of alkali-soluble resin, and an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. can be added to a side chain. The containing polymer is also useful. Although the example of the polymer containing these polymerizable groups is shown, if an alkali-soluble group, such as a COOH group, an OH group, and an ammonium group, contains an unsaturated bond between carbon, it is not limited to the following.

As a specific example, in the copolymer of 2-hydroxyethyl acrylate which has an OH group, for example methacrylic acid containing a COOH group, and monomers, such as an acryl-type or vinyl type compound copolymerizable with these, an OH group The compound etc. which are obtained by making a compound (for example, glycidyl acrylate compounds etc.) which have an epoxy ring which has reactivity with the unsaturated carbon-to-carbon unsaturated bond group react can be used. In reaction with an OH group, the compound which has an acid anhydride, an isocyanate group, and an acryloyl group can also be used besides an epoxy ring. Moreover, saturated or unsaturated polybasic acid anhydride is reacted with the compound obtained by making unsaturated carboxylic acid, such as acrylic acid, react with the compound which has the epoxy ring of Unexamined-Japanese-Patent No. 6-102669 and 6-1938. The reactant obtained by making it available can also be used. As a compound which also has an alkali solubilizer and a carbon-to-carbon unsaturated group, such as a COOH group, For example, Diamond NR series (made by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co. Ltd., product); Biscot R-264, KS Resist 106 (all manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.); Cyclomer P Series and Flexel CF200 Series (both manufactured by Daicel Kagaku Kogyo Co., Ltd.); Ebecry 13800 (made by Daicel Yushibi Co., Ltd.), etc. are mentioned.

Photosensitive polymerization component

It is preferable that the photocurable coloring composition for LCDs in this invention contains at least 1 sort (s) of the photosensitive polymerization component. As the photosensitive polymerization component, a compound having an ethylenically unsaturated group capable of at least one addition polymerization and having a boiling point of 100 ° C. or higher at normal pressure is preferred, and an acrylate compound having four or more functional groups is more preferable.

As said "compound which has at least 1 addition-polymerizable ethylenically unsaturated group and has a boiling point of 100 degreeC or more under normal pressure", For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as cyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethol propane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japan Urethane acrylates described in Japanese Patent Application Laid-Open No. 50-6034, Japanese Patent Laid-Open No. 51-37193, and Japanese Patent Publication No. 48-64183, Japan Polyfunctional acrylates and meta, such as the polyester acrylates described in each of Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490, and epoxy acrylate which is a reaction product of epoxy resin and (meth) acrylic acid. Acrylate is mentioned. In addition, Japan Adhesion Society Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also be used.

Further, as a compound obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol (meth) acrylate, general formula (1) or (&lt; / RTI &gt; What was described as 2) can also be used as a photosensitive polymerization component.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable.

Moreover, an oligomer type is also preferable and the acryl-type oligomer whose repeating unit of a monomer is 3-20 (preferably 3-10) is preferable. In particular, the repeating unit of the compound represented by the following general formula (I), that is, an alkyl compound having a trimethol group such as trimetholpropane or pentaerythritol is 3 to 10, and is represented by Y (ether, ester, urethane) The compound which has at least 1 of a bond and has 7 or more acryloyl groups is preferable.

In the said general formula (I), A represents a C1-C5 alkyl compound or pentaerythritol which has a trimetholol group, X represents an acryloyl group, a hydrogen atom, a C1-C8 alkyl group, and Y is -O-, group derived from the compound which has a divalent or more carboxylic acid, group derived from the compound which has a divalent or more isocyanate, and R <_1> represents (poly) alkylene oxide and (poly) caprolactam. n represents an integer from 1 to 18, m represents 0 or 1 (1 represents when A is pentaerythritol), and 1 represents 0 or 1.

When the acrylic oligomer is used as the photosensitive polymerization component, the exposure sensitivity is large and the polymerization strength is increased. Therefore, the pattern peeling when developing with a developing solution is less likely to occur, and thus, the development latitude is increased. You can widen it.

In addition, said photosensitive polymerization component can be used not only 1 type individually but in combination of 2 or more types.

Photoinitiator

It is preferable that the photocurable coloring composition for LCDs in this invention contains at least 1 sort (s) of a photoinitiator. As a photoinitiator, active halogen compounds, such as halomethyloxadiazole and halomethyl-s-triazine, a 3-aryl substituted coumarin compound, at least 1 type of lophine dimer, etc. are mentioned. Especially halomethyl-s-triazine type compound is preferable. Hereinafter, these compounds are demonstrated in detail.

Among the active halogen compounds such as halomethyl oxadiazole and halomethyl-s-triazine, as the halomethyl oxadiazole compound, 2-halomethyl represented by the following general formula II described in Japanese Patent Publication No. 57-6096 -5-vinyl-1,3,4-oxadiazole compound is mentioned.

In the general formula (II), W represents a substituted or unsubstituted aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, and Y represents a fluorine atom, a chlorine atom or a cancel atom. n represents the integer of 1-3.

As a specific example of the compound represented by the said General formula (II), 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5- (p-cyanostyryl) -1 , 3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, and the like.

As a halomethyl-s-triazine type compound, the vinyl-halomethyl-s-triazine compound represented by following General formula III described in Unexamined-Japanese-Patent No. 59-1281, and Unexamined-Japanese-Patent No. 53-133428 are described. 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by formula IV below and 4- (p-aminophenyl) -2 represented by formula V below And a 6-di-halomethyl-s-triazine compound.

In Formula III, Q represents Br or Cl, P represents -CQ ₃ (Q represents Br or Cl), -NH ₂ , -NHR, -N (R) ₂ , or -OR, wherein R represents a phenyl or alkyl group). W represents the aromatic group which may be substituted, the heterocyclic group which may be substituted, or the monovalent group represented by the following general formula IIIa.

In the general formula (IIIa), Z represents -O- or -S-, and R represents a phenyl or alkyl group.

In the general formula (IV), X represents Br or Cl. m and n respectively independently represent the integer of 0-3. R 'represents a group represented by the following general formula (IVa).

In the general formula (IVa), R ¹ represents a hydrogen atom or ORc (Rc represents an alkyl, cycloalkyl, alkenyl, aryl group), R ² represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group. .

In the general formula V, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by the following general formula Va or Vb, which may be the same as or different from each other. . R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and these may be the same as or different from each other. X and Y each independently represent Cl or Br, and may be the same as or different from each other. m and n each independently represent 0, 1 or 2, which may be the same as or different from each other.

In said general formula Va and Vb, R <^5> , R <^6> and R <^7> respectively independently represent an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Examples of the substituent in the substituted alkyl group and the substituted aryl group include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, and the like. Can be.

In the above general formula (V), R ¹ and R ² may form a heterocyclic ring composed of a nonmetallic atom together with the nitrogen atom which is bonded to them, and in that case, those shown below may be mentioned as heterocycles.

Specific examples of the compound represented by the general formula III include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,4-bis (trichloromethyl) -6- (1-p-dimethyl aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, etc. are mentioned. have.

As a specific example of the compound represented by the said general formula (IV), 2- (naphtho-1-yl) -4 6-bis-trichloromethyl-s-triazine and 2- (4-methoxy-naphtho-1- Il) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxy ethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-tri Azine, 2- [4- (2-butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1 -Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s -Triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-tria Gin, 2- (4,7-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and the like Can be mentioned.

As a specific example of the compound represented by the said General formula V, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarba Carbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s -Triazine, 4- [mN, N-di (ethoxy) Cycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonyl Methyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [O-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (t Chloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m -Bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m- (bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN -Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o -Chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trickle) Roromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bro Parent-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl ) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloro Ethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-tri Azine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

A sensitizer can be used together for said photoinitiator. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluolinone, 2-chloro-9-fluolinone, 2-methyl-9-fluolenonon, 9-anthrone, 2-bro Parent-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6 -Dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylke Ton, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or mihiraketone), p- (diethylamino) benzophenone, benzoanthrone, etc. And benzothiazole compounds described in JP-A-51-48516.

As said 3-aryl substituted coumarin compound mentioned above as a photoinitiator, the compound represented by the following general formula VI is mentioned, for example.

In general formula VI, R <^8> represents a hydrogen atom, a C1-C8 alkyl group, a C6-C10 aryl group (preferably, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group), and R <^9> represents hydrogen Atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIa (preferably a methyl group, an ethyl group, a propyl group, a butyl group, a group represented by the following general formula VIa, especially Preferably, the group represented by the following general formula (VIa) is shown.

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, etc.), and a haloalkyl group having 1 to 8 carbon atoms (eg, For example, a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, etc.), a C1-C8 alkoxy group (for example, a methoxy group, an ethoxy group, butoxy group etc.), the C6-C10 aryl group which may be substituted (Eg, a phenyl group), an amino group, -N (R ¹⁶ ) (R ¹⁷ ), and a halogen atom (eg, Cl, Br, F, etc.). Preferably, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl ^{group, -N (R 16) (R} 17), Cl.

R <^12> in the said General formula VI represents the C6-C16 aryl group (for example, a phenyl group, a naphthyl group, a tolyl group, a cumyl group, etc.) which may be substituted. Examples of the substituent in the case of substitution include an amino group, -N (R ¹⁶ ) (R ¹⁷ ), an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, octyl group, etc.) A haloalkyl group of 8 (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group, etc.), hydroxy group, cyano group And halogen atoms (for example, Cl, Br, F, etc.).

R ¹³ and R ¹⁴ in the general formula VIa and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group, etc.) These may be the same as or different from each other. R ¹³ and R ¹⁴ and R ¹⁶ and R ¹⁷ are bonded to each other to form a heterocyclic ring (for example, piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring together with a nitrogen atom). Etc.) may be formed.

In general formula VIa, R <^15> is a hydrogen atom, a C1-C8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, etc.), a C1-C8 alkoxy group (for example, methoxyl Time period, ethoxy group, butoxy group, etc.), an optionally substituted aryl group having 6 to 10 carbon atoms (e.g., phenyl group), amino group, N (R ¹⁶ ) (R ¹⁷ ), halogen atom (e.g., Cl, Br , F and the like).

Zb in the general formula VI represents = O, = S or = C (R ¹⁸ ) (R ¹⁹ ). Preferably it is = O, = S, = C (CN) ₂ , Especially preferably, it is = O. R ¹⁸ and R ¹⁹ may be the same or different and each independently represent a cyano group, -COOR ²⁰ , or -COR ²¹ . R ²⁰ and R ²¹ each independently represent an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group, etc.), a haloalkyl group having 1 to 8 carbon atoms (eg, chloromethyl group, Fluoromethyl group, trifluoromethyl group, etc.) and the C6-C10 aryl group (for example, phenyl group) which may be substituted.

Particularly preferred examples of the 3-aryl substituted coumarin compound include {(s-triazin-2-yl) amino} -3-arylcoumalin compounds represented by the following general formula VII. Here, R ¹³ in the formula VII, R ^14, and R ¹⁵ is the same as R ^13, R ^14, and R ¹⁵ in formula VIa.

The above-mentioned lophine dimer mentioned as a photoinitiator means the 2,4,5-triphenyl imidazolyl dimer which consists of two lophine residues, The basic structure is shown below.

Specific examples thereof include 2- (o-crophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, and 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4, 5-diphenyl imidazolyl dimer etc. are mentioned.

In this invention, other well-known compounds other than the photoinitiator mentioned above can also be used. For example, the bisinal polyketolaldenyl compounds described in US Pat. No. 2,367,660, the α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367 670, and the acyl described in US Pat. No. 2,448 828 Inethers, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, and triallyl described in US Pat. No. 3,549,367. The combination of midazole dimer / p-aminophenyl ketone and the benzothiazole type compound / trihalomethyl-s-triazine type compound of Unexamined-Japanese-Patent No. 51-48516 are mentioned. In addition, Adeka Optomer SP-150, 151, 170, 171, N-1717, N1414, etc. manufactured by Asahi Denka Co., Ltd. can also be used as a polymerization initiator.

As content in the photocurable coloring composition for LCD of the said photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid (mass) of the said composition, More preferably, it is 0.5-5.0 mass%. When the said content is less than 0.1 mass%, superposition | polymerization may become difficult to progress, and when it exceeds 10.0 mass%, film strength may weaken.

-solvent-

At the time of preparation of the photocurable coloring composition for LCDs in this invention, it contains a solvent (also called an "organic solvent" in this specification) generally. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the photocurable coloring composition for LCD, but is preferably selected in consideration of the solubility, coating property, and safety of the colorant and the resin component.

Examples of the solvent include esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl acid butyrate, ethyl butyrate, butyl butyrate and alkyl Esters, methyl lactate, ethyl lactate, methyl oxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, ethoxy acetate, ethyl ethoxy acetate, and the like; 3-oxypropionate alkyl esters, such as 3-oxymethylpropionate and 3-oxyethylpropionate, for example, 3-methoxypropionate, 3-methoxyethylpropionate, 3-ethoxypropionate and 3-ethoxy Ethyl propionate and the like; 2-oxypropionate alkyl esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate and 2-methoxypropionic acid Propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate, 2-e Ethyl oxy-2-methyl propionate and the like; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like; Ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like are preferable.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable. These solvents may be used alone or in combination of two or more thereof.

Various additives

Various additives, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like, can be added to the photocurable coloring composition for LCD according to the present invention. have.

Specific examples of these additives include fillers such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, addition of acid anhydride to a polymer having a hydroxyl group, formed of alcohol soluble nylon, bisphenol A and epicrohydrin Alkali-soluble resins such as phenoxy resins; Surfactants, such as a nonionic, cationic, and anionic type, specifically, phthalocyanine derivative (EFKA-745 by Morishitasan Co., Ltd.): organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid type ( Cationic surfactants such as copolypolymer No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yutaka Shoji); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Esters (Pluronic L10, Copper L31, Copper L61, Copper L62, Copper 10R5, Copper 17R2, Copper 25R2, Tetronic 304, Copper 701, Copper 704, Copper 901, Copper 904, Copper 150R1 from BASF, etc.) Ionic surfactants: F-top EF301, copper EF303, copper EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), mega pack F-141, copper F-142, copper F-143, copper F-144 (Dainippon Ink Kagaku Kogyo ( Fluorine-based surfactants such as the following products); anionic surfactants such as W004, W005, and W017 (manufactured by Yutaka Shoji); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401 To EFKA polymer 450 (more than Morishita Sangyo), disperse aid 6, disperse Polymeric dispersants such as id 8, disperse aid 15, and disperse aid 9100 (manufactured by Sanofucco); Solsper's 3000, copper 5000, copper 9000, copper 12000, copper 13240, copper 13940, copper 17000, copper 24000, copper 26000 Various solvent dispersants (products made by Geneca) such as Copper, 28000, etc .; Adeka Pluronic L31, Copper F38, Copper L42, Copper L44, Copper L61, Copper L64, Copper F68, Copper L72, Copper P95, Copper F77, Copper P84, copper F87, copper P94, copper L101, copper P103, copper F1 08, copper L121, copper P-123 (manufactured by Asahi Denka Co., Ltd.), and isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.); vinyltrimethoxysilane , Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, 3-chloro Methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane trimethoxysilane, 3-mercaptopropyl trimethoxy silane adhesion promoter, such as; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And anti-agglomerating agents such as sodium polyacrylate.

Moreover, when promoting alkali solubility of a non-image part and improving further developability of the photocurable coloring composition for LCDs in this invention, the said composition has an organic carboxylic acid, Preferably, the molecular weight of 1000 or less is low molecular weight. An organic carboxylic acid can be added.

Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetate, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, azipine acid, pimeric acid, subberic acid, azelaic acid, sebacic acid, brazilian, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid, sheet Aliphatic dicarboxylic acids such as laconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconic acid and canhoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemeric acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, meropanic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydratropic acid, hydra cinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildenic acid, cumal acid, and undelane Can be mentioned.

Moreover, it is preferable to further add a thermal polymerization inhibitor to the photocurable coloring composition for LCD in this invention, for example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, Di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

The photocurable coloring composition for LCD in this invention mixes a coloring agent, an alkali-soluble resin, the photosensitive polymerization component, and a photoinitiator, and the various additives used as needed with a general solvent, and uses various mixers and a disperser. It can prepare by mixing and disperse | distributing.

For example, it can manufacture preferably as follows. That is, the photocurable coloring composition for LCD of this invention mixes and disperse | distributes an alkali-soluble resin and a solvent, or further adds a surface modifier or a dispersing agent to a coloring agent as needed.

The apparatus used for kneading | dispersing kneading | mixing is two rolls, three rolls, a ball mill, a disper, a kneader, a homogenizer, a blender, etc., and disperse | distributing, giving a strong shear force. Subsequently, a photosensitive polymerization component, a photopolymerization initiator, and a solvent, a dispersant, an alkali-soluble resin, and other components are further added to the obtained kneaded dispersion, and are mainly 0.1 using a sand grinder, a pin mill, a slit mill, an ultrasonic disperser, and the like. Beads made of glass, zirconia, or the like having a particle diameter of ˜10 mm are microdispersed as a dispersion medium. It is also possible to omit the kneading dispersion process. In that case, it disperse | disperses with a coloring agent, a dispersing agent, or a surface treating agent, alkali-soluble resin, and a solvent.

Moreover, about the detail of kneading dispersion, T.C. Patton's book, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

Manufacturing Method

The color filter of the present invention uses at least four types of colored compositions each containing the photocurable cyan composition, the photocurable red composition, the photocurable green composition, and the curable blue composition according to the present invention. After applying any one selected from the colored composition of the species on the substrate, it is exposed through a mask, and developed to form a pixel of the first color, and after forming the pixel of the first color, the color selected from the colored composition Another color different from the first color pixel was applied onto the substrate, and then exposed through a mask, developed to form a second color pixel, and again after the formation of the second color pixel, the coloring composition. Another one different in color from the first color and the second color selected from is applied onto the substrate, and then exposed through a mask and developed to form a third color pixel. , Will then finally form the pixels of the third saekjjae, after applying the coloring composition of the remaining on the substrate, and exposed through a mask, developing it is obtained by forming pixels of the fourth saekjjae. That is, four types of pixels are formed by further adding a fourth color (cyan) to three colors of conventional RGB.

That is, at least four color compositions of the photocurable cyan composition, the photocurable green composition, the photocurable red composition, and the photocurable blue composition for LCD according to the present invention are rotated on a substrate in a predetermined color order, It is applied by a coating method such as flexible coating or roll coating and dried to form a radiation-sensitive layer (light), which is then exposed to light through a predetermined mask pattern and developed with a post-exposure developer. The step of forming a pixel forming a predetermined pattern can be obtained by repeating at least four times in accordance with the number of colored compositions. At this time, if necessary, a step of curing the formed pixel by heating and / or exposure can be provided.

The said exposure can be performed by irradiation of radiation, and especially as said radiation, ultraviolet rays, such as g line | wire, h line | wire, i line | wire, are used preferably.

As described above, using the photocurable coloring composition for LCD, it consists of four types of pixels of red (R), green (G), blue (B), and cyan (C), and CIE 1931 of the pixel. The CIE marker value of the XYZ display system is red (R): x = 0.50-0.70, y = 0.28-0.36, green (G): x = 0.220-0.33, y = 0.50-0.73, blue (B): x = 0.13- The color filter for LCD of this invention which is 0.17y = 0.04-0.11, cyan (x): x = 0.08-0.20, y = 0.25-0.70 can be produced and provided.

The x and y values of the CIE chromaticity coordinates of the cyan (C) are as described above.

The x and y values of the CIE chromaticity coordinates of the red (R) need to be in the above range, but the preferred x and y values are x = 0.55 to 0.70 and y = 0.29 to 0.36, and particularly preferably , X = 0.60-0.69, y = 0.30-0.35.

In addition, although the x value and y value of said CIE chromaticity coordinate of green (G) need to be in the said range, preferable x and y values are x = 0.23-0.33 and y = 0.53-0.80, Especially preferably, Is x = 0.25-0.32 and y = 0.55-0.65.

In addition, although the x value and y value of said CIE chromaticity coordinate of green (B) need to be in the said range, preferable x and y values are x = 0.13-0.15 and y = 0.05-0.10, Especially preferably, , x = 0.25 to 0.32, y = 0.55 to 0.65. By expanding the CIE marking values of red (R), green (G), blue (B), and cyan (C) within the above ranges, sufficient enlargement of the color reproduction area can be achieved.

The thickness of the colored film which comprises the color filter of this invention can be comprised with the thin film of 2.5 micrometers or less (preferably 2.3 micrometers or less) so that a color density may not be impaired. In addition, since it is not necessary to increase the total amount (content) of the coloring agent in a composition as mentioned above, the characteristic as coating films, such as image development characteristics, does not fall.

The color reproduction region can be enlarged by about 30% by the color filter for LCD of the present invention in which the pixels of four colors having the above characteristics are formed.

As the substrate constituting the color filter, for example, soda glass, pyrex (R) glass, quartz glass used for liquid crystal display devices and the like, and a transparent conductive film attached thereto, or a TFT (thin film transistor) is formed on the surface. Glass substrates; and the like. Plastic substrates may also be mentioned. These substrates may be provided with black stripes separating each pixel.

As the developer, any one can be used as long as it dissolves the uncured portion of the photocurable colored composition for LCD of the present invention and the cured portion is not dissolved. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As said organic solvent, the above-mentioned solvent used for preparation of the photocurable coloring composition for LCD of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etheramine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. The solution which melt | dissolved alkaline compounds, such as choline, a pyrrole, and piperidine, so that concentration may be 0.001-10 mass%, Preferably it is 0.01-1 mass% is preferable. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with water after image development.

Especially the photocurable coloring composition for LCDs in this invention can be used suitably for formation of the colored pixel of the color filter used for liquid crystal display devices (LCDs), such as a monitor and a TV.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

Example 1

Alkaline soluble resin

Benzyl methacrylate / methacrylic acid copolymer; 80 copies

(Weight average molecular weight 30000, acid value 120)

Cyan colorant

C.I. Pigment Blue 15: 3 (PB15: 3)… 50 copies

C.I. Pigment Yellow 150 (PY150). 50 copies

solvent

Propylene glycol monomethyl ether acetate... 500 copies

Was dispersed overnight with a sand mill.

Then, the following component was added.

Photosensitive polymerizable component

Dipentaerythritol hexaacrylate (DPHA); 80 copies

Photopolymerization initiator

4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine… Part 5

7-[{4-chloro-6- (diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin

… Part Two

Thermal polymerization inhibitor

Hydroquinone monomethyl ether... 0.01 part

solvent

Propylene glycol monomethyl ether acetate... 500 copies

After mixing the above components uniformly, the filter was filtered through a filter having a pore diameter of 5 µm to obtain a cyan composition for LCD of the present invention. This composition was apply | coated so that a dry film thickness might be set to 2.4 micrometers using the spin coater on the glass substrate for color filter manufacture, and it dried at 120 degreeC for 2 minutes, and formed the uniform coating film.

Next, using an exposure apparatus, the coating film was irradiated with the exposure amount of 300mJ / cm <2> through a 100-micrometer mask at a wavelength of 365 nm. After irradiation, the solution was developed at 26 ° C. for 60 seconds using 10% CD (manufactured by Fujifilm Arch). Subsequently, after rinsing with running water for 20 seconds, it was dried with an air knife and heat-treated at 220 ° C. for 60 minutes to form a cyan pattern image (cyanide pixel).

Instead of 100 parts of the cyan colorant described above, this operation was performed as C.I. Pigment Red 254 (PR254) / C.I. Pigment Red 177 (PR177) (= 100/50) 100 parts, as a green colorant, C.I. Pigment Green 36 (PG36) / C.I. Pigment Yellow 150 (PY150) (= 100/50) is 100 parts, as a blue colorant, C.I. Pigment Blue 15: 6 (PB15: 6) / C.I. Except for 75 parts of Pigment Violet 23 (PV23) (= 100/20), the photocurable red composition, the photocurable green composition, and the photocurable blue composition were adjusted under the same prescription and conditions as those of the above-mentioned photocurable cyan composition. By the same operation, the red pattern image (green pixel), the blue pattern image (green pixel), and the blue pattern image (blue pixel) were formed sequentially on the same board | substrate, and the color filter of this invention was obtained.

(Examples 2 to 12 and Comparative Example 1)

A color filter was produced under the same conditions as in Example 1, except that the cyan colorant of Example 1 was used as the cyan colorant of Table 1 below. The evaluation results are shown in Table 1 below.

(evaluation)

(a) Evaluation of chromaticity

As described above, for the coating film of each color formed on the glass substrate, the CIE chromaticity (x value, y) was used for the coating film of the unexposed state which is evaluation of chromaticity (product of Otsuka Denshi Co., Ltd.). Value). The measurement results are shown in Table 1 below.

(b) Evaluation of color reproduction

Four colors including the area of the triangle surrounded by three points of the CIE marker value (x, y) and the C (cyan) color of the embodiment on the CIE 1931 standard indicator chromaticity diagram of each color of the color filter of the comparative example The area of the square surrounded by four points of the marker values (x, y) was obtained. As the reference value, the area of the triangle of RGB three colors determined by the NTSC system was set to 100, and the areas of the examples and the comparative examples with respect to the area of the reference value were defined as color reproducibility. The evaluation results are shown in Table 1 below.

As can be seen from Table 1, in the examples, high color reproducibility is exhibited in all, and in particular, in Example 1, the color reproducibility is 110%, and it can be seen that the color reproduction area can be widened by 30% with respect to the comparative example. .

According to the present invention, it is possible to provide an LCD color filter capable of exhibiting sufficient color reproducibility applicable to TV applications.

Claims (7)

In a color filter for an LCD comprising a plurality of pixels formed on a substrate, the pixels of the plurality of colors are formed of pixels of red (R), green (G), blue (B), and cyan (C), and the pixels The CIE marker value in CIE chromaticity diagram of the following is a range of the following. Red (R): x = 0.50 to 0.70, y = 0.28 to 0.36 Green (G): x = 0.20 to 0.33, y = 0.50 to 0.73 Blue (B): x = 0.13 to 0.17, y = 0.04 to 0.11 Cyan (C): x = 0.08 to 0.20, y = 0.25 to 0.70 The color filter for LCD according to claim 1, wherein the pixel of cyan (C) contains at least one of the following colorants. Colorant (i): C.I. Pigment Green 7 (PG7) Colorant (ii): C.I. Pigment Green 7 (PG7) and C.I. Mixture of Pigment Yellow 150 (PY150) Colorant (iii): C.I. Pigment Blue 15: 3 (PB15: 3) and C.I. Mixture of Pigment Yellow 150 (PY150) Colorant (iv): aluminum phthalocyanine and C.I. Mixture of Pigment Yellow 150 (PY150) Colorant (v): C.I. Pigment Green 7 (PG7) and C.I. A mixture of Pigment Blue 15: 6 (PB15: 6) Colorant (vi): C.I. Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. Mixture of Pigment Yellow 150 (PY150) The color filter for LCD of Claim 1 or 2 whose mixing ratio of PG7 and PY150 in the said coloring agent (ii) is 100/5-100/100 (mass ratio). The color filter for LCD as described in any one of Claims 1-3 whose mixing ratio of PB15: 3 and PY150 in the said coloring agent (iii) is 100/5-100/400 (mass ratio). . The aluminum phthalocyanine and C.I. in any one of Claims 1-4 in said coloring agent (iv). Pigment Yellow 150 (PY150) The mixing ratio of the color filter for LCD, characterized in that 100/5 to 100/100 (mass ratio). C.I. in any one of Claims 1-5 in the said coloring agent (v). Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) The mixing ratio of the color filter for LCD, characterized in that 100/10 to 100/50 (mass ratio). C.I. in any one of Claims 1-6 in the said coloring agent (vi). Pigment Green 7 (PG7) and C.I. Pigment Blue 15: 6 (PB15: 6) and C.I. Pigment Yellow 150 (PY150) The mixing ratio of the color filter for LCD, characterized in that 100/5/5 to 100/50/50 (mass ratio).