TWI422559B - Blue coloring composition for color filter, color filter and color display - Google Patents

Description

Color filter with blue coloring composition, color filter and color display

The present invention relates to a blue coloring composition for producing a color filter such as a color display or a color image sensor, a color filter including a filter segment formed of the blue coloring composition, and a color filter. A color display of the color filter. Further, the blue coloring composition can be used not only for producing a blue filter segment but also for producing a cyan filter segment.

The liquid crystal display has a configuration in which, for example, a liquid crystal layer is sandwiched between a pair of polarizing plates. In such a liquid crystal display, the alignment state of the liquid crystal molecules is utilized to change the polarization state of the polarizing plate that has penetrated one of them, thereby controlling the amount of light penetrating through the other polarizing plate.

The display mode of the liquid crystal display includes a VA (Vertically Aligned) mode, an IPS (In-Plane Switching) mode, an OCB (Optically Compensated Bend) mode, and a TN (Twisted Nematic) mode. Among these, the TN mode is the mainstream.

These liquid crystal displays can display color images by providing color filters between polarizing plates. In recent years, color liquid crystal displays have gradually used various devices such as monitors for television viewers and personal computers. Therefore, the color filter is required to have high contrast and high definition, and the requirements for a wide range of color reproduction areas and high reliability are also increased.

Further, the color filter has a structure in which two or more kinds of filter segments having different hue are disposed on a transparent substrate such as glass. Each filter segment is fine to a width of a few microns to several hundred microns. In the filter section, various shapes and configurations such as strip arrangement and triangular arrangement can be performed. Either way, the filter segments are arranged in an orderly arrangement in each hue in a defined arrangement.

Further, in a color imaging device using a C-MOS (Complementary Metal Oxide Semiconductor) or a CCD (Charge Coupled Device), generally, three primary colors, that is, blue, are disposed on the light receiving surface of the imaging element. ), green (G) and red (R) colors, or color filters of complementary colors such as yellow (Y), magenta (M), and cyan (C) color filter segments. In recent years, for color filters used in color photographing apparatuses, demands for color characteristics such as high transmittance, that is, high definition, and a wide color reproduction area have also been increased.

The method for producing a color filter includes, for example, a dyeing method using a salt-forming coloring method, a method of using a dye as a coloring agent in a dye dispersion method, a pigment dispersion method using a pigment as a coloring agent, a printing method, and electricity. Deposition method.

In the pigment dispersion method, a color resist obtained by dispersing a pigment particle, that is, a pigment particle, in a transparent resin, and mixing a sensitizer, an additive, or the like therein is used. Then, the color resist is applied onto the substrate by a coating device such as a spin coater, and then the coating film is selectively exposed through a mask using an alignment machine or a stepper. The exposed coating film is sequentially subjected to alkali development and heat hardening treatment, thereby obtaining a filter segment pattern. The above operation is repeated for each color to complete the color filter.

Conventionally, indigo pigments having excellent resistance and color tone have been used for the blue filter segment and the cyan filter segment. Since the indigo pigment has various crystal forms such as α-type, β-type, δ-type, and ε-type, and has excellent properties of high chroma and coloring power, it is suitable as a coloring agent for color filters.

As the indigo pigment, various center metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among them, copper indigo pigments are widely used because of their highest chroma. In addition, dissimilar metal indigo pigments such as metal-free indigo pigments, zinc indigo pigments, aluminum indigo pigments, and cobalt indigo pigments are also being put into practical use.

In a conventional liquid crystal display using a cold cathode tube type backlight, for example, in a blue filter segment or a cyan filter segment, by using a copper indigo pigment and two A combination of pigments to achieve a high brightness and wide color display area. However, as described above, a color filter is required to have a higher brightness and a wider color reproduction area.

In order to solve the above problems, JP-A No. 6-75375 discloses a technique in which a dye is dissolved in a resin or the like as a coloring agent, not a pigment. Further, in Japanese Patent Laid-Open No. Hei 8-327811, it is described that it contains an indigo dye and A dye-based color filter ink. Further, in Japanese Laid-Open Patent Publication No. Hei 11-223720, it is described that a triphenylmethane dye is used in combination with a blue filter segment of a color filter. Is a dye. However, dyes have a problem of poor heat resistance, light resistance, and solvent resistance as compared with pigments.

An amine salt of an acid dye such as a copper indigo acid dye or a sulfonamide compound of an acid dye is used as a coloring agent for a color filter, in Japanese Patent Application Laid-Open No. Hei 6-51115, No. Hei. use. However, the salt-forming products disclosed herein have poor solvent solubility and are not sufficient in heat resistance and light resistance.

An object of the present invention is to provide a color filter excellent in color characteristics, heat resistance, light resistance, and solvent resistance, a color display including such a color filter, and a blue coloring used in the manufacture of a conventional color filter. Composition.

The inventor of the present invention, etc., worked hard to solve the aforementioned problems, and found that by using A product obtained by salting an acid dye with a compound having a cationic group as a coloring composition, can achieve a high-definition and wide color reproduction region, and can also achieve heat resistance, light resistance, and solvent resistance. Excellent performance. Moreover, based on this finding, the invention of the following first to third aspects was achieved.

That is, the first aspect of the present invention relates to a blue colored composition for a color filter comprising a binder resin and a color former, and the colorant contains a blue pigment and a salt-forming product, and the salt-forming product By It is formed by an acid dye and a compound having a cationic group.

The compound having a cationic group may contain at least one selected from the group consisting of a quaternary ammonium compound, an amine, and a resin having a cationic group in a side chain.

The compound having a cationic group may contain the following quaternary ammonium compound represented by the formula (1).

General formula (1):

[In the formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y- represents an inorganic or organic anion. ]

The molecular weight of the cation of the aforementioned quaternary ammonium compound represented by the general formula (1) may be in the range of from 190 to 900.

In the formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and 2 or more of R ₁ to R ₄ may have 5 to 20 carbon atoms. .

The compound having a cationic group contains the above-mentioned resin having a cationic group in the side chain, and the resin having a cationic group in the side chain may be an acrylic resin containing a structural unit represented by the following general formula (2).

General formula (2):

[In the formula (2), R ₅ represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R ₆ to R ₈ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and two of R ₆ to R ₈ may also be each other Bonding to form a ring. Q represents an alkylene group, an extended aryl group, -CONH-R ₉ -, or -COO-R ₉ -, and R ₉ represents an alkylene group. Y- represents an inorganic or organic anion. ]

The compound having a cationic group includes an amine, and the amine may be at least one selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine.

The molecular weight of the aforementioned amine may range from 129 to 591.

The aforementioned amine may be represented by the following formula (3).

General formula (3):

R ₁₀ R ₁₁ R ₁₂ N

[In the general formula (3), two of R ₁₀ to R ₁₂ each independently represent an alkyl group or a benzyl group having 8 to 22 carbon atoms, and one of them represents a hydrogen atom or a carbon atom number of 1 to 22 Alkyl or benzyl. ]

The salt-forming product may be a resin having a cationic group in the side chain in an aqueous solution and the foregoing Mixing an acid dye and removing the relative anion of the resin having a cationic group in the side chain as described above A compound obtained by using a salt composed of a relative cation of an acid dye.

The blue pigment may be an indigo pigment and/or a triarylmethane lake pigment.

The blue pigment contains an indigo pigment, and the indigo pigment may be C.I. Pigment Blue 15:6.

The foregoing Acid dyes can also be classified as CI acid red.

The foregoing The acid dye may be any one selected from the group consisting of CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI Acid Red 388.

The aforementioned coloring agent may further comprise C.I. Pigment Violet 23.

The aforementioned coloring agent may further comprise two It is a pigment.

It may further comprise a copper indigo amine compound.

The copper azurin compound may have a structure represented by the formula (4).

General formula (4):

P-Lm

[In the formula (4), P is an m-valent copper indigo pigment residue, m is an integer of 1 to 4, and L is a group selected from the substituents represented by the general formulae (5) to (7) Any of the groups. ]

General formula (5):

General formula (6):

General formula (7):

[In the general formulae (5) to (7), X is -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, or direct bonding, Y ⁰ is -NH-, -O-, or directly bonded, n is an integer from 1 to 10, Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ -, or directly bonded, R ⁹ and R ¹⁰ Each independently is a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z represents an alkylene group having 1 to 20 carbon atoms or 1 to 1 carbon atom. 20 of the aryl group.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ^{2 are} integrated to further contain nitrogen, oxygen, or a heterocyclic ring of a sulfur atom, R ³ , R ⁴ , R ⁵ and R ⁶ each independently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 6 carbon atoms R aryl group to 20, R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and R ⁸ is a substituent represented by the formula (5), or The substituent represented by the formula (6), Q represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a substituent represented by the formula (5), or a substituent represented by the formula (6). ]

The foregoing The mass ratio of the dye to the aforementioned copper indigo amine compound may also be in the range of 0.3 to 1.5.

The aforementioned blue pigment may also be a copper indigo pigment.

The foregoing The dye can also be a rose red dye.

When the content of the blue pigment is 100 parts by mass, the amount of the effective dye component in the salt-forming product (A) may be in the range of 5 to 150 parts by mass.

The color filter may be a blue coloring composition, and may further comprise a photopolymerizable compound and/or a photopolymerization initiator.

The color filter is a blue coloring composition, and may further contain an organic solvent containing propylene glycol monomethyl ether acetate as a main component.

The coating film formed of the coloring composition and having a spectral transmittance of 3% at a wavelength of 570 nm may have the following spectral characteristics: a wavelength of 50% of the spectral transmittance is 490 to 510 nm, and a wavelength of 450 nm. The spectral transmittance is 85% or more, and the spectral transmittance at a wavelength of 540 nm is 11% or less.

A second aspect of the present invention relates to a color filter comprising: a green filter segment; a red filter segment; and a blue filter formed by the blue colored composition of the first aspect Light section.

Color filters can also be used for solid-state imaging components.

Color filters can also be used for organic EL displays.

White light is emitted from the white light-emitting organic electroluminescent element, and the white light has an emission spectrum having a maximum value of two or more in a wavelength range of 400 to 700 nm, and a wavelength in the range of 430 to 485 nm and a wavelength of 580 to 620 nm. within the scope of having a light emission intensity exhibits a peak of the wavelength maximum of λ ₁ and λ _2, to the emission intensity at the wavelength λ ₂ of I ₂ and to the emission intensity at the wavelength λ ₁ of I ₁ ratio I ₂ / I ₁ 0.4 to 0.9 Within the range; when the white light is incident on the blue filter segment, the chromaticity coordinates (xB, yB) of the transmitted light emitted by the blue filter segment in the CIE color system are also satisfied. The relationship between inequality xB ≦ 0.160 and yB ≦ 0.100.

White light is emitted from the white light-emitting organic electroluminescent element, and the white light has an emission spectrum having a maximum value of two or more in a wavelength range of 400 to 700 nm, and a range of wavelengths of 430 to 485 nm and a wavelength of 580 to 620 nm. within each having a light emission intensity exhibits a peak of the wavelength maximum of λ ₁ and λ _2, and in the emission intensity at the wavelength λ ₂ of I ₂ and to the emission intensity at the wavelength λ ₁ of I ₁ ratio I ₂ / I ₁ 0.4 to 0.9 Within the range; when the white light is incident on the red, green, and blue filter segments, the transmitted light emitted by each of the blue, green, and red filter segments is at a chromaticity coordinate of the CIE color system When (xR, yR), (xG, yG), and (xB, yB) are plotted on the xy chromaticity diagram, and the triangles that are used as vertices are drawn, the area of the triangle may also be the coordinates of the vertices (0.67). , 85% or more of the area of the triangles of 0.33), (0.21, 0.71), and (0.14, 0.08).

The red filter segment may also include at least one of C.I. Pigment Red 177 and C.I. Pigment Red 179.

The green filter segment may further comprise at least one green pigment selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58, and is selected from the group consisting of CI Pigment Yellow. 139. At least one yellow pigment of the group consisting of CI Pigment Yellow 150 and CI Pigment Yellow 185.

A third aspect of the invention relates to a color display comprising: a color filter of a second aspect; and a light-emitting device comprising a white light-emitting organic electroluminescence element as a light source.

[Formation of the Invention]

The aspect of the invention will be described below.

Here, "(meth)acryloyl group", "(meth)acrylic group", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acrylamide" Unless otherwise stated, each means "acryloyl and/or methacrylic acid", "acrylic and/or methacrylic", "acrylic and/or methacrylic", "acrylate" and/or Or methacrylate" and "acrylamide and/or methacrylamide". Further, "C.I." means the dye index 吖 (C.I.).

○The first aspect

First, the first aspect will be described.

The color filter of the first aspect is a blue coloring composition containing a binder resin and a coloring agent. The colorant contains a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group. In this aspect, a quaternary ammonium compound is used as the compound having a cationic group.

When the blue colored composition of the first aspect is used in the production of a color filter, a high-definition and wide color reproduction region can be achieved, and excellent heat resistance, light resistance, and solvent resistance can be achieved. performance.

Also, a combination of conventional copper sapphire blue pigments and two The color filter of a color filter such as a pigment has a breakthrough spectrum of a blue coloring composition, and the peak position is present at around 450 nm, and the transmittance is rapidly lowered on the short wavelength side of 450 nm or less.

In contrast, when using the color filter of the present aspect to color the composition with blue, it is compared with the use of the combined copper phthalocyanine blue pigment and the second In the case of a pigment, a high transmittance on the short-wavelength side of 450 nm or less can be achieved. Further, an emission spectrum of a plurality of backlights such as a cold cathode tube has, for example, a peak wavelength in or near a wavelength range of 425 to 440 nm. Therefore, the filter segment obtained by the blue coloring composition of the color filter of the present aspect can achieve high brightness.

<colorant>

The color filter of the present aspect is a coloring agent for the blue coloring composition, and contains It is a salt-forming product (A) composed of an acid dye and a quaternary ammonium compound and a blue pigment.

By using the salt-forming product (A) in combination with the blue pigment, as described above, high transmittance can be achieved in the wavelength range of 425 to 440 nm or in the vicinity thereof. Yes, compared to the combination of copper indigo pigment and two The conventional filter section of the pigment enables high brightness and wide color reproducibility. Again, by It is a salt of an acid dye and a quaternary ammonium compound, and can also achieve high heat resistance, light resistance and solvent resistance.

(by a salt-forming product (A) composed of an acid dye and a quaternary ammonium compound

First, the salt-forming product (A) will be explained. by Used in the salt forming product (A) composed of an acid dye and a quaternary ammonium compound It is an acid dye that appears red to purple and has the form of a dye.

Red to purple It is an acid dye and belongs to acid dyes such as CI Acid Red and CI Acid Violet, or direct dyes such as CI Direct Red and CI Direct Violet. Here, since the direct dye has a sulfonic acid group, it is regarded as a form of an acid dye in this aspect.

Salt-forming product (A), by It is an acid dye (also including a direct dye) which forms a salt with a quaternary ammonium compound which produces a relative ion, and which is a salt-forming dye which is denatured as needed.

[ Acid dye]

Description A dye-based acid dye. Dye-based acid dye, preferably used: CI Acid Red 51 (Erythrosine (Edible Red No. 3)), CI Acid Red 52 (Acid Rhodamine), CI Acid Red 87 (I Red (eosin) G (edible red 103)), CI acid red 92 (acid phloxine PB (edible red 104)), CI acid red 289, CI acid red 388, Bengal rose (rose Bengal) B (Edible Red No. 5), Acid Rose Red G, CI Acid Violet 9, CI Acid Violet 9, CI Acid Violet 30.

Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388 are preferably used.

An acid dye having a transmittance of 90% or more for light having a wavelength of 650 nm, a transmittance of 75% or more for light having a wavelength of 600 nm, and a transmittance of 5% or less for light having a wavelength of 550 nm. It is preferable that the transmittance of light having a wavelength of 400 nm is 70% or more. More preferably, the transmittance for light having a wavelength of 650 nm is 95% or more, the transmittance for light having a wavelength of 600 nm is 80% or more, and the transmittance for light having a wavelength of 550 nm is 10% or less, for wavelength. The transmittance of light of 400 nm is 75% or more.

also, It is preferred to use an rosin-based acid dye from the viewpoint of excellent color developability.

[Quaternary ammonium compound]

Next, the quaternary ammonium compound will be explained. Since the quaternary ammonium compound has an amine group, its ion is used as a relative ion of an acid dye.

Preferred quaternary ammonium compounds are colorless or white.

Here, the colorless or white color means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. That is, the quaternary ammonium compound must not interfere with the color development of the dye component and does not cause color change.

The cationic component of the quaternary ammonium compound, i.e., the molecular weight of the counter ion, is preferably in the range of from 190 to 900. Here, the cationic moiety corresponds to a moiety of (NR ₁ R ₂ R ₃ R ₄ ) ⁺ in the following general formula (1). When a cationic moiety having a molecular weight of less than 190 is used, it is difficult to achieve high light resistance and heat resistance, and the solubility in a solvent is also low. Moreover, when the molecular weight is more than 900, the ratio of the chromonic component in the molecule is lowered, the color developability is lowered, and the brightness is also lowered. More preferably, the molecular weight of the opposite portion is in the range of 240 to 850. More preferably, the relative portion has a molecular weight in the range of from 350 to 800.

Here, the molecular weight is calculated according to the structural formula, and the atomic weight of C is 12, and the atomic weight of H is 1, and the atomic weight of N is 14.

As the quaternary ammonium compound, the following formula (1) can be used.

General formula (1):

(In the formula (1), R ¹ to R ⁴ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and 2 or more C numbers of R ¹ to R ⁴ are 5 to 20. Y represents Inorganic or organic anions.)

When the C number of two or more of R ¹ to R ⁴ is 5 to 20, the solubility in a solvent is good. When there are three or more alkyl groups having a C number of less than 5, the solubility in a solvent is deteriorated, and a coating film foreign matter is likely to be generated. Further, when an alkyl group having a C number of more than 20 is present, the color developability of the salt-forming product (A) is impaired.

Specifically, the quaternary ammonium compound is preferably, for example, tetramethylammonium chloride (having a molecular weight of a cationic moiety of 74), tetraethylammonium chloride (having a molecular weight of a cationic moiety of 122), and monostearyl Methyl ammonium chloride (having a molecular weight of 312 for the cationic moiety), distearyl dimethyl ammonium chloride (having a molecular weight of 550 for the cationic moiety), and tristea monomethylammonium chloride (the molecular weight of the cationic moiety is 788). ), cetyltrimethylammonium chloride (molecular weight of the cationic moiety is 284), trioctylmethylammonium chloride (molecular weight of the cationic moiety is 368), dioctyldimethylammonium chloride (cationic moiety) The molecular weight is 270), monolauryl trimethyl ammonium chloride (the molecular weight of the cationic moiety is 228), dilauryl dimethyl ammonium chloride (the molecular weight of the cationic moiety is 382), and trilauryl methyl ammonium chloride ( The molecular weight of the cationic moiety is 536), triamylbenzylammonium chloride (molecular weight of the cationic moiety is 318), trihexylbenzylammonium chloride (molecular weight of the cationic moiety is 360), trioctylbenzylammonium chloride ( The molecular weight of the cationic moiety is 444), trilaury benzyl ammonium chloride (cationic moiety) The molecular weight is 612), benzyldimethyl stearyl ammonium chloride (the molecular weight of the cationic moiety is 388), and benzyldimethyloctyl ammonium chloride (the molecular weight of the cationic moiety is 248), or a dialkyl group. (Alkyl group is C14 to C18) dimethylammonium chloride (hardened tallow) (the molecular weight of the cationic moiety is 438 to 550).

The component constituting the anion Y- may be any of an inorganic anion and an organic anion, and is preferably a halogen, and is usually chlorine.

Commercially available quaternary ammonium compounds such as QUARTAMIN 24P, QUARTAMIN 86P conc, QUARTAMIN 60W, QUARTAMIN 86W, QUARTAMIN D86P, SANIZOL C and SANIZOL B-50 manufactured by Kao Corporation, and Arquad 210-80E, 2C-75, 2HT manufactured by LION Corporation -75, 2HT FLAKE, 2O-75I, 2HP-75 and 2HP FLAKE, which in turn are QUARTAMIN D86P (distearyldimethylammonium chloride) and Arquad 2HT-75 (dialkyl (alkyl is C14 to C18) Dimethyl ammonium chloride is preferred.

[salt treatment]

A salt-forming product of an acid dye and a quaternary ammonium compound can be synthesized by a conventionally known method. A specific method has been disclosed in Japanese Patent Laid-Open No. Hei 11-72969.

For example, After the acid dye is dissolved in water, a quaternary ammonium compound is added, and the salting treatment is carried out while stirring. here, The sulfonic acid group (-SO ₃ H) which is an acid dye is combined with the ammonium group (NH ₄ ⁺ ) of the quaternary ammonium compound to obtain a salt-forming product. In the case of salification, the solvent may also use methanol or ethanol instead of water.

The amount of the salt-forming product (A) is preferably in the range of 1 to 80 parts by mass, more preferably in the range of 5 to 60 parts by mass, per 100 parts by mass of the blue pigment. When the amount of the salt-forming product (A) is less than 1 part by mass, the reproducible chromaticity region is narrowed, and if it exceeds 80 parts by mass, the desired hue may not be obtained.

In particular, the salt-forming product (A) of the quaternary ammonium compound having a molecular weight of from 350 to 800 in the CI acid red 289 and the cationic portion is excellent in solvent solubility, and when used in combination with the blue pigment, excellent heat resistance can be achieved. , light resistance and solvent resistance. Further, the reason why the salt-forming product (A) and the blue pigment are used in combination to achieve good performance is that the salt-forming product (A) is adsorbed to the blue pigment in a state of being dissolved or dispersed in a solvent.

(blue pigment)

As the blue pigment, an indigo pigment and/or a triarylmethane-based lake pigment or the like can be used. For the indigo pigment, it is preferred to use a copper phthalocyanine pigment.

Copper bismuth blue pigment, cited CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6, etc. A pigment in which a copper phthalocyanine blue pigment having an ε-type or an α-type structure is preferred. Such preferred pigments are, in particular, C.I. Pigment Blue 15:6 and C.I. Pigment Blue 15:1.

Triaryl methane-based lake pigment, which is CI Pigment Blue 1, CI Pigment Blue 1:2, CI Pigment Blue 1:3, CI Pigment Blue 2, CI Pigment Blue 2:1, CI Pigment Blue 2:2, CI Pigment Blue 3, CI Pigment Blue 8, CI Pigment Blue 9, CI Pigment Blue 10, CI Pigment Blue 10: 1, CI Pigment Blue 11, CI Pigment Blue 12, CI Pigment Blue 18, CI Pigment Blue 19, CI Pigment Blue 24, CI Pigment Blue 24:1, CI Pigment Blue 53, CI Pigment Blue 56, CI Pigment Blue 56:1, CI Pigment Blue 57, CI Pigment Blue 58, CI Pigment Blue 59, and CI Pigment Blue 61, CI Pigment Blue 62, etc. .

It is preferred to use C.I. Pigment Blue 15:6.

[Micronization of pigments]

The blue pigment used in the blue coloring composition of the present aspect and any other pigment used arbitrarily can be subjected to salt milling treatment to be fine. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of good dispersion in the colorant carrier. Further, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly preferred range is 25 to 85 nm.

Further, the primary particle diameter of the pigment was determined by an electron micrograph of a TEM (transmission electron microscope) of the pigment. Specifically, first, one pigment particle is selected from the TEM image as the primary particle that is visible to the whole. Next, select the line segment having the longest length among the line segments connecting the two points on the outline of the pigment particle image. The line segment is treated as the first line segment. Next, among the line segments connecting the two points on the outline of the pigment particle image, a line segment perpendicularly intersecting the first line segment is selected. Use this line segment as the second line segment. And, obtaining a length of _a second line segment to the length L of the average as the average length L _{AV 2,} further obtains the average length of one side equal to the length L _AV cubic volume of the first line segment L V. The above measurement and calculation were performed on 100 or more pigment particles, and the average of the volume V was determined as the average volume V _av . The length of one side of the cube having the average volume V _av is taken as the average primary particle diameter of the pigment particles.

The salt grinding treatment refers to a mixture of a pigment and a water-soluble inorganic salt and a water-soluble organic solvent, and a kneading machine such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a grinder, and a sand mill. After mechanically kneading on the heating side, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid. In salt milling, the pigment is broken by the high hardness of the inorganic salt. By optimizing the conditions at which the pigment salt is milled, it is possible to obtain a pigment having a very small primary particle size, a narrow distribution range, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, cesium chloride, potassium chloride, sodium sulfate or the like can be used. From the viewpoint of price, it is preferred to use sodium chloride (salt). The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000 parts by mass, more preferably from 300 to 1000 parts by mass, in terms of both the treatment efficiency and the production efficiency, when the total mass of the pigment is 100 parts by mass.

The water-soluble organic solvent is used for moistening a pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is easily evaporated, it is preferred to use a high boiling point solvent having a boiling point of 120 ° C or higher from the viewpoint of safety. For example, 2-methylaminoethanol, 2-butoxyethanol, 2-(isopentylamino)ethanol, 2-(hexylamino)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol can be used. Monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methylamino-2-propanol, 1-ethylamino-2-propanol, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, or liquid polypropylene glycol. In the case of the water-soluble organic solvent, when the total mass of the pigment is 100 parts by mass, the amount of 5 to 1000 parts by mass is preferably used, and the amount of 50 to 500 parts by mass is more preferably used.

When the pigment is subjected to a salt milling treatment, a resin may also be added. The kind of the resin is not particularly limited, and for example, a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin is preferably solid at room temperature and is water-insoluble, and more preferably partially soluble in the above organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by mass, based on 100 parts by mass of the total mass of the pigment.

(other colorants)

In the blue coloring composition of the present aspect, other organic pigments may be added as long as the effect obtained is not hindered.

The organic pigment is preferably used, for example, two A pigment, an anthraquinone pigment, an azo pigment, or a quinophthalone pigment. Among them, use two A pigment is preferred. two For the pigment, it is preferred to use CI Pigment Violet 23. If you use two The pigment is a blue coloring composition which is excellent in heat resistance, light resistance, and solvent resistance, and which is high in stability and stability.

The organic pigment is also preferably used in the form of a salt mill or the like as described above.

<Resin>

The resin is such that the colorant is especially dispersed as a salt product, or the salt forming product is dyed or impregnated. The resin is a thermoplastic resin, a thermosetting resin, or the like.

The resin has a spectral transmittance of 80% or more and more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. When the blue coloring composition is used in the form of an alkali-developing type colored resist material, an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is preferably used. Moreover, in order to improve the light sensitivity, an active energy ray-curable resin having a vinyl bond can also be used.

In particular, when an active energy ray-curable resin having a vinyl bond in a side chain is used in an alkali-developing resist for a color filter, a coating film formed by applying such a film does not generate foreign matter and forms a salt-forming product in the resist. The stability of (A) is improved and is preferred. When a linear resin having no vinyl bond in its side chain is used, in a liquid in which a resin and a dye are mixed, the dye is less likely to be trapped in the resin, and aggregation and precipitation tend to occur. When the active energy ray-curable resin having a vinyl bond in its side chain is used, the dye is easily trapped in the resin in the liquid in which the resin and the dye are mixed, so that aggregation and precipitation are less likely to occur. Further, in this case, when the coating film is exposed by the active energy ray, the resin is crosslinked in three dimensions, and the position of the dye molecules is fixed. Therefore, even if the solvent is removed in the subsequent development step, the dye is less likely to cause aggregation and precipitation.

The weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to allow the coloring agent (B) to be well dispersed. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the ratio Mw/Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 10 or less.

When the blue coloring composition is used as a coloring composition for a color filter, it is used as a coloring agent adsorption base from the viewpoints of dispersibility or solubility of a pigment and a salt-forming product, and developability and heat resistance. The balance between the carboxyl group which acts on the alkali-soluble group at the time of development, and the aliphatic group and the aromatic group which act as an affinity group for a coloring agent carrier and a solvent are important. It is preferred to use a resin having an acid value of 20 to 300 mgKOH/g. A resin having an acid value of less than 20 mgKOH/g is inferior in solubility in a developing solution, and it is difficult to form a fine pattern. When the acid value exceeds 300 mgKOH/g, both the exposed portion and the unexposed portion may be removed by development.

When the total mass of the coloring agent is 100 parts by mass, the amount of the resin used is preferably 30 parts by mass or more from the viewpoint of achieving excellent film formability and resistance, and a high colorant concentration and a good color are achieved. The viewpoint of the characteristics is preferably in an amount of 500 parts by mass or less.

(thermoplastic resin)

The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or the like. Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose , polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

The vinyl alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer may, for example, be a resin having an acidic group such as a carboxyl group or a mercapto group. The alkali-soluble resin may specifically be an acrylic resin having an acidic group, an α-olefin-maleic acid (anhydride) copolymer, a styrene-styrenesulfonic acid copolymer, or an ethylene-(meth)acrylic acid copolymer. Or an isobutylene-maleic acid (anhydride) copolymer or the like. Among them, at least one type of resin selected from an acrylic resin having an acidic group and a styrene-styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, can be suitably used because of its high heat resistance and transparency.

The active energy ray-curable resin having a vinyl bond may, for example, be a resin obtained by introducing a vinyl bond by the method (a) or (b) shown below.

[method (a)]

In the method (a), for example, a monomer having an epoxy group and a vinyl bond is first copolymerized with one or more other monomers, whereby a copolymer having an epoxy group in a side chain is obtained. Next, a carboxyl group of an unsaturated unit acid having a vinyl bond and a carboxyl group is added to react with an epoxy group of a side chain, and an acid anhydride is allowed to react with the generated hydroxyl group. Thus, a resin into which a vinyl bond and a carboxyl group are introduced can be obtained.

Examples of the monomer having a cyclic amino group and a vinyl group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and 2-epoxypropoxyethyl (meth)acrylate. Ester, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated unit acid of the next step, bis(meth)acrylic acid propyl acrylate is preferred.

Examples of the unsaturated unit acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and the α-position hydrogen atom of (meth)acrylic acid is substituted with a haloalkyl group or an alkoxy group. A monocarboxylic acid such as a halogen atom, a nitro group or a cyano group. These may be used alone or in combination of two or more.

Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more.

Instead of an acid anhydride having two carboxyl groups or an acid anhydride having two carboxyl groups, an acid anhydride having three or more carboxyl groups, for example, a tricarboxylic acid anhydride such as benzene trimellitic anhydride or a tetracarboxylic acid such as pyromellitic dianhydride may be used. anhydride. In this case, the anhydride group remaining after the reaction of the hydroxyl group with the acid anhydride may also be hydrolyzed.

As the acid anhydride, an acid anhydride having a vinyl bond such as tetrahydrophthalic anhydride or maleic anhydride can be used. In this way, the vinyl bond can be further increased.

Further, a method similar to the method (a), for example, has the following method. First, a monomer having a carboxyl group and a vinyl bond is copolymerized with one or more other monomers to obtain a copolymer having a carboxyl group in a side chain. Next, a monomer having a vinyl bond and an epoxy group is subjected to an addition reaction with a part of carboxyl groups of the side chain. Thus, a resin into which a vinyl bond and a carboxyl group are introduced can be obtained.

[method (b)]

In the method (b), for example, first, a monomer having a hydroxyl group and a vinyl bond is copolymerized with an unsaturated unit acid or another monomer having a carboxyl group and a vinyl bond.

A copolymer having a hydroxyl group in a side chain is obtained. Next, the hydroxyl group of the side chain is reacted with the isocyanate group of the monomer having an isocyanate group and a vinyl bond. Thus, a resin into which a vinyl bond and a carboxyl group are introduced can be obtained.

The monomer having a hydroxyl group and a vinyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3-(meth)acrylate or 4-hydroxybutyl ester, glyceryl (meth)acrylate, and hydroxyalkyl (meth)acrylate such as cyclohexanedimethanol mono(meth)acrylate. These may be used alone or in combination of two or more. Further, a compound obtained by addition polymerization of an oxyalkyl (meth) acrylate to an oxide such as ethylene oxide, propylene oxide or butylene oxide, for example, a polyether mono(meth)acrylate, or a (poly)ester monoester of at least one of (meth) hydroxyalkyl acrylate addition (poly) γ-valerolactone, (poly) ε-caprolactone, and (poly) 12-hydroxystearic acid ( Methyl) acrylate. From the viewpoint of suppressing the incorporation of foreign matter into the coating film, 2-hydroxyethyl (meth)acrylate or glyceryl (meth)acrylate is preferred.

Examples of the monomer having an isocyanate group and a vinyl bond include 2-(meth)acryloxyethyl isocyanate and 1,1-bis[(meth)acryloxy]ethyl isocyanate. These may be used alone or in combination of two or more.

(thermosetting resin)

The thermosetting resin may, for example, be an epoxy resin or a benzoquinone. Resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

<solvent>

In the blue coloring composition of the present aspect, for example, the coloring agent is sufficiently dispersed or dissolved in the colorant carrier, and applied to a substrate such as a glass substrate to have a dry film thickness of 0.2 to 5 μm, and a filter region is formed. The segment can be made to contain a solvent.

The solvent may, for example, be ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol or 1,3-butanediol diacetic acid. Ester, 1,4-two Alkane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , 3-ethylaminopropionic acid ethyl ester, 3-methyl-1,3-butanediol, 3-methylamino-3-methyl-1-butanol, 3-methoxy-3-methylbutyl Acetate, 3-methylaminobutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamidine Amine, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene , p-diethylbenzene, t-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoiso Propyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether , ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol single Diisopropyl ether, diethylene glycol monoethyl ether acetate , diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, two Propylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triethylene glycol glycerol, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Acid esters, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, from the viewpoints of good dispersibility and solubility of the pigment and the salt-forming product (A), ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monomethyl ether B are used. A diol acetate such as an acid ester or an ethylene glycol monoethyl ether acetate, an aromatic alcohol such as benzyl alcohol or a ketone such as cyclohexanone is preferred.

The solvent may be used alone or in combination of two or more. Further, the solvent is 800 to 4000 parts by mass when the total mass of the colorant is 100 parts by mass from the viewpoint that the coloring composition can be adjusted to an appropriate viscosity to form a desired filter layer having a uniform film thickness. The amount is better.

<scatter>

The blue coloring composition can be preferably dispersed with a pigment derivative by a coloring agent carrier comprising a blue pigment and a salt-forming product (A) in a resin and a solvent to be used as needed. The auxiliaries are produced together by treatment with various dispersing tools such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. Further, the blue coloring composition may be produced by dispersing a plurality of coloring agents in a coloring agent carrier, and then mixing them.

(dispersion aid)

When the colorant is dispersed in the colorant carrier, a dispersing aid such as a dye derivative, a resin type dispersant, or a surfactant can be suitably used. The dispersing aid has an excellent ability to disperse the colorant, and has a large effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, when a coloring composition in which a coloring agent is dispersed in a pigment carrier by a dispersing aid is used, a color filter having a high spectral transmittance can be obtained.

Further, in this aspect, the salt-forming product (A) functions as a dispersing aid for the blue pigment.

Pigment derivatives, which can be exemplified in organic pigments, hydrazine, acridone in three A compound having a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced.

Among these, a pigment derivative is preferred. Its structure is as shown in the following general formula (2).

P-Ln type (2)

Here, P represents an organic pigment residue, an anthracene residue, an acridone residue or three Residue, L represents a basic substituent, an acidic substituent, or a phthalimidomethyl group which may also have a substituent, and n is an integer of 1 to 4.

Examples of the organic pigment constituting the organic dye residue include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; copper indigo, copper halide indigo, and metal-free antimony; Indigo pigments such as phthalocyanine; amine guanidine, diamino dioxime, pyrimidine, flavonthrone, anthanthrone, indanthrone, pyranthrone and Anthraquinone pigments such as Violanthrone; quinophthalone pigments; Pigment; perinone pigment; lanthanide pigment; thioindigo pigment; isoporphyrin pigment; isoindolinone pigment; quinophthalone pigment; reduction (Threne) Pigments; and metal complex pigments.

For the pigment derivative, for example, those described in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5-9469 can be used. . These may be used alone or in combination of two or more.

The blending amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 mass, from the viewpoint of improving the dispersibility, when the total amount of the colorant is 100 parts by mass. More than one. In addition, the blending amount of the dye derivative is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, based on the total amount of the coloring agent, from the viewpoint of heat resistance and light resistance.

The resin type dispersant has a coloring agent affinity site having a property of adsorbing to a coloring agent and a site which is miscible with the coloring agent carrier, and is a function of adsorbing the coloring agent to stabilize the dispersion of the coloring agent carrier. . As the specific resin type dispersant, for example, polycarboxylates such as polyurethanes and polyacrylates, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and ammonium polycarboxylates can be used. Salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, hydroxyl group-containing polycarboxylate, the modified substance, poly(lower alkylene imine) and free An oily dispersant such as guanamine or a salt thereof formed by reacting a carboxyl group-containing polyester, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid Water-soluble resin such as copolymer, polyvinyl alcohol or polyvinylpyrrolidone or water-soluble polymer compound, polyester-based dispersant, modified polyacrylate-based dispersant, ethylene oxide/propylene oxide addition compound, and phosphoric acid Ester-based dispersant. These may be used alone or in combination of two or more. The resin type dispersant is not necessarily limited to these.

The commercially available resin type dispersant may, for example, be Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK吖 Japan. , 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150 and 2155, Anti-Terra-U, 203 and 204, BYK -P104, P104S, 220S and 6919, Lactimon, Lactimon-WS and Bykumen, etc., and SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, manufactured by LUBRIZOL, Japan. , 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, and 76500, and EFKA-46, 47, 48, 452, manufactured by Ciba Japan. 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502 and 1503, and taste Finetechno Inc. AJISPER PA111, PB711, PB821, PB822 and PB824.

Surfactant, for example: sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, Sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate Anionic surfactant such as ester; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and poly a nonionic surfactant such as ethylene glycol monolauryl ester; a cationic quaternary surfactant such as an alkyl quaternary ammonium salt or such an ethylene oxide adduct; an alkylbetaine such as an alkyl dimethylaminoacetic acid betaine; And an amphoteric surfactant such as alkyl imidazoline. These may be used alone or in combination of two or more. The surfactant is not necessarily limited to this.

When the amount of the resin-type dispersant and/or the surfactant is added, the amount is preferably from 0.1 to 55 parts by mass, more preferably from 0.1 to 45 parts by mass, based on 100 parts by mass of the total amount of the colorant. . When the blending amount is less than 0.1 part by mass, the effect of the resin type dispersant and/or the surfactant is difficult to obtain. When the blending amount is more than 55 parts by mass, the dispersion may be affected by an excessive amount of the dispersing agent.

In the blue coloring composition of the present aspect, a photopolymerizable compound and/or a photopolymerization initiator may be further added, and the color filter may be used as a coloring composition for a color filter.

<Photopolymerizable compound>

The photopolymerizable compound contains a monomer or oligomer which is cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. The blending amount of the photopolymerizable compound is preferably from 5 to 400 parts by mass, and from 10 to 300 parts by mass, from the viewpoints of photocurability and developability, when the total mass of the colorant is 100 parts by mass. The range is better.

Monomer or oligomer, for example: methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) Cyclohexyl acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, di(meth)acrylic acid Triethylene glycol ester, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol tri(meth)acrylate, neopentyl tetra(meth)acrylate Alcohol ester, 1,6-hexanediol diglycidyl ether di(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, neopentyl glycol diglycidyl ether II Methyl) acrylate, dipentaerythritol hexa(meth)acrylate, dineopentaerythritol penta(meth)acrylate, tricyclodecyl (meth)acrylate, ester acrylate, methylolation Various acrylates and methacrylates such as melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl Vinyl ether, Glycol divinyl ether, neopentyl alcohol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl methamine, acrylonitrile, etc. (methyl) Monomers other than acrylates; and such oligomers. These may be used alone or in combination of two or more. The monomer or oligomer is not necessarily limited to this.

<Photopolymerization initiator>

When a filter segment of a color filter is formed from a blue coloring composition by photolithography using ultraviolet light irradiation, the coloring composition is added with, for example, a photopolymerization initiator or the like, and is solvent-developed or alkali-developed. The form of the colored resist material is used. When the photopolymerization initiator is used, when the total amount of the colorant is 100 parts by mass, the blending amount is preferably from 5 to 200 parts by mass, and from the viewpoints of photocurability and developability, More preferably in the range of 10 to 150 parts by mass.

The photopolymerization initiator may, for example, be 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethylaminoacetophenone or 1-(4-isopropyl group). Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-N- Polinyl propan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-N- Acetophenone-based compounds such as phenylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal Affinity system; benzophenone, benzhydryl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylylated benzophenone, 4-phenyl a benzophenone compound such as mercapto-4'-methyldiphenylsulfide and 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chloro a thioxanthone compound such as thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; ,4,6-trichloro-s-three 2-phenyl-4,6-bis(trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three , 2-mallowyl-4,6-bis(trichloromethyl)-s-three 2,4-bis(trichloromethyl)-6-styryl-s-three ,2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three , 2-(4-methylamino-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-three , 2,4-trichloromethyl-(sunflower based)-6-three And 2,4-trichloromethyl-(4'-methoxystyryl)-6-three Wait three Compound; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenehydrazide)] and O-(ethinyl)-N-(1-benzene Anthracene ester compound such as amino-2-(4'-methylamino-naphthyl)ethylene)hydroxylamine; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide And a phosphine compound such as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; an anthraquinone compound such as 9,10-phenanthrenequinone, camphorquinone, and ethylhydrazine; a boric acid ester compound; An oxazole compound; an imidazole compound; and a dicyclopentadienyl titanium compound.

These photopolymerization initiators may be used singly or in combination of two or more kinds in any ratio. When the amount of the photopolymerization initiator to be used is 100 parts by mass based on the total amount of the coloring agent in the coloring composition for color filter, it is preferably used in an amount of 5 to 200 parts by mass, from photocurability and From the viewpoint of developability, it is more preferable to use an amount of 10 to 150 parts by mass.

<sensitizer>

The color filter may further contain a sensitizer with a blue coloring composition.

Examples of the sensitizer include unsaturated ketones such as a ketone derivative and dibenzylideneacetone; and 1,2-diketone derivatives represented by diphenylethylenedione and camphorquinone, and benzene. Acridine derivatives, anthracene derivatives, naphthoquinone derivatives, anthracene derivatives, (xanthene) derivative; sulfur derivative, a ketone derivative; a thioxanthone anthracene derivative, a coumarin derivative, a ketocoumarin derivative, an anthocyanin derivative, a merocyanin derivative, an oxonol derivative, or the like Polymethine pigment, acridine derivative, hydrazine Derivative, thiophene derivative, Derivatives, porphyrin derivatives, anthracene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, four Benzoporphyrin derivative; tetrapyridyl And Derivatives, indigo derivatives, tetraterpenoids Derivative, tetraquine Porphyrin Derivative, naphthoquinone derivative, subphthalocyanine derivative, pyryl quinone derivative, thiapyranidine derivative, tetraporphyrin derivative, annulene derivative, spiropyran derivative ,screw Derivatives, thixopyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, rice ketone derivatives, α-decyloxy esters, fluorenylphosphine oxides, methylphenylglyoxylates, Diphenylethylenedione, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4,4'-diethylm-xylylenedione, 3,3', or 4,4'-tetra (third Butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

More specifically, the "Chemicals Handbook" (1986, Kodansha), Ohara Shinko, etc., "Chemistry of Functional Pigments" (1981, CMC); and Chissen Chung San-lang, etc. Sensitizers described in "Special Functional Materials" (1986, CMC). However, the sensitizer is not limited to these. Further, the colored composition may contain a sensitizer which exhibits absorption of light in the ultraviolet to near-infrared region.

The sensitizer may be used in any ratio of two or more kinds. When the sensitizer is used, when the total mass of the photopolymerization initiator contained in the coloring composition is 100 parts by mass, the blending amount of the sensitizer is preferably 3 to 60 parts by mass, and photocurability is used. From the viewpoint of developability, 5 to 50 parts by mass is more preferable.

<Amine compound>

In the color filter of the present aspect, the coloring composition may further contain an amine compound having an action of reducing dissolved oxygen.

Examples of such an amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-di Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<leveling agent>

In the colored composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to further add a leveling agent. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in its main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include, for example, FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by BYK Corporation. Specific examples of the dimethyl methoxy olefin having a polyester structure in the main chain include, for example, BYK-310 and BYK-370 manufactured by BYK. A dimethyl methoxy alkane having a polyether structure in the main chain and dimethyl methoxy alkane having a polyester structure in the main chain may also be used in combination. The content of the leveling agent is usually in the range of 0.003 to 0.5% by mass, based on 100% by mass of the total mass of the coloring composition.

The leveling agent is a compound having a hydrophobic group and a hydrophilic group in the molecule, and is a so-called surfactant. Although it has a hydrophilic group, it has little solubility in water, and when added to a colored composition, it exhibits the ability to reduce surface tension. Low characteristics, and especially useful for glass sheets with good moisture permeability. Among them, it is preferred that the amount of addition of the coating film defect due to foaming does not sufficiently suppress the static electricity. A leveling agent having such a preferred property is, for example, a dimethylpolysiloxane having a polyoxyalkylene unit. The polyoxyalkylene unit has, for example, a polyoxyethylene unit and a polyoxypropylene unit. The dimethyl polysiloxane may also have both a polyoxyethylene unit and a polyoxypropylene unit.

The bonding form of the polyoxyalkylene unit and dimethyl polyoxyalkylene may be a pendant type or a polyoxyalkylene unit bond in which a polyoxyalkylene unit is bonded in a repeating unit of dimethyl polyoxyalkylene. The terminal modified type at the terminal of dimethyl polyoxyalkylene and the linear block copolymer type in which the polyoxyalkylene unit and the dimethylpolyoxyalkylene are alternately and repeatedly bonded. a dimethyl polyoxane having a polyoxyalkylene unit, such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, commercially available from Toray Dow Corning Co., Ltd. And FZ-2207. The dimethyl polyoxyalkylene having a polyoxyalkylene unit is not limited thereto.

In the leveling agent, an anionic, cationic, nonionic, or amphoteric surfactant may be added in an auxiliary manner. The surfactant may be used in combination of two or more kinds.

Examples of the anionic surfactant to be added to the leveling agent in an auxiliary manner include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, and an alkyl naphthalene. Sodium sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene - Monoethanolamine of acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

A cationic surfactant that is auxiliaryly added to the leveling agent, for example, an alkyl quaternary ammonium salt or an ethylene oxide adduct thereof. A nonionic surfactant that is auxiliaryly added to the leveling agent, for example, polyoxyethylene ether ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbent An amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alcohol anhydride monostearate, polyethylene glycol monolaurate or alkyldimethylaminoacetate betaine; and a fluorine-based or polyoxane-based surfactant. Surfactant.

<hardener and hardening accelerator>

In order to assist the hardening of the thermosetting resin, the coloring composition may contain a curing agent, a curing accelerator, and the like as necessary.

A curing agent such as a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, and a sulfonic acid compound is useful. The hardener is not particularly limited to this. Any hardener may be used as long as it is reactive with the thermosetting resin. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferred.

The hardening accelerator may, for example, be dicyanodiamine, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methylamino-N,N- An amine compound such as dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine; a quaternary ammonium salt compound such as triethylbenzylammonium chloride; a blocked isocyanate such as dimethylamine Compound; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole And an imidazole derivative such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, a bicyclic hydrazine compound and a salt thereof; a phosphorus compound such as triphenylphosphine; melamine, amide, and acetaminophen Amine, and benzene Isobaric amine compound; and 2,4-diamino-6-methylpropenylaminoethyl-S-three 2-vinyl-2,4-diamino-S-three 2-vinyl-4,6-diamino-S-three ‧Iso-cyanuric acid adduct, and 2,4-diamino-6-methylpropenyloxyethyl-S-three ‧Iso-cyanuric acid adducts, etc. S-three derivative. The curing accelerator may be used singly or in combination of two or more. The content of the hardening accelerator is preferably in the range of 0.01 to 15% by mass based on the total amount of the thermosetting resin.

<Other additive ingredients>

In the blue coloring composition of the present aspect, the storage stabilizer may be contained in order to keep the viscosity of the composition substantially constant for a long period of time. Further, in the colored composition, an adhesion enhancer such as a decane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

Examples of the storage stabilizer include benzyltrimethyl chloride; tetrabasic ammonium chloride such as diethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and methyl ether; and tert-catechol (pyrocatechol). ; an organic phosphine such as tetraethylphosphine or tetraphenylphosphine; and a phosphite. The storage stabilizer may be used in an amount of, for example, 0.1 to 10 parts by mass based on 100 parts by mass of the coloring agent in the coloring composition.

Examples of the adhesion enhancer include vinyl quinone (β-methylaminoethoxy) decane, vinyl ethoxy decane, and vinyl decane such as vinyl trimethoxy decane; γ-methyl propylene oxime (meth) propylene decyl oxane such as oxypropyltrimethylaminodecane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)methyl Trimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3,4-epoxycyclohexyl)methyltriethylaminononane, γ-glycidylamino Ethylene decane such as propyltrimethylaminononane and γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β (Aminoethyl) γ-aminopropyltriethylaminononane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxy An alkane decane such as decane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethylaminononane, and N-phenyl-γ-aminopropyltriethylaminodecane; And decane couples such as γ-mercaptopropyltrimethoxydecane and γ-mercaptopropyltriethylaminodecane mixture. The adhesion-increasing agent can be used in an amount of, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent in the coloring composition.

<antioxidant>

In the blue coloring composition of the present aspect, in order to increase the transmittance of the coating film, it is preferred to further contain an antioxidant.

The antioxidant prevents the photopolymerization initiator or the thermosetting resin contained in the photosensitive blue coloring composition from being deteriorated by the heat treatment in the heat curing step and the tempering step of ITO (indium tin oxide). yellow. Therefore, if the coloring composition contains an antioxidant, the transmittance of the coating film can be improved.

As the antioxidant, for example, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant or a thioether-based antioxidant is preferably used, and a hindered phenol-based antioxidant, a hindered amine-based antioxidant or a phosphorus-based antioxidant is more preferably used. These may be used alone or in combination of two or more.

The hindered phenol-based antioxidant may, for example, be neopentyl alcohol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[( Laurylthio)methyl]-o-cresol, 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-para (4-third Butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylaniline Base)-1,3,5-three .

The hindered amine-based antioxidant may, for example, be bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate or bis(N-methyl-2,2,6,6 -tetramethyl-4-piperidinyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylene Diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidin Pyridyl) propylamine, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) (1,2,3,4-butanetetracarboxylate, poly[{6-(1, 1,3,3-tetramethylbutyl)imido-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethyl{(2,2,6,6-tetramethyl-4) -piperidinyl)imido}], poly[(6-N- Lolinyl-1,3,5-three -2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene{(2,2,6,6-tetramethyl- a polycondensate of 4-piperidinyl)imido}], dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and N,N'-4,7-肆[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1 , 3,5-three -2-yl]-4,7-diin-1,10-diamine.

Examples of the phosphorus-based antioxidant include: [2-[[2,4,8,10-肆(1,1-dimethylethyl)dibenzo[d,f][1,3,2 ]two Phosphonium-6-yl]oxy]ethyl]amine, ginseng [2-[(4,6,9,11-tetra-t-butyldibenzo[d,f][1,3,2] Phosphonium-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, and the like.

The thioether-based antioxidant may, for example, be 2,2-sulfan-diethylidene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2, 4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

When the total amount of the solid components of the blue coloring composition is 100 parts by mass, the antioxidant is preferably used in an amount of 0.1 to 5 parts by mass.

<Removal of large particles>

It is preferable to remove large particles of 5 μm or more from the colored composition by a method such as centrifugation, sintering filtration, or membrane filtration, and it is preferably a large particle of 1 μm or more, more preferably a large particle of 0.5 μm or more, and dust mixed therein. As such, the colored composition preferably contains substantially no particles of 0.5 μm or more. Further, the colored composition is more preferably substantially free of particles of 0.3 μm or more.

<Color Filter>

Next, the color filter of this aspect will be described.

The color filter of this aspect contains a plurality of filter segments which are typically regularly arranged in different absorption spectra. The color filter of one form includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The color filter of another form includes at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment. In the color filter of this aspect, at least one of the filter sections, for example, the blue filter section, is formed of the coloring composition for the color filter.

The red filter segment can be formed, for example, from a typical red colored composition containing a red pigment and a colorant carrier. For red pigments, for example, C.1. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81 can be used: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Salt-forming products of red basic dyes and acid dyes can also be used.

The red coloring composition may also contain orange pigments such as CI Pigment Oranges 43, 71 and 73, and CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, One or more of yellow pigments such as 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, and 221 . Salt-forming products of basic dyes and acid dyes which are orange and/or yellow can also be used.

The green filter segment can be formed, for example, from a typical green coloring composition comprising a green pigment and a colorant carrier. For the green pigment, for example, C.I. Pigment Green 7, 7, 36, 37 or 58 can be used.

In the green coloring composition, a yellow pigment may be used in combination. Yellow pigments such as: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36 , 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151 , 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185 , 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, and 221. A salt-forming product of a yellow basic dye and an acid dye may also be used in combination.

<Method of Manufacturing Color Filter>

The color filter can be produced, for example, by a printing method or photolithography.

When the printing method is used, only the printing and drying of the coloring composition prepared as the printing ink can be repeated to form a patterned filter segment. Therefore, the printing method is low in cost and excellent in mass productivity. Further, due to the development of printing technology, it is possible to form fine patterns with high dimensional accuracy and smoothness by printing.

The ink used for printing should preferably have a composition that does not dry and cure on the printing plate or blanket. Further, in the printing method, it is also important to control the fluidity of the ink on the printing machine. The fluidity of the ink can be controlled by adjusting the viscosity of the ink using a dispersant or an extender pigment.

According to photolithography, a color filter can be manufactured with higher precision than a printing method.

When a filter segment is formed by photolithography, a coloring composition which is a solvent developing type or an alkali developing type coloring resist is prepared, and a coating method such as spray coating, spin coating, slit coating, or roll coating is used. It is coated on a transparent substrate so that the dried film thickness is, for example, in the range of 0.2 to 5 μm. The coating film is dried as needed, and the coating film is exposed to ultraviolet rays by a mask having a predetermined pattern which is provided in contact or non-contact with the coating film. Thereafter, the coating film is immersed in a solvent or an alkali developing solution, or a solvent or an alkali developing solution is sprayed onto the coating film to remove the uncured portion from the coating film. Thereby, a filter segment corresponding to a certain color can be obtained. A film pattern corresponding to the remaining filter segments is formed by repeating the same operation as described above except that the color filter composition is used with the filter segments of other colors. Thereafter, the color filter is obtained by firing the film patterns. In addition, firing can be performed each time a thin film pattern is formed.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as the alkali developer. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.

Further, in order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied onto the colored resist film obtained by applying and drying the colored resist. The coating film was dried, followed by ultraviolet exposure. A coating film composed of a water-soluble or alkali-soluble resin prevents the colored resist film from interfering with polymerization due to oxygen.

The color filter can also be produced by a method other than printing or photolithography. For example, a color filter can be produced by an electrodeposition method or a transfer method. The above colored composition can be used in any method.

Further, when the color filter is manufactured by the electrodeposition method, a substrate having a transparent conductive film on one of the main faces is prepared, and the transparent conductive film is used as an electrode, and the colloidal particles are electrophoresed on the transparent conductive film. This forms a filter segment. Further, when the color filter is manufactured by the transfer method, a filter segment is formed in advance on the main surface of the transfer substrate having a release property on one of the main faces, and the filter segment is formed in advance. Transfer from the transfer substrate to the substrate.

A black matrix that is a light-shielding pattern may also be formed on the transparent substrate before the filter segments are formed. For the black matrix, for example, a metal film such as a chromium film, a multilayer film such as a chromium/chromium oxide film, or an inorganic compound film such as a titanium nitride film, or a resin film obtained by dispersing a light shielding material in a resin can be used.

Circuits such as active matrix circuits containing thin film transistors (TFTs) may also be formed on the transparent substrate prior to forming the filter segments. Further, other layers such as an overcoat film and a transparent conductive film may be formed on the color filter as needed.

[Example A]

The present invention will be described below based on the examples, but the present invention is not limited to these. Also, "parts" means "parts by mass" unless otherwise specified. Further, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. Further, tetrahydrofuran (THF) was used to develop a solvent.

First, the acrylic resin solution, the fine pigment, and the salt-forming product (A) used in the examples and the comparative examples, a compound, a pigment dispersion, a resin solution containing a salt-forming product, and a A method of producing a resin solution of a compound, a red resist material, and a green resist material will be described.

<Method of Manufacturing Acrylic Resin Solution 1A to 4A> (Preparation of Acrylic Resin Solution 1A)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 70.0 parts of cyclohexanone was placed in the reaction container. The temperature was raised to 80 ° C, and the inside of the reaction vessel was replaced with nitrogen. Then, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 4.3 parts of methacrylic acid were added dropwise to the tube for 2 hours. A mixture of 7.4 parts of cumene phenol oxyethylene modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26,000. After the resin solution was cooled to room temperature, about 2 g was sampled. This was dried by continuously heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured. Based on the content of the nonvolatile component obtained in this manner, propylene glycol monomethyl ether acetate (PGMAC) was added to the previously synthesized resin solution, and the nonvolatile content was made 20% by mass to prepare an acrylic resin solution 1A.

(Preparation of Acrylic Resin Solution 2A)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 207 parts of cyclohexanone was placed in the reaction container. After the temperature was raised to 80 ° C and the inside of the reaction vessel was replaced with nitrogen, 20 parts of methacrylic acid and isopropyl phenol phenol ethylene oxide modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) 20 were added dropwise thereto by dropping the tube for 2 hours. A mixture of 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution.

Second, the supply of nitrogen gas is stopped. To the total amount of the copolymer resin solution, dry air was injected while stirring for 1 hour. Thereafter, the mixture was cooled to room temperature, and 6.5 parts of 2-methylpropenyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and cyclohexanone were added dropwise at 70 ° C for 3 hours. 26 parts of the mixture.

Approximately 2 g of the resin solution was sampled, dried by heating at 180 ° C for 20 minutes, and the amount of the nonvolatile component was measured. The content of the non-volatile component obtained in this manner was adjusted to 20% by mass of cyclohexanone in the previously synthesized resin solution to prepare an acrylic resin solution 2A. Further, the acrylic resin contained in the resin solution 2A had a weight average molecular weight (Mw) of 18,000.

(Preparation of Acrylic Resin Solution 3A)

207 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device. After the temperature was raised to 80 ° C and the inside of the reaction vessel was replaced with nitrogen, 20 parts of methacrylic acid and isopropyl phenol phenol ethylene oxide modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) 20 were added dropwise thereto by dropping the tube for 2 hours. A mixture of 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution.

Next, the supply of nitrogen gas was stopped, and dry air was injected for one hour while stirring the total amount of the copolymer resin solution. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methylpropenyloxyethyl isocyanate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C for 3 hours.

Approximately 2 g of the resin solution was sampled, dried by heating at 180 ° C for 20 minutes, and the amount of the nonvolatile component was measured. The content of the nonvolatile component obtained in this manner was adjusted by adding cyclohexanone to the previously synthesized resin solution and making the nonvolatile component 20% by mass to prepare an acrylic resin solution 3A. Further, the acrylic resin contained in the resin solution 3A had a weight average molecular weight (Mw) of 19,000.

(Preparation of Acrylic Resin Solution 4A)

370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device. After the temperature was raised to 80 ° C and the inside of the reaction vessel was replaced with nitrogen, 18 parts of p-cumylphenol oxyethylene modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and benzyl methacrylate were added dropwise for 2 hours. A mixture of 10 parts of ester, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further carried out at 100 ° C for 3 hours. Next, a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added to the solution, and the mixture was further reacted at 100 ° C for 1 hour. Thereafter, the inside of the reaction vessel was replaced with air, and 9.3 parts of acrylic acid (100% of epoxy propyl group) and 0.5 part of dimethylaminophenol and 0.1 part of hydroquinone were placed in the container. The reaction was continued at 120 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5. Next, to the solution thus obtained, 19.5 parts of tetrahydrophthalic anhydride (100% of the produced hydroxyl group) and 0.5 part of triethylamine were added, and the mixture was reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin.

After cooling the resin solution to room temperature, about 2 g of the sample was sampled, and it was dried by heating at 180 ° C for 20 minutes, and the amount of the nonvolatile component was measured. The acrylic resin solution 4A was prepared by adding cyclohexanone to the previously synthesized resin solution to a nonvolatile content of 20% by mass in accordance with the content of the nonvolatile component obtained in this manner. Further, the acrylic resin contained in the resin solution 4A had a weight average molecular weight (Mw) of 19,000.

<Method for Producing Micronized Pigment> (Production of blue fine pigment 1A)

Indigo blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Co., Ltd., specific surface area 60 m ² /g) 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol The stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was placed and kneaded at 80 ° C for 6 hours. Next, the kneaded product was put into 8 liters of warm water, and the mixture was stirred while heating to 80 ° C for 2 hours to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of blue fine pigment 1A. The blue fine pigment 1A had a specific surface area of 80 m ² /g.

(production of blue fine pigment 2A)

200 parts of triphenylmethane-based blue pigment CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was put into 8 liters of warm water, and stirred while heating to 80 ° C for 2 hours to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of blue fine pigment 2A. The blue fine pigment 2A has a specific surface area of 65 m ² /g.

(Production of purple fine pigment 1A)

Will be two 200 parts of purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.) The mixture was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of purple fine pigment 1A. The purple fine pigment 1A has a specific surface area of 95 m ² /g.

(Production of red fine pigment 1A)

200 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("IRGAZIN吖RED吖2030" manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), kneading was carried out at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of red fine pigment 1A. The red fine pigment 1A has a specific surface area of 70 m ² /g.

(Production of yellow fine pigment 1A)

500 parts of isoporphyrin yellow pigment CI Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 120 ° C for 8 hours. Next, the kneaded product was put into 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 80 ° C for one day and night to obtain 490 parts of yellow fine pigment 1A. The yellow fine pigment 1A has a specific surface area of 70 m ² /g.

(Production of green fine pigment 1A)

200 parts of indigo green pigment CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of green fine pigment 1A. The green fine pigment 1A had a specific surface area of 75 m ² /g.

(Production of yellow fine pigment 2A)

200 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by Lanxess Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue Co., Ltd.). ), kneading was carried out at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of yellow fine pigment 2A. The yellow fine pigment 2A has a specific surface area of 65 m ² /g.

<Method for Producing Salt-Forming Product (A)> (salt-forming product (A-1A))

A salt-forming product (A-1A) composed of C.I. Acid Red 289 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt is removed from the salt-forming product remaining on the filter paper using a dryer to obtain a salt-forming product of C.I. Acid Red 289 and distearyldimethylammonium chloride, i.e., a salt-forming product (A-1A).

(salt-forming product (A-2A))

A salt-forming product (A-2A) composed of C.I. Acid Red 289 and dilauryldimethylammonium chloride (having a molecular weight of 382 in the cationic portion) was produced by the following procedure.

C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, dilauryl dimethyl ammonium chloride was added dropwise in small portions. An aqueous solution can also be used for dilauryl dimethyl ammonium chloride. After the dropwise addition of dilauryldimethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The end point of the reaction was determined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt is removed from the salt-forming product remaining on the filter paper using a dryer to obtain a salt-forming product of C.I. Acid Red 289 and dilauryldimethylammonium chloride, i.e., a salt-forming product (A-2A).

(salt-forming product (A-3A))

A salt-forming product (A-3A) consisting of C.I. Acid Red 289 and tristearate monomethylammonium chloride (having a molecular weight of 788 in the cationic moiety) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, tristearate monomethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for tristearate monomethylammonium chloride. After the dropwise addition of tristearate monomethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and tristearate monomethylammonium chloride, that is, a salt-forming product (A-3A).

(salt-forming product (A-4A))

A salt-forming product (A-4) composed of C.I. Acid Red 52 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

The C.I. acid red 52 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 52 and distearyldimethylammonium chloride, that is, a salt-forming product (A-4A).

(salt-forming product (A-5A))

A salt-forming product (A-5A) composed of C.I. Acid Red 87 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

C.I. Acid Red 87 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 87 and distearyldimethylammonium chloride, that is, a salt-forming product (A-5A).

(salt-forming product (A-6A))

A salt-forming product (A-6A) composed of C.I. Acid Red 92 and trilaurylbenzylammonium chloride (having a molecular weight of the cationic moiety of 612) was produced by the following procedure.

The C.I. Acid Red 92 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, trisodium lauryl benzyl ammonium chloride was added dropwise in small portions. An aqueous solution can also be used for trilaurylbenzylammonium chloride. After the dropwise addition of trilaurylbenzylammonium chloride was completed, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 92 and trilaurylbenzylammonium chloride, that is, a salt-forming product (A-6A).

(salt-forming product (A-7A))

A salt-forming product (A-7A) composed of C.I. Acid Red 388 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

The C.I. Acid Red 388 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 388 and distearyldimethylammonium chloride, that is, a salt-forming product (A-7A).

(salt-forming product (A-8A))

A composition consisting of CI Acid Red 289 and a dialkyl (alkyl group having 14 to 18 carbon atoms) dimethylammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 of a cationic moiety) was produced by the following procedure. Salt product (A-8A).

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Arquad 2HT-75 was added dropwise in small portions. Aqueous solutions can also be used with Arquad 2HT-75. After the completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of CI acid red 289 and a dialkyl group (having an alkyl group having 14 to 18 carbon atoms) of dimethyl ammonium chloride. Salt-forming product (A-8A).

(salt-forming product (A-9A))

A salt formed from CI Acid Red 52 and a dialkyl (14 to 18 atomic number of alkyl group) dimethylammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 of a cationic moiety) was produced by the following procedure. Product (A-9A).

The C.I. acid red 52 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Arquad 2HT-75 was added dropwise in small portions. Aqueous solutions can also be used with Arquad 2HT-75. After the completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by using a dryer to obtain a salt-forming product of CI acid red 52 and a dialkyl group (having an alkyl group having 14 to 18 carbon atoms) of dimethyl ammonium chloride. Salt-forming product (A-9A).

(salt-forming product (A-10A))

A salt-forming product (A-10A) composed of C.I. Acid Red 289 and monolauryl trimethylammonium chloride (having a molecular weight of 228 of a cationic moiety) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, monolauryl trimethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for monolauryl trimethylammonium chloride. After completion of the dropwise addition of monolauryl trimethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point coefficient was set as the time point at which the reaction liquid was dropped on the filter paper without oozing out. That is, when the exudation disappears, it is judged that a salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and monolauryltrimethylammonium chloride, that is, a salt-forming product (A-10A).

(salt-forming product (A-11A))

A salt-forming product (A-11A) composed of C.I. Acid Red 289 and tetraethylammonium chloride (having a molecular weight of the cationic moiety of 122) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, tetraethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for tetraethylammonium chloride. After the dropwise addition of tetraethylammonium chloride was completed, the solution was stirred at 70 to 90 ° C for 60 minutes. The end point of the reaction was determined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and tetraethylammonium chloride, that is, a salt-forming product (A-11A).

< Method for producing a compound > ( Compound (C-1A))

The CI acid red 289 is sulfonated and chlorinated according to the usual method, and then it is made into two The alkane is reacted with a theoretical equivalent of dodecylamine to obtain a sulfonamide compound of CI acid red 289 ,, ie Compound (C-1A) (according to the description of JP-A-6-194828).

( Compound (C-2A))

CI acid red 52 is sulfonated and chlorinated according to the usual method. The alkane is reacted with a theoretical equivalent of dodecylamine to obtain a sulfonamide compound of CI Acid Red 52, ie Compound (C-2A) (according to Japanese Patent Application Laid-Open No. Hei 6-194928).

<Method for Producing Pigment Dispersion> (Preparation of pigment dispersion (DP-1A))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersion treatment was carried out for 5 hours using an Eigermill ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.). Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DP-1A).

Blue Fine Pigment 1A (C.I. Pigment Blue 15:6) 11.0

Acrylic resin solution 1A 40.0

Propylene glycol monomethyl ether acetate (PGMAC) 48.0

Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.) 1.0

(Preparation of pigment dispersions (DP-2A) to (DP-7A))

Pigment dispersions (DP-2A) to (DP-7A) were prepared in the same manner as in the above pigment dispersion (DP-1A) except that the blue fine pigment 1A was changed to the pigment shown in Table 1.

<Resin solution containing salt-forming product and containing Method for producing resin solution of compound> (Preparation of resin solution (DA-1A) containing salt-forming product)

After the following mixture was stirred uniformly, it was filtered with a 5.0 μm filter to obtain a resin solution (DA-1A) containing a salt-forming product.

Salt-forming product (A-1A) 11.0 parts

Acrylic resin solution 1A 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC) 49.0 parts

(Preparation of resin solution (DA-2A) to (DA-11A) containing salt-forming product)

A resin solution containing a salt-forming product (DA-) was prepared in the same manner as the salt-forming product-containing resin solution (DA-1A) except that the salt-forming product (A-1A) was changed to the salt-forming product shown in Table 2. 2A) to (DA-11A).

(contain Preparation of resin solutions (DC-1A) and (DC-2A)

In addition to changing the salt-forming product (A-1A) to the one shown in Table 2. In addition to the above-mentioned compound, it is carried out in the same manner as the above-mentioned resin solution (DA-1A) containing a salt-forming product, and is prepared and contained. A resin solution (DC-1A) and (DC-2A) of the compound.

<Method of Manufacturing Red and Green Resist Material> (Preparation of red resist material)

The following mixture was stirred well, and then filtered through a 1.0 μm filter to obtain a red resist material.

Pigment Dispersion (DP-4A) 50.0 parts

Pigment Dispersion (DP-5A) 10.0 parts

Acrylic resin solution 1A 11.0 parts

Trimethylolpropane triacrylate 4.2 parts

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.)

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a green resist.

Pigment dispersion (DP-6A): 45.0 parts

Pigment dispersion (DP-7A): 15.0 parts

Acrylic resin solution 1A: 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.)

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1A to 11A and Comparative Examples 1A and 2A] (Example 1A: Colored composition (DB-1A))

After the following mixture was uniformly stirred, it was filtered with a 5.0 μm filter to obtain a mixed coloring composition (DB-1A).

Resin solution containing salt-forming product (DA-1A): 2.2 parts

Pigment dispersion (DP-1A): 8.8 parts

Acrylic resin solution 1A: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Examples 2A to 1A and Comparative Examples 1A and 2B: Colored Compositions (DB-2A) to (DB-13A))

The resin solution (DA-1) containing the salt-forming product is changed to a resin solution containing a salt-forming product as shown in Table 3 or contains In the same manner as the coloring composition (DB-1A), a coloring composition (DB-2A) to (DB-13A) was prepared, except that the resin solution of the compound was used.

(coating film foreign body test)

With respect to the above colored composition, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, the colored composition was applied onto a transparent substrate to a dry film thickness of about 2.0 μm, and this was heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Then, the number of identifiable particles is calculated in any five fields of view, and the total number of particles is obtained. The results are shown in Table 3.

In Table 3, the symbols in the "coated foreign matter" column have the following meanings.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

When the total number of particles is less than 20, coating unevenness due to foreign matter hardly occurs. In addition, when the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. In addition, when the total number of particles is 100 or more, coating unevenness (speckle) due to foreign matter occurs.

The coating film obtained from the coloring composition (DB-1A) to (DB-11A) has a small amount of foreign matter (undissolved foreign matter). On the other hand, the coating film obtained from the coloring composition (DB-12A) and (DB-12B) has a large amount of foreign matter. That is, When a dye is formed into a salt with a quaternary ammonium compound, it is replaced by a In the case of a functional group of a dye, more excellent properties can be achieved.

In Examples 1A to 9A, more excellent performance can be achieved than in Examples 10A and 11A. The salt-forming product of the coloring composition used in Example 10A contained only one alkyl chain having 5 or more carbon atoms in the quaternary ammonium moiety thereof. Further, the salt-forming product of the colored composition used in Example 11A was not contained in the quaternary ammonium moiety of the alkyl chain having 5 or more carbon atoms. Then, the salt-forming products of the coloring compositions used in Examples 1A to 9A contained two or more alkyl chains having 5 or more carbon atoms in the quaternary ammonium portion thereof. Therefore, it is preferred that the quaternary ammonium moiety of the salt-forming product contains two or more alkyl chains having 5 or more carbon atoms.

[Examples 12A to 24A and Comparative Examples 3A to 5A] (Example 12: Resist material (R-1A))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-1A).

Resin solution containing salt-forming product (DA-1A): 12.0 parts

Pigment dispersion (DP-1A): 48.0 parts

Acrylic resin solution 1A: 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.)

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13A to 24A and Comparative Examples 3A to 5A: Resist materials (R-2A) to (R-16A))

In the same manner as the resist material (R-1A), the type of the resin solution and the pigment dispersion containing the colorant and the amount of the pigment dispersion were changed as shown in Table 4, and an alkali-developing resist was obtained. Materials (R-2A) to (R-16A). Further, in all of the resist materials, the total amount of the resin solution containing the colorant and the pigment dispersion was 60 parts.

(Examples 25A to 30A: Resist materials (R-17A) to (R-22A))

In the same manner as the resist material (R-10A), the alkali-developing resist material (R-17A) and (R-17A) were obtained, except that the acrylic resin solution 1A was changed to the acrylic resin solutions 2A, 3A, and 4A. R-18A) and (R-19A).

In addition, the acrylic resin solution 1A was changed to the acrylic resin solutions 2A, 3A, and 4A, and the alkali-developing resist material (R-20A) was obtained in the same manner as the resist material (R-11A). (R-21A) and (R-22A).

(evaluation of resist material)

A coating film was formed from the resist materials (R-1A) to (R-22A), and for each of the coating films, the chromaticity, the amount of foreign matter, heat resistance, light resistance, and solvent resistance were examined by the following methods.

(coating film foreign body test)

With respect to the above-mentioned resist material, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, a resist material was applied onto a transparent substrate to have a dry film thickness of about 2.5 μm, and the coating film was entirely exposed to ultraviolet light. Thereafter, the mixture was heated at 230 ° C for 20 minutes in the oven, and then allowed to cool to obtain an evaluation substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is calculated. The results are shown in Table 5.

In addition, in Table 5, the meaning of the mark in the "coating foreign matter" column is as follows.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

When the total number of particles is less than 20, coating unevenness due to foreign matter hardly occurs. In addition, when the total number of particles is 20 or more and less than 100, foreign matter is large, but there is no problem in use. In addition, when the total number of particles is 100 or more, coating unevenness due to foreign matter may occur.

(Evaluation of color characteristics)

A resist material is coated on the glass substrate. Specifically, the resist material was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.060. The substrate was heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). Table 5 shows the results.

(coating film heat resistance test)

The resist material was applied onto the transparent substrate to a dry film thickness of about 2.5 μm, and the coating film was exposed to ultraviolet light by passing through a mask having a predetermined pattern. The alkali developer is sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, it was heated in an oven at 230 ° C for 20 minutes. After cooling, the color of the obtained coating film under a C light source was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1), b*( 1)). Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was further measured.

Using these chromaticities, the color difference ΔEab* is calculated according to the following calculation formula. Further, the heat resistance of the coating film was evaluated in the following four stages based on the color difference ΔEab*.

◎: ΔEab* is less than 1.5

o: ΔEab* is 1.5 or more and less than 3.0

△: ΔEab* is 3.0 or more and less than 5.0

×: ΔEab* is 5.0 or more

The results are shown in Table 5.

(coating film light resistance test)

The test substrate was prepared in the same manner as the coating film heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a* (1), b*(1)). Thereafter, the substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIK1 Co., Ltd.), and left for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using these chromaticities, the color difference ΔEab* was calculated in the same manner as the coating film heat resistance test, and the light resistance of the coating film was evaluated in four stages on the same basis as the heat resistance. Table 5 shows the results.

(film resistance test)

The test substrate was produced in the same procedure as the heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1) ), b*(1)). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the chromaticity was used in the same manner as the coating film heat resistance test, and calculation was performed. The color difference ΔEab* was evaluated in the solvent resistance of the coating film in four stages using the same criteria as the heat resistance. Table 5 shows the results.

The coloring layer obtained from the resist materials (R-1A) to (R-12A) and (R-14A) to (R-19A) exhibits excellent light resistance. Moreover, the coloring layer obtained from the resist material (R-13A) is excellent in color characteristics. Further, the coloring layer obtained from the resist material (R-13A) is somewhat low in heat resistance, light resistance, and solvent resistance, but is used at a level where the color filter is not problematic.

On the other hand, the coloring layer obtained from the resist materials (R-14A) and (R-15A) has many foreign matters. Further, the coloring layer obtained from the resist material (R-16) is colored compared to those obtained from the resist materials (R-1A) to (R-13A) and (R-17A) to (R-22A). Layer, brightness (Y) is low.

Further, from the results obtained with respect to the resist materials (R-17A) to (R-22A), it is understood that if an active energy ray-curable resin having a vinyl bond is used, the foreign matter of the coating film can be reduced.

[Examples 31A to 49A and Comparative Examples 6A to 8A] (Example 31A: Color filter (CF-1A))

A black matrix of a light-shielding pattern was formed on the glass substrate, and then a red resist was applied using a spin coater. The red resist material was applied such that the film thickness was such that the chromaticity under the C light source was x=0.640 and y=0.330. For the coating film, an ultraviolet ray was irradiated with an ultrahigh pressure mercury bulb through a reticle at an exposure amount of 300 mJ/cm ² . Next, the coating film was supplied to a spray developing using an alkali developing solution composed of a 0.2% by mass aqueous sodium carbonate solution, the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

Next, a green resist material was applied on the substrate by the same method as described above. The green resist material was applied so that the chromaticity under the C light source became a film thickness of x=0.300 and y=0.600. The coating film was exposed, developed, washed, and fired in the same manner as the above-described red filter segment to form a green filter segment.

Further, a blue resist (R-1A) was applied to the substrate in the same manner as described above. The blue resist (R-1A) was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.06. The coating film was exposed, developed, washed, and fired in the same manner as the red filter segment to form a blue filter segment. As described above, a color filter (CF-1A) was obtained.

(production of liquid crystal display)

An electrode made of indium tin oxide (ITO) was formed on a color filter (CF-1A), and an alignment layer made of polyimide was formed thereon. Further, a TFT array and a pixel electrode were formed on one surface of the separately prepared glass substrate, and an alignment layer made of polyimide was formed thereon.

Next, on the surface of the glass substrate on which the electrode is provided, a sealant is used to form a frame-like pattern having a passage connecting the inside and the outside of the frame. Then, the substrates are bonded to each other with the spacer beads interposed therebetween so that the electrodes face each other.

Next, in the internal space of the cell obtained in this manner, the liquid crystal composition was injected from the previous via. After the via was sealed, a polarizing plate was attached to both sides of the unit cell to obtain a liquid crystal display panel.

Thereafter, the liquid crystal display panel is combined with a backlight unit including a 3-wavelength CCFL (cold catho de fluorescent lamp) or the like to complete the liquid crystal display.

(Examples 32A to 49A and Comparative Examples 6A to 8A)

A color filter (CF-2A) was produced in the same manner as the color filter (CF-1A) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 6. To (CF-22A) and LCD display.

(Evaluation of color filters (CF-1A) to (CF-22A))

The liquid crystal display was displayed in a color image, and the brightness of the region corresponding to the red, green, and blue filter segments was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Further, the brightness displayed in white is obtained from the brightness. The results are shown in Table 6.

The blue filter segment of the liquid crystal display of Comparative Example 8A is composed of a copper indigo pigment and two It is formed by the resist of the pigment. As shown in Table 6, the liquid crystal displays of Examples 31A to 49A were able to display white images with higher brightness than the liquid crystal display of Comparative Example 8A.

Further, in the liquid crystal displays of Comparative Examples 6A and 7A, white images can be displayed with high brightness. However, as described above, the resist materials used in Comparative Examples 6A and 7A are not practical because many foreign matters are generated in the filter segments.

(Example 50A)

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-50A).

Resin solution containing salt-forming product (DA-1A): 12.0 parts

Pigment dispersion (DP-1A): 48.0 parts

Acrylic resin solution 1A: 10.5 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.)

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Antioxidant neopentyl alcohol-肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]: 0.5 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

The resist (R-50A) was subjected to the same evaluation as that of the resist (R-1A). As a result, the lightness (Y) was 6.9, and very good performance (?) was achieved in all of the coating foreign matter, heat resistance, light resistance, and solvent resistance. That is, the brightness is improved due to the use of the antioxidant.

○Second aspect

Next, the second aspect will be described.

The blue coloring composition of the color filter of the second aspect contains a binder resin and a coloring agent and an amine compound of copper indigo. The colorant contains a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group.

When a color filter is produced using the blue coloring composition of the second aspect, high definition and a wide color reproduction area can be achieved, and excellent performance can be achieved also for heat resistance and light resistance. Further, when the color filter is produced using the blue coloring composition, generation of fluorescence can be suppressed, and a high contrast ratio can be achieved. This blue coloring composition is especially useful in blue filter segments.

As described above, the conventional combination of copper enamel blue pigment and two The color filter of a color filter such as a pigment has a transmission spectrum of a blue coloring composition, and the peak position exists in the vicinity of 450 nm, and the transmittance on the short wavelength side of 450 nm or less sharply decreases.

On the other hand, the color filter of the present aspect suppresses the fluorescence in the region of 550 to 650 nm with the blue coloring composition. Further, the blue colored composition has a high transmittance on the short wavelength side of 450 nm or less, and is higher than the copper indigo blue pigment and the second at 450 nm. The blue coloring composition is a combination of pigments and has a high transmittance.

The luminescence spectrum of a backlight such as a cold cathode tube has a peak wavelength in or near a wavelength range of, for example, 425 to 440 nm. Further, the light emission spectrum of the backlight such as the light-emitting diode has a peak wavelength in a wavelength region of, for example, about 450 nm.

Therefore, the color filter obtained by the colored filter of the present aspect can achieve a high brightness ratio and a high contrast ratio.

"Colorant"

The color filter of the present aspect is a coloring agent for the blue coloring composition, and contains It is a salt-forming product composed of an acid dye and a compound having a cationic group, and a blue pigment.

By using blue pigment together An acid dye, as described above, achieves high transmittance in or near the wavelength range of 425 to 500 nm. Yes, compared to the combination of copper phthalocyanine pigments and two A conventional filter segment made of a pigment can achieve high brightness and wide color reproducibility.

<blue pigment>

The blue pigment can be used, for example, in the first aspect.

<Other pigments>

The blue colored composition of this aspect is the same as the first aspect, and other organic pigments may be added as long as the effect is not hindered. This organic pigment can be used, for example, in the first aspect.

[Micronization of pigments]

The blue pigment used in the blue coloring composition of this aspect and the other pigments used arbitrarily can be subjected to salt milling treatment in the same manner as in the first aspect to be fine. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of good dispersion in the colorant carrier. Further, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly preferred range is 25 to 85 nm.

Further, the primary particle diameter of the pigment was determined from an electron micrograph of a pigment by TEM (transmission electron microscope). Specifically, first, the pigment particles were sampled on a grid to prepare a sample for TEM observation. Next, this sample was observed by TEM, and the short axis diameter and the major axis diameter of the primary particles were individually measured for 100 or more pigment particles. And the average of these is regarded as the primary particle diameter of the pigment particles.

< Acid dyes>

Preferred in this aspect It is an acid dye which is red or purple and has any form of acid dye and direct dye.

Red or purple It is an acid dye and belongs to acid dyes such as CI Acid Red and CI Acid Violet, or direct dyes such as CI Direct Red and CI Direct Violet. Here, since the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, it is a form of an acid dye in this aspect.

The dye-based acid dye can be used, for example, in the first aspect. Among the acid dyes, it is particularly preferable because the rose red dye is excellent in color developability and resistance.

Used in this aspect An acid dye having a transmittance of 90% or more for light having a wavelength of 650 nm, a transmittance of 75% or more for light having a wavelength of 600 nm, a transmittance of 5% or less for light having a wavelength of 550 nm, and a wavelength of 400 nm for a wavelength of 400 nm. A light transmittance of 70% or more is preferred. More preferably, the transmittance for light having a wavelength of 650 nm is 95% or more, the transmittance for light having a wavelength of 600 nm is 80% or more, the transmittance for light having a wavelength of 550 nm is 10% or less, and light for a wavelength of 400 nm. The penetration rate is 75% or more.

also, The acid dye has a spectral characteristic having a high transmittance in a wavelength region of 400 to 450 nm. that is, Acid dyes have good spectroscopic properties. but, It is an acid dye which, like a general dye, lacks light resistance and heat resistance, and is not very satisfactory when used in an image display which requires high reliability for a color filter. Therefore, in order to improve the shortcomings of these dyes, The acid dye is preferably in the form of, for example, a salt-forming product with a quaternary ammonium compound, a tertiary amine, a secondary amine or a primary amine. It is particularly preferred that the acid dye is formed into a salt product with a quaternary ammonium compound.

( a salt-forming product of an acid dye and a quaternary ammonium compound) ‧Quaternary ammonium compound

The quaternary ammonium compound can be used in the same manner as the first aspect, for example, in the first aspect.

‧ salt treatment

The salt-forming product of an acid dye and a quaternary ammonium compound can be obtained in the same manner as described in the first aspect.

Among the salt-forming products, in particular, a salt-forming product of a quaternary ammonium compound having a molecular weight of from 350 to 800 in the range of from CI to 289 and a cationic moiety, is excellent in solvent solubility, and when used in combination with a blue pigment, excellent heat resistance can be achieved. Sex, lightfastness and solvent resistance. Further, the reason why the salt-forming product is used in combination with the blue pigment to achieve good performance is that the salt-forming product is adsorbed to the blue pigment in a state of being dissolved or dispersed in a solvent. From such a viewpoint, the primary particle diameter of the blue pigment is preferably in the range of 20 to 100 nm.

The amount of the salt-forming product of the acid dye and the quaternary ammonium compound is preferably in the range of 1 to 80 parts by mass, more preferably in the range of 5 to 60 parts by mass, per 100 parts by mass of the blue pigment. When the amount of the salt-forming product is less than 1 part by mass, the reproducible chromaticity region is narrowed, and if it exceeds 80 parts by mass, the desired hue may not be obtained.

Copper Azurin Compound (C)

As far as colorants are concerned, when When a salt product of an acid dye and a quaternary ammonium compound is used in combination with a blue pigment, transparency is high due to the solubility of the dye, and a filter segment having a higher brightness can be obtained than when only a pigment is used. . However, conversely, the dye itself will fluoresce and there is a problem that the contrast ratio is lowered. The main reason is that the brightness of the black display is improved by the fluorescent light.

In the case of a coloring agent, a coloring composition containing only a pigment is a blue coloring composition, and in order to improve the dispersibility of the blue pigment, it is known that a copper indigo compound having an acidic substituent or a base is conventionally added. A copper indigo compound of a sexual substituent.

Moreover, since the copper phthalocyanine compound having a substituent has a high transmittance in a wavelength region of 400 to 450 nm, it is suitable as a component to be added to the blue coloring composition. However, when it will be more brighter When a dye is used together with a blue pigment, it will be produced because The fluorescent luminescence of the dye causes a problem of a decrease in the contrast ratio. When a copper indigo compound having an acidic substituent at the end is used (for example, a copper phthalocyanine compound or the like), no effect of solving the problem is observed.

The inventors of the present invention have studied the problem of reducing the contrast caused by the fluorescent light emission. As a result, the inventors of the present invention found that in addition to containing blue pigment and " A coloring agent which is a salt-forming product of an acid dye and a quaternary ammonium compound, by using a copper indigo amine compound (C) as described later in detail The fluorescence of the dye does not affect the display, that is, the luminance at the time of black display can be lowered, and high contrast can be achieved.

The reason why the fluorescent matting effect is remarkable when these substances are used is not known, but the inventors of the present invention consider the following reasons. Copper azurin compound (C), relative to The dye or copper indigo pigment has high mutual solubility and is highly efficient in fluorescence extinction. In particular, copper bismuth sulfonate amide compound is easy to The dye forms a charge transporting complex, and therefore, in addition to the above effects, the fluorescent light itself can be effectively suppressed. As a result, an extremely high fluorescence extinction effect can be obtained. Moreover, in addition to the matting effect of the above-mentioned fluorescent light, when the copper phthalocyanine decylamine compound is used, since the dye and the copper phthalocyanine blue pigment exhibit high mutual solubility, the copper phthalocyanine particles and the dye are more inhibited in the resist. Light scattering due to uneven presence. As a result, the luminance at the time of black display becomes extremely low, and a very high contrast ratio can be achieved.

A copper ruthenium amine compound (C), for example, a basic compound having a basic substituent (copper phthalocyanine decylamine compound), or a salt forming product of an acidic substituent and a quaternary ammonium salt (copper phthalocyanine sulfonic acid) An ammonium salt) or a compound having a phthalimidomethyl group which may have a substituent. The details will be described below.

The copper phthalocyanine compound (C) used in this aspect, the copper phthalocyanine pigment is preferably a basic compound having a basic substituent, especially a copper sulfonium sulfonate ammonium salt, a copper phthalocyanine tertiary amine, or a copper phthalocyanine The sulfonate amide compound is preferred.

Specifically, the copper indigo amine compound (C) represented by the following general formula (4) can be suitably used.

General formula (4):

P-Lm

[In the formula (4), P is a m-valent copper indigo pigment residue, m is an integer of 1 to 4, and L is a group selected from the substituents represented by the general formulae (5) to (7) Any of them. ]

[In the general formulae (5) to (7), X is -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, or direct bonding, Y ⁰ is -NH-, -O-, or directly bonded, n is an integer from 1 to 10, Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ -, or directly bonded, R ⁹ and R ¹⁰ Each independently is a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z represents an alkylene group having 1 to 20 carbon atoms or 1 to 1 carbon atom. 20 of the aryl group.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ^{2 are} integrated to further contain nitrogen, oxygen or sulfur. a heterocyclic ring of an atom, each of R ³ , R ⁴ , R ⁵ and R ^{6 is} independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a carbon number of 6 to 20 The aryl group, R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and R ⁸ is a substituent represented by the formula (5), or a formula (6) A substituent represented by Q, which represents a hydroxyl group, an alkylamino group having 1 to 20 carbon atoms, a substituent represented by the formula (5), or a substituent represented by the formula (6). ]

An amine component used to form a substituent represented by the general formulae (5) to (7), for example, dimethylamine, diethylamine, methylethylamine, N,N-ethylisopropylamine, N,N- Ethyl propylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisopropylamine, dipropylamine, N,N-second butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, N,N-isobutyl-second butylamine, diamylamine, diisoamylamine, dihexylamine , dicyclohexylamine, bis(2-ethylhexyl)amine, dioctylamine, N,N-methyloctadecylamine, diamine, diallylamine, N,N-ethyl-1,2-di Methylpropylamine, N,N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethyl Aminopentylamine, N,N-dimethylaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N-diethylaminohexylamine, N, N-diethylaminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminopropylamine, N,N-dibutylaminoethylamine , N,N-dibutylaminobutylamine, N,N-diisobutylaminopentanamine, N,N-methyllauryl propylamine, N,N-ethylhexylaminoethylamine , N,N-distearate ethylamine, N,N-dioleylamine, N,N-distearate, butyridine, 2-methylpiperidine, 3-methyl Piperidine, 4-methylpiperidine, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, piperidinecarboxylic acid, 4-piperidinic acid, methyl 4-piperidinecarboxylate, ethyl 4-piperidinecarboxylate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-Aminoethyl-4-methylpiperidine, N-Aminoethyl Porphyrin, N-aminopropyl piperidine, N-aminopropyl-2-methylpiperidine, N-aminopropyl-4-methylpiperidine, N-aminopropyl Porphyrin, N-methyl pipe N-butylperidazole N-methyl risperazine 1-cyclopentylperidazole 1-amino-4-methylper 1-cyclopentylperidine .

A copper indigo amine compound having a basic substituent can be synthesized in various synthetic routes. For example, after introducing any one of the substituents represented by the following formulas (8) to (11), it may be reacted with the above substituents to form a substituent represented by the general formulae (5) to (7). The above amine component, such as N,N-dimethylaminopropylamine, N-methylpiperidone , diethylamine, or 4-[4-hydroxy-6-[3-(dibutylamino)propylamino]-1,3,5-three Obtained by the reaction of 2-ylamino]aniline.

Formula (8): -SO ₂ Cl

Formula (9): -COCl

Formula (10): -CH ₂ NHCOCH ₂ Cl

Formula (11): -CH ₂ Cl

When the substituent of the formula (8) to (11) is reacted with the above amine component, a part of the substituents of the formulae (8) to (11) may be hydrolyzed, and the chlorine may be substituted by a hydroxyl group. In this case, the substituents of the formulae (8) and (9) each become a sulfonic acid group and a carboxylic acid group, but either of them may maintain a free acid, or may be a metal having a valence of 1 to 3 or a monoamine as described above. salt.

The substituent represented by the formula (7) can be synthesized by various synthetic routes. For example, at least one of the cyanuric chloride and the amine component forming the substituent represented by the formula (5) or (6), for example, N, N, can be obtained by using cyanuric chloride as a starting material. -dimethylaminopropylamine or N-methylpiperidine The reaction is then carried out by reacting the remaining chlorine of cyanuric chloride with various amines or alcohols and the like.

Among the copper phthalocyanine compounds used in this aspect, the best form is a copper phthalocyanine sulfonamide compound which is a copper phthalocyanine compound.

The copper phthalocyanine decylamine compound refers to the above copper indigo compound having a basic substituent, X is -SO ₂ - or -CH ₂ NHSO ₂ CH ₂ -, Y ⁰ is -NH- or direct bonding , n is an integer from 1 to 10, and Y ¹ is a compound of -NH- or -NR ⁹ -Z-NR ¹⁰ -.

(herein, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is a carbon number of 1 to 20 The alkyl group is preferably an alkylene group having 1 to 10 carbon atoms or an extended aryl group having 1 to 20 carbon atoms, preferably an extended aryl group having 1 to 10 carbon atoms, and may, for example, be exemplified For example, methylene, ethyl, propyl and phenyl.)

The copper indigo amine compound (C) to be used in the present invention may be used alone or in combination of two or more.

The blending amount of the copper indigo amine compound (C) used in this aspect is, when the total amount of the coloring agent is 100 parts by mass, from the viewpoint of quantum yield and solubility of the fluorescent dye derived from the dye, It is preferably in the range of 0.01 to 200 parts by mass, more preferably in the range of 1 to 100 parts by mass.

In the coloring agent composition of the present aspect, the copper indigo amine compound (C) and " The mass ratio of the salt product of the acid dye to the quaternary ammonium compound (the mass of the amine compound (C) /" It is preferred that the salt product of the acid dye and the quaternary ammonium compound is from 0.3 to 1.5. When it is less than 0.3, the contrast between the phosphoric acid and the copper indigo amine compound (C) is insufficient, and the contrast is lowered. When it exceeds 1.5, the color characteristics are affected and the brightness is low. A better mass ratio is from 0.4 to 1.2, and an optimum mass ratio is from 0.5 to 1.1.

Resin (B)

In the case where the resin is dispersed, dyed, or impregnated with the coloring agent, the same as those described in the first aspect may be used, and examples thereof include a thermoplastic resin and a thermosetting resin. Further, in addition to the above main resin, rosin ester can also be used as the auxiliary resin. That is, the resin (B) is composed of a main resin and an optional auxiliary resin.

[thermoplastic resin]

The thermoplastic resin can be used in the same manner as described in the first aspect. The method (a) or (b) described using the first aspect is preferred.

[thermosetting resin]

The thermosetting resin is the same as the first aspect, and examples thereof include an epoxy resin, a benzoheptamine resin, a melamine resin, a urea resin, and a phenol resin.

[rosin ester]

The coloring composition of the present aspect, as described above, in addition to the aforementioned resin, in order to improve pigment dispersibility and improve and maintain It is a dye-resistant and can also contain rosin ester as an auxiliary resin.

Rosin ester, for example, gum rosin based on rosin acid, neo-abietic acid, levopimaric acid, hydrogenated rosin acid, pimaric acid, dextran rosin acid, etc. , pine oil rosin, wood rosin, uneven rosin, hydrogenated rosin, partially heterogeneous rosin, maleated rosin and mixtures thereof and esters of polyols (glycerides, pentaerythritol esters, diethylene glycol esters, etc.) , especially good for pentaerythritol ester).

The rosin ester which can also be used in this aspect can be obtained, for example, by the following method.

A refined rosin such as refined gum rosin, refined wood rosin, refined polymerized rosin, refined uneven rosin, and refined pine oil rosin is used as a starting material, and these are esterified with an alcohol, whereby a rosin ester can be obtained. The esterification reaction can be carried out directly under ordinary conditions. For example, the esterification reaction is carried out under a flow of a passive gas, and the refined rosin and the following alcohol are heated to, for example, 150 to 300 ° C to cause a reaction to remove the produced water to the outside of the system.

The alcohol component used for the esterification is not particularly limited, and examples thereof include a unit alcohol such as n-octanol, 2-ethylhexanol, decyl alcohol and lauryl alcohol; ethylene glycol, diethylene glycol, propylene glycol, and neopentyl a glycol such as an alcohol or cyclohexanedimethanol; a trihydric alcohol such as glycerin, trimethylolethane or trimethylolpropane; and a tetrahydric alcohol such as pentaerythritol or diglycerin. Among them, it is preferred to use a ternary or quaternary polyol. These may be used alone or in combination of two or more.

Further, an esterification catalyst or an antioxidant may be used as needed. Examples of the esterification catalyst include acid catalysts such as acetic acid and p-toluenesulfonic acid, hydroxides of alkali metals such as calcium hydroxide, and metal oxides such as calcium oxide and magnesium oxide.

Commercially available rosin esters which can be used include, for example, the following.

(rosin ester)

Arakawa Chemical Industry Co., Ltd. manufactures PENSEL A, AZ, ESTERGUM AAG, AAL, A, AAV, 105, HS, AT, etc.

NEOTALL G2, 101K, NT-15, 125HK, HARIESTER TF, NL, S, P, C, DS-70L, DS-90, DS-130, etc., manufactured by Nippon Chemical Co., Ltd.

(Polymerized rosin ester)

Arakawa Chemical Industry Co., Ltd. made PENSEL D-125, D-135, D-160 and so on.

Harima Chemical Co., Ltd. HARIESTER KT-2.

(uneven rosin ester)

Arakawa Chemical Industry Co., Ltd., SUPER ESTER A-75, A-100, A-115, -125, T-125, etc.

(rosin modified maleic acid resin, rosin modified fumarate resin)

MALKYD NO.1, 2, 5, 6, 8, 30A, 31, 32, 33, 34, 3002, etc., manufactured by Arakawa Chemical Industry Co., Ltd.

Harimato T-80, R-100, M-453, M-130A, 135GN, 145P, R-120AH, etc. (hydrogenated rosin ester) manufactured by Harima Chemical Co., Ltd.

Arakawa Chemical Industry Co., Ltd. ESTERGUM H, HP, HD, etc.

Among them, a polymerized rosin ester, a heterogeneous rosin ester, or a rosin-modified maleic acid resin (containing a rosin-modified fumaric resin) is preferred.

The rosin ester used in this aspect preferably has an acid value of 100 mgKOH/g or less. More preferably, it is a rosin ester having an acid value of 40 mgKOH/g or less. The acid value is particularly preferably in the range of 5 to 40 mgKOH/g, and if it is within this range, it can effectively act on The performance of the acid dye is maintained.

Further, in consideration of compatibility with the above-mentioned main resin, storage stability and productivity, the rosin ester is preferably in a range of 70 to 150 ° C in terms of a softening point of the ring and ball method. When it is lower than 70 ° C, the storage stability is lowered, and the blue coloring composition is liable to aggregate. Moreover, when it exceeds 150 ° C, the adhesiveness of a color filter will fall. Here, the main resin means the above-mentioned thermoplastic resin and/or thermosetting resin.

The amount of the rosin ester added is preferably from 0.3 to 5 parts by mass based on 100 parts by mass of the above-mentioned main resin. When the amount of the rosin ester added is less than 0.3 parts by mass, the effect may not be obtained. Further, if the amount added is more than 5 parts by mass, the resin properties may be adversely affected.

Solvent

In the blue coloring composition of the present aspect, in order to sufficiently disperse and impregnate the coloring agent in the colorant carrier, it is easy to apply it to a substrate such as a glass substrate to form a dry film thickness of 0.2 to 5 μm in the same manner as in the first aspect. The filter section may contain a solvent.

The solvent can be used in the same manner as in the first aspect.

Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol are used from the viewpoint of good dispersibility, solubility, and permeability of the coloring agent. A diol acetate such as diethyl ether acetate, an aromatic alcohol such as benzyl alcohol, or a ketone such as cyclohexanone is preferred. Among them, cyclohexanone is preferably used.

"dispersion"

In the blue coloring composition of the present aspect, the coloring agent can be finely dispersed in the resin (B) and copper indigo by using various dispersing tools such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. The amine compound (C) and a solvent carrier which is optionally used as a solvent are produced. Further, the blue coloring composition of the present aspect may be produced by dispersing a plurality of coloring agents in a colorant carrier.

[Dispersing Aid]

When the coloring agent (A) is dispersed in the coloring agent carrier, a dispersing aid such as a resin type dispersing agent or a surfactant may be used in the same manner as in the first aspect. The dispersing aid is excellent in the ability to disperse the pigment component in the coloring agent, and has a large effect of preventing re-aggregation of the coloring agent after dispersion. When a blue coloring composition obtained by dispersing a coloring agent in a coloring agent carrier by a dispersing aid is used, a color filter having a high spectral transmittance can be obtained.

In the blue coloring composition of the present aspect, a photopolymerizable compound and/or a photopolymerization initiator may be further added, and a photosensitive blue coloring composition (blue resist material) may be used as a color filter.

Photopolymerizable compound

In this aspect, for example, the photopolymerizable compound described in the first aspect can be used in the same manner as in the first aspect.

Photopolymerization initiator

In the color filter of the present aspect, the blue coloring composition is used, and when the filter segment is formed by photolithography which is cured by ultraviolet irradiation of the composition, photopolymerization can be added in the same manner as in the first aspect. The initiator or the like is adjusted in the form of a solvent developing type or an alkali developing type colored resist.

Sensitizer

In the blue coloring composition of the color filter of this aspect, the sensitizer can be further contained as in the first aspect.

Oxygen Reductive Amine Compounds

Further, the blue colored composition of the present aspect may contain an oxygen-reductive amine compound having an action of reducing dissolved oxygen.

Such an oxygen-reductive amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

Leveling agent

In the blue coloring composition of the present aspect, in order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent in the same manner as in the first aspect.

"hardener, hardening accelerator"

In addition, in order to assist the hardening of the thermosetting resin, the blue coloring composition of the present aspect may contain a curing agent, a curing accelerator, and the like in the same manner as in the first aspect.

Other Additives

In the blue colored composition of this aspect, in order to keep the viscosity of the composition substantially constant, the storage stabilizer may be contained in the same manner as in the first aspect. Further, in order to improve the adhesion to the transparent substrate, an adhesion enhancer such as a decane coupling agent may be contained in the same manner as in the first aspect.

<<Antioxidants>>

In order to increase the transmittance of the coating film, the blue coloring composition of the present aspect preferably contains an antioxidant similarly to the first aspect.

"Method for Producing Photosensitive Blue Coloring Composition"

When the color filter of the present aspect is used as a photosensitive blue coloring composition in the form of a solvent developing type or an alkali developing type coloring resist material, for example, it can be contained by a blue coloring composition. Pigments and A coloring agent which is a salt forming product of an acid dye and a compound having a cationic group, and a mixture of a coloring agent carrier containing a resin (B), a copper indigo amine compound (C), and an organic solvent to be used as needed, A blue coloring composition is prepared by treating various blue dispersing tools such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and an open roll type continuous kneader, and in the blue coloring composition It is obtained by mixing a photopolymerizable compound, a photopolymerization initiator, and other resins, solvents, dispersants, additives, and the like as needed.

"Removal of Large Particles"

It is preferable to remove a large particle of 5 μm or more, preferably a large particle of 1 μm or more, more preferably 0.5 μm, by a method of centrifugation, sintering filtration, or membrane filtration from a blue coloring composition of the color filter of the present aspect. The above large particles and mixed dust. As described above, it is preferable that the color filter for the color filter contains substantially no particles of 0.5 μm or more. More preferably, all particles are substantially 0.3 μm or less. In addition, these particle diameters are the values measured by the particle size distribution measuring apparatus "Nano-S (SYSMEX (share))" by the dynamic light-scattering method.

Color Filter

The color filter of the aspect has, for example, at least one red filter segment, at least one green filter segment, at least one blue filter segment, and the at least one blue filter The sheet segments were formed using the color filter of this aspect with a blue coloring composition.

The red filter segment can be formed using a general red coloring composition containing a red pigment and a pigment carrier, as in the first aspect. Further, in the red colored composition, an orange pigment and/or a yellow pigment may be used in combination as in the first aspect.

The green filter segment can be formed using a general green coloring composition containing a green pigment and a pigment carrier, as in the first aspect.

Further, in the green coloring composition, a yellow pigment may be used in combination as in the first aspect.

"Manufacturing method of color filter"

The color filter of this aspect can be produced by a printing method or a photolithography method similarly to the first aspect.

[Example B]

This aspect will be described below based on the embodiments, but the aspect is not limited to these. In addition, "parts" means "parts by mass" unless otherwise specified.

First, the acrylic resin solution and colorant used in the examples and comparative examples will be described. A dye and a fine pigment), a pigment dispersion, a dye-containing resin solution, a copper indigo amine compound (C), and a method for producing a red and green resist used in the production of a color filter.

Here, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. Further, tetrahydrofuran (THF) was used as a developing solvent.

The degree of refinement of the pigment was evaluated by the specific surface area of the pigment particles and the average primary particle diameter. The measurement of the specific surface area was carried out by a BET (Brunauer-Emmett-Teller) method using nitrogen adsorption using an automatic vapor adsorption amount measuring device ("BELSORP18" manufactured by BEL Corporation, Japan).

The contrast ratio of the coating film was measured in accordance with the following method.

(measurement method of contrast ratio of coating film)

The light emitted from the backlight unit of the liquid crystal display is incident on the first polarizing plate, and the linearly polarized light that has penetrated the first polarizing plate penetrates the dried coating film of the coloring composition, and is then incident on the second polarizing plate. Further, the luminance of the second polarizing plate is measured such that the transmission axes of the first and second polarizing plates are parallel to each other (corresponding to white display) and the transmission axes of the first and second polarizing plates are orthogonal to each other. The situation (equivalent to black display) both. The contrast ratio is a ratio of the luminance when the transmission axes of the first and second polarizing plates are parallel, and the luminance when the transmission axes are orthogonal to each other.

Here, the luminance meter is a color luminance meter ("BM-5A" manufactured by TOPCON Co., Ltd.), and the first and second polarizing plates are "NPF-G1220DUN" manufactured by Nitto Denko Corporation. In addition, in order to shield unwanted light, a black mask having a hole of 1 cm square was placed on the second polarizing plate, and the region corresponding to the hole was performed.

Further, when the linear polarized light penetrates the dried coating film of the colored composition, it is scattered by the pigment particles to become elliptically polarized light. As a result, when the transmission axes of the first and second polarizing plates are parallel, the amount of light penetrating through the second polarizing plate is reduced, that is, when the scattering of the pigment in the coating film occurs, the luminance when the transmission axis is parallel is lowered. When the transmission axis is orthogonal, the luminance increases, so the contrast ratio becomes lower.

<Method for Producing Acrylic Resin Solution 1B to 4B> (Preparation of Acrylic Resin Solution 1B)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 69.4 parts of cyclohexanone was placed in the reaction container. After the temperature was raised to 80 ° C and the inside of the reaction vessel was replaced with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate and 4.3 parts of methacrylic acid were added dropwise thereto by dropwise addition of a tube for 2 hours. A mixture of 7.4 parts of cumene phenol oxidized ethylene modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. Then, 0.6 parts of a polymerized rosin ester "PENSEL D-125" (manufactured by Arakawa Chemical Industries Co., Ltd.) was added to the solution, and the mixture was stirred at 80 ° C for 30 minutes.

After the resin solution was cooled to room temperature, about 2 g was sampled. This was dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured. The acrylic resin solution 1B was prepared by adding cyclohexanone to the previously synthesized resin solution to a nonvolatile content of 20% by mass based on the content of the nonvolatile component obtained in this manner.

(Preparation of Acrylic Resin Solution 2B)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 205 parts of cyclohexanone was placed in the reaction container. After the temperature was raised to 80 ° C and the inside of the flask was replaced with nitrogen, 20 parts of methacrylic acid and 20 parts of cumene phenol oxyethylene modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) were added dropwise for 2 hours. A mixture of 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, the supply of nitrogen gas was stopped, and the dry air was injected for 1 hour while stirring the total amount of the copolymer solution, and then cooled to room temperature, and 2-methylpropenylaminoethyl isocyanate was added dropwise at 70 ° C for 3 hours (Showa Denko) A mixture of 6.5 parts of Karenz MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone. Then, 2.0 parts of a polymerized rosin ester "PENSEL D-125" (manufactured by Arakawa Chemical Co., Ltd.) was added to the solution, and the mixture was stirred at 80 ° C for 30 minutes.

After the resin solution was cooled to room temperature, about 2 g was sampled. This was dried by heating at 180 ° C for 20 minutes, and the amount of the nonvolatile component was measured. The acrylic resin solution 2B was prepared by adding cyclohexanone to the previously synthesized resin solution to a nonvolatile content of 20% by mass based on the content of the nonvolatile component obtained in this manner. Further, the acrylic resin contained in the resin solution 2B had a weight average molecular weight (Mw) of 18,000.

(Preparation of Acrylic Resin Solution 3B)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 207 parts of cyclohexanone was placed in the reaction container. After the temperature was raised to 80 ° C and the inside of the flask was replaced with nitrogen, 20 parts of methacrylic acid and 20 parts of cumene phenol oxyethylene modified acrylate (ARONI M110 manufactured by Toagosei Co., Ltd.) were added dropwise for 2 hours. A mixture of 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, the supply of nitrogen gas was stopped, and dry air was injected for one hour while stirring the total amount of the copolymer solution. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methylpropenyloxyethyl isocyanate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C for 3 hours. Then, 2.0 parts of a polymerized rosin ester "PENSEL D-125" (manufactured by Arakawa Chemical Co., Ltd.) was added to the solution, and the mixture was stirred at 80 ° C for 30 minutes.

After the resin solution was cooled to room temperature, about 2 g was sampled. This was dried by heating at 180 ° C for 20 minutes, and the amount of the nonvolatile component was measured. The acrylic resin solution 3B was prepared by adding cyclohexanone to the previously synthesized resin solution to a nonvolatile content of 20% by mass in accordance with the content of the nonvolatile component obtained in this manner. Further, the acrylic resin contained in the resin solution 3B had a weight average molecular weight (Mw) of 19,000.

(Preparation of Acrylic Resin Solution 4B)

A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable four-necked flask, and 370 parts of cyclohexanone was placed in the reaction container. After the temperature was raised to 80 ° C and the inside of the flask was replaced with nitrogen, 18 parts of p-cumylphenol oxyethylene modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and benzyl methacrylate were added dropwise for 2 hours. A mixture of 10 parts, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the temperature was raised to 100 ° C and reacted at this temperature for 3 hours. Thereafter, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (100% of epoxy propylene), 0.5 part of dimethylaminophenol, and 0.1 part of hydroquinone were placed in the above container. The reaction was continued at 120 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5. Next, 19.5 parts of tetrahydrophthalic anhydride (100% of the produced hydroxyl group) and 0.5 part of triethylamine were added to the solution thus obtained, and the mixture was reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin. Then, 2.0 parts of a polymerized rosin ester "PENSEL D-125" (manufactured by Arakawa Chemical Industries Co., Ltd.) was added to the solution, and the mixture was stirred at 80 ° C for 30 minutes.

After cooling the resin solution to room temperature, about 2 g of the sample was sampled, and the mixture was heated at 180 ° C for 20 minutes to dry, and the amount of the nonvolatile component was measured. The acrylic resin solution 4B was prepared by adding the cyclohexanone to the previously synthesized resin solution to a nonvolatile content of 20% by mass. Further, the acrylic resin contained in the resin solution 4B had a weight average molecular weight (Mw) of 19,000.

< Method for producing dyes> ( Dye ([A2]-1B): rose red salt product)

Manufactured from CI Acid Red 289 and Dialkyl (alkyl C14 to C18) dimethylammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 in the cationic moiety) by the following procedure Is a dye ([A2]-1).

The CI Acid Red 289 was dissolved in 7 to 15 mol% of a sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Arquad 2HT-75 was added dropwise in small portions. Aqueous solutions can also be used with Arquad 2HT-75. After the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. The mixture was allowed to cool to room temperature while stirring, and then subjected to suction filtration and water washing. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of CI Acid Red 289 and a dialkyl (alkyl group C14 to C18) dimethyl ammonium chloride, that is, A dye ([A2]-1B).

( Dye ([A2]-2B): rose red salt product)

Manufactured from CI Acid Red 289 and distearyl dimethyl ammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 for the cationic moiety) by the following procedure A dye ([A2]-2B).

The CI Acid Red 289 was dissolved in 7 to 15 mol% of a sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the dropwise addition of QUARTAMIN D86P was completed, the solution was stirred at 70 to 90 ° C for 60 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of CI Acid Red 289 and distearyl dimethyl ammonium chloride. A dye ([A2]-2B).

( Dye ([A2]-4B): Salt-forming product)

Manufactured from CI Acid Red 87 and distearyl dimethyl ammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 for the cationic moiety) by the following procedure A dye ([A2]-4B).

The CI Acid Red 87 was dissolved in 7 to 15 mol% of a sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the dropwise addition of QUARTAMIN D86P was completed, the solution was stirred at 70 to 90 ° C for 60 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by using a dryer to obtain a salt-forming product of CI Acid Red 87 and distearyl dimethyl ammonium chloride. A dye ([A2]-4B).

<Method for Producing Micronized Pigment> (Production of blue fine pigment ([A1]-1B))

200 parts of triphenylmethane-based blue pigment CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a blue fine pigment ([A1]-1B). The blue fine pigment ([A1]-1B) had a specific surface area of 65 m ² /g, and the average primary particle diameter observed by TEM was 55 nm.

(Production of blue fine pigment ([A1]-2B))

200 parts of indigo blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1 gallon kneading process made of stainless steel. The machine (manufactured by Inoue Seisakusho Co., Ltd.) was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a blue fine pigment ([A1]-2B). The blue fine pigment ([A1]-2B) had a specific surface area of 80 m ² /g, and the average primary particle diameter observed by TEM was 50 nm.

(Production of red fine pigment)

200 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a red fine pigment. The red fine pigment had a specific surface area of 65 m ² /g, and the average primary particle diameter observed by TEM was 54 nm.

(Production of green fine pigment)

200 parts of indigo green pigment CI Pigment Green 36 ("Leonol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a green fine pigment. The green fine pigment had a specific surface area of 75 m ² /g, and the average primary particle diameter observed by TEM was 51 nm.

(Production of yellow fine pigment 1B)

500 parts of isoporphyrin yellow pigment CI Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was kneaded at 120 ° C for 8 hours. Next, the kneaded product was put into 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 80 ° C for a day and night to obtain 490 parts of yellow fine pigment 1B. The yellow fine pigment 1B had a specific surface area of 80 m ² /g, and the average primary particle diameter observed by TEM was 49 nm.

(Production of yellow fine pigment 2B)

200 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by Lanxess Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.). ), kneading was carried out at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of yellow fine pigment 2B. The yellow fine pigment 2B had a specific surface area of 70 m ² /g, and the average primary particle diameter observed by TEM was 53 nm.

(Production of purple fine pigment)

Will be two 200 parts of purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.) The mixture was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a purple fine pigment. The purple fine pigment had a specific surface area of 95 m ² /g, and the average primary particle diameter observed by TEM was 45 nm.

<Method for Producing Pigment Dispersion> (Production of Pigment Dispersion (P-1B))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersion treatment was carried out for 5 hours using an Eiger mill ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.). Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (P-1B).

(Preparation of pigment dispersions (P-2B) to (P-7B))

A pigment dispersion (P-2B) to (P-) was prepared in the same manner as in the above pigment dispersion (P-1B) except that the blue fine pigment ([A1]-1B) was changed to the pigment shown in Table 7. 7B).

<Manufacture of Resin-Containing Resin Solution> (Preparation of dye-containing resin solution (DA-1B))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersion treatment was carried out for 5 hours using an Eiger mill ("Minimodel M2 50 MKII" manufactured by Eiger Japan Co., Ltd.). Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a dye-containing resin solution (DA-1B).

Salt-forming product 1B 11.0 parts

Acrylic resin solution 1B 40.0 parts

Cyclohexanone 49.0 parts

(Preparation of dye-containing resin solution (DA-2B) to (DA-4B))

Change the salt-forming product 1B to the one shown in Table 8. A dye-containing resin solution (DA-2B) and (DA-4B) were prepared in the same manner as the dye-containing resin solution (DA-1B) except for the dye.

<Method of Manufacturing Red and Green Resist Material> (Preparation of red resist material)

The following mixture was stirred well, and then filtered through a 1.0 μm filter to obtain a red resist.

Pigment dispersion (P-3B): 50.0 parts

Pigment dispersion (P-5B): 10.0 parts

Acrylic resin solution 1B: 11.0 parts

Trimethylolpropane triacrylate

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.): 4.2 copies

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a green resist.

Pigment dispersion (P-4B): 45.0 parts

Pigment dispersion (P-6B): 15.0 parts

Acrylic resin solution 1B: 11.0 parts

Trimethylolpropane triacrylate

("NK ESTER ATMPT" by New Nakamura Chemical Co., Ltd.): 4.2 copies

Photopolymerization initiator

("Irgacure 907" by Ciba Japan): 1.2 copies

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

<Method for Producing Copper Azurin Compound (C)>

Commercially available substances are used for the copper ruthenium amine compounds (C-1B) and (C-2B). The specific substance name or chemical structure is shown in Table 9.

(Production of copper phthalocyanine compound (C-3B): copper phthalocyanine sulfonamide compound)

30 parts of copper indigo was poured into 300 parts of chlorosulfonic acid to completely dissolve it. Next, 24 parts of sulfinium chloride was added to the solution, and the temperature was gradually raised to 101 ° C, and the reaction was allowed to proceed at this temperature for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered, and washed with water. The obtained press cake was dispersed in 300 parts of water to form a slurry, and 15 parts of N,N-dimethylaminopropylamine was added to the slurry, and the mixture was stirred at room temperature for 3 hours, followed by stirring at 60 ° C for 2 hours. Thereafter, the mixture was filtered, washed with water and dried to obtain 36 parts of a copper phthalic acid sulfonamide compound (E-3). The composition of the obtained copper phthalocyanine sulfonamide compound was analyzed by a liquid chromatography mass spectrometer platform LCZ manufactured by Waters Corporation. As a result, the product does not contain a compound having three or more substituents, and is a copper phthalocyanine sulfonamide compound (C-3B-D1) having one substituent of the following formula (12) and having two or less The copper oxalate sulfonate oxime compound (C-3B-D2) having a substituent of the formula (12) is a mixture contained in a mass ratio of 85:15.

(Production of copper azurin compound (C-4B) to (C-6B): copper phthalocyanine sulfonamide compound)

The copper oxalate sulfonate amide compound (C) was prepared in the same manner as the copper oxalate sulfonamide compound (C-3B) except that the N,N-dimethylaminopropylamine was changed to the starting material shown in Table 9. -4B) to (C-6B).

In Table 9, "CuPc" represents a copper indigo residue. In addition, in Table 9, the copper phthalocyanine compound (D-1B) is described as "SOLSPERSE 12000" (manufactured by LUBR IZOL Co., Ltd., Japan).

[Examples 1B to 6B and 8B to 15B and Comparative Examples 1B, 2B and 4B] <Production of blue coloring composition> (Example 1B: Blue coloring composition (DB-1B))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersion treatment was carried out for 5 hours using an Eiger mill ("Minimodel M2 50 MKII" manufactured by Eiger Japan Co., Ltd.). Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a coloring composition for color filter (DB-1B).

Dye-containing resin solution (DA-1B): 10.0 parts

Pigment dispersion (P-1B): 50.0 parts

Acrylic resin solution 1B: 11.0 parts

Cyclohexanone: 27.4 parts

Resin type dispersant

("EFKA4300" manufactured by Ciba Japan): 1.0 part

Copper indigo amine compound (C-1B)

("SOLPERSE5000" manufactured by LUBRIZOL Co., Ltd.; copper sulfonium sulfonate ammonium salt): 0.6 parts

(Examples 2B to 6B and 8B to 15B and Comparative Examples 1B, 2B and 4B: Blue Colored Compositions (DB-2B) to (DB-6B), (DB-8B) to (DB-13B), and (DB) -15B))

The dye-containing resin solution (DA-1B) and the pigment dispersion (P-1B) and the copper indigo amine compound (C-1B) were each changed to the dye-containing resin solution and pigment dispersion shown in Table 10. The blue coloring composition (DB-2B) to (DB-6B) and (DB-8B) were prepared in the same manner as the blue coloring composition (DB-1B) except for the copper phthalocyanine compound. To (DB-13B) and (DB-15B). In addition, two or more pigment dispersions are used in a part of the blue coloring composition, but the total mass parts of the dye-containing resin solution and the pigment dispersion are 60 parts in all the blue coloring compositions. The blending of the obtained blue coloring composition is shown in Table 10.

[Evaluation of Blue Colored Compositions (DB-1B) to (DB-6B), (DB-8B) to (DB-13B) and (DB-15B) for Color Filters]

The blue coloring compositions (DB-1B) to (DB-6B), (DB-8B) to (DB-13B), and (DB-15B) were respectively coated in a vertical and horizontal dimension of 100 mm × 100 mm using a spin coater. On a glass substrate with a thickness of 1.1 mm. Each of the blue coloring compositions was applied so that the chromaticity under the C light source was y = 0.06. The substrates were then heated at 230 ° C for 20 minutes to form a blue colored layer on the substrate. Thereafter, the contrast ratio was determined by the above method for each of the substrates on which the coloring layer was formed. The results are shown in Table 11.

The blue coloring composition (Examples 1B to 6B and 8B to 11B) containing the copper indigo amine compound (C) is used in comparison with the blue coloring composition using the copper indigo-free amine compound (C). In the case of the materials (Comparative Examples 1B, 2B, and 4B), a high contrast ratio can be achieved. Among these, when blue colored compositions (DB-3B) to (DB-6B) and (DB-8B) to (DB-11B) containing a copper phthalocyanine decylamine compound are used, achievable Very high contrast ratio.

[Examples 12B to 20B and 23B to 26B and Comparative Examples 5B to 6B and 8B] <Production of Resist Material> (Example 12B: Resist material (R-1B))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain a resist (R-1B).

Blue coloring composition (DB-1B): 60.0 parts

Acrylic resin solution 1B: 11.6 parts

Trimethylolpropane triacrylate

("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.): 3.6 copies

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13B to 20B and 23B to 26B and Comparative Examples 5B to 6B and 8B: Resist materials (R-2B) to (R-9B), (R-12B) to (R-17B), and (R- 19B))

The blue coloring composition (DB-1B) and the acrylic resin solution 1B were changed to the blue coloring composition and the acrylic resin solution shown in Table 11, respectively, and the same procedure as in the resist material (R-1B) was carried out. The alkali-developable resist materials (R-2B) to (R-9B), (R-12B) to (R-17B) and (R-19B) were obtained. The composition of these resist materials is shown in Table 11.

[Evaluation of resist materials (R-1B) to (R-9B), (R-12B) to (R-17B) and (R-19B)]

Evaluation of color characteristics (lightness) and contrast ratio of resist materials (R-1B) to (R-9B), (R-12B) to (R-17B) and (R-19B) and heat resistance test, in accordance with The following methods are performed.

(Evaluation of color characteristics)

Each of the above resist materials was applied onto a glass substrate to have a film thickness of y=0.06 under a C light source. The substrates were heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). Table 11 shows the results.

(contrast ratio evaluation)

The contrast ratio was measured in accordance with the above method for each of the above substrates on which the coloring layer was formed. The results are shown in Table 11.

(Method of coating film heat resistance test)

The resist material was applied onto the transparent substrate to a dry film thickness of about 2.5 μm, and the coating film was exposed to ultraviolet rays through a mask having a predetermined pattern. The alkali developer was sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, this was equal to heating in an oven at 230 ° C for 20 minutes. After cooling, the color of the obtained coating film under a C light source was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1), b*( 1)). Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the chromaticity 2 (L*(2), a*(2), b*(2)) under a C light source was measured.

Using these chromaticities, the color difference ΔEab* is calculated according to the following calculation formula. Further, the heat resistance of the coating film was evaluated in the following four stages based on the color difference ΔEab*.

◎: ΔEab* is less than 1.5

0: ΔEab* is 1.5 or more and less than 3.0

△: ΔEab* is 3.0 or more and less than 5.0

×: ΔEab* is 5.0 or more

The results are shown in Table 11.

Same as the evaluation result of the colored composition, using blue pigment and a coloring agent which is a salt-forming product of an acid dye and a quaternary ammonium compound, and a resist material (R-1B) to (R-9B) and (R-12B) containing a copper indigo amine compound (C) When (R-15B) is used, it is higher than when using resist materials (R-16B), (R-17B), and (R-19B) containing no copper indigo amine compound (C). Contrast ratio. Among these, it is possible to achieve a particularly high degree of use of the resist materials (R-3) to (R-9B) and (R-12B) to (R-15B) containing the copper phthalocyanine sulfonamide compound. Contrast ratio. It is speculated that this is because There is electrostatic attraction between the dye and the copper phthalocyanine decylamine compound, so that the fluorescent extinction of the dye can be efficiently performed, and the miscibility of the dye with the copper phthalocyanine pigment is good, so the copper phthalocyanine particles and The dye does not distribute unevenly in the resist, so that light scattering is suppressed.

Also, copper azurin compound (C) and " In Example 3B in which the mass ratio of the acid dye to the quaternary ammonium compound was from 0.3 to 1.5, the copper indigo amine compound (C) had little influence on the color characteristics of the blue coating film. Specifically, in Example 3B, higher brightness can be achieved than in Example 4B in which the mass ratio is more than 1.5. Further, in Example 3B, compared with Example 5B in which the mass ratio is less than 0.3, the ability to suppress fluorescence is excellent, and a higher contrast ratio can be achieved.

Examples 13B to 20B and 23B to 26B used copper indigo pigment C.I. Pigment Blue 15:6 as a blue pigment. Therefore, in Examples 13B to 20B and 23B to 26B, more excellent heat resistance can be achieved than in Example 12B using C.I. Pigment Blue 1 of a triarylmethane system as a blue pigment.

On the other hand, use a fine pigment (CI Pigment Violet 23) instead In Comparative Example 8B of the dye, it was confirmed that the brightness was lowered and the contrast ratio was lowered.

About heat resistance, when When using rose red salt products in dyes, it is better than using When a salt dye (Example 26B) was used or when a fine pigment (CI Pigment Violet 23) was used, it was confirmed that more excellent heat resistance can be achieved. Further, excellent heat resistance can also be achieved in Examples 17B to 19B. The reason for this is considered to be that the hardenability of the coating film is improved because the resin solution contains an active energy ray-curable resin having a vinyl bond.

From these results, it is understood that the use of the resist material of the color composition of the present aspect can achieve excellent color characteristics (lightness), high contrast ratio, and heat resistance.

[Examples 27B to 35B and 38B to 41B and Comparative Examples 9B to 10B and 12B]

A color filter was produced using the obtained resist material.

(Example 27B: Color filter (CF-1B))

A black matrix of a light-shielding pattern was formed on the glass substrate, and then a red resist was applied using a spin coater. The red resist material was applied such that the chromaticity under the C light source became a film thickness of x = 0.640. The coating film was irradiated with ultraviolet rays at an exposure amount of 300 mJ/cm 2 through a mask using an ultrahigh pressure mercury lamp. Next, the coating film was subjected to spray development using an alkali developing solution composed of a 0.2% by mass aqueous sodium carbonate solution, and the unexposed portion was removed and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

Next, a green resist material was applied on the substrate by the same method as described above. The green resist material was applied so that the chromaticity under the C light source was y = 0.600. The coating film is subjected to the same exposure, development, cleaning, and firing as described above for the red filter segment to form a green filter segment.

Further, a blue resist (R-1B) was applied on the substrate in the same manner as described above. The blue resist (R-1B) was applied so that the chromaticity under the C light source became a film thickness of y=0.06. The coating film was subjected to the same exposure, development, cleaning, and firing as described above for the red filter segment to form a blue filter segment. The color filter (CF-1B) was obtained in the above manner.

(production of liquid crystal display)

An electrode made of ITO was formed on a color filter (CF-1B), and an alignment layer made of polyimide was formed thereon. Further, a TFT array and a pixel electrode were formed on one surface of a separately prepared glass substrate, and an alignment layer made of polyimide was formed thereon.

Next, on the surface of the glass substrate on which the electrode is provided, a sealant is used to form a frame-like pattern having a passage connecting the inside and the outside of the frame. Then, the substrates are bonded to each other such that the electrodes are opposed to each other with the electrodes facing each other.

Next, in the internal space of the unit cell obtained in this manner, the liquid crystal composition was injected from the previous passage. After the via was sealed, a polarizing plate was attached to both sides of the unit cell to obtain a liquid crystal display panel.

Thereafter, the liquid crystal display panel is combined with a backlight unit or the like to complete the liquid crystal display.

(Examples 28B to 35B and 38B to 41B and Comparative Examples 9B to 10B and 12B: color filters (CF-2B) to (CB-9B), (CB-12B) to (CB-17B), and (CF- 19B))

A color filter (CF-2B) was produced in the same manner as the color filter (CF-1B) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 12. To (CB-9B), (CB-12B) to (CB-17B) and (CF-19B) and liquid crystal displays. Figure 1 shows the luminescence spectrum of the backlight used herein.

[Evaluation of color filters (CF-1B) to (CB-9B), (CB-12B) to (CB-17B) and (CF-19B)]

The liquid crystal display was displayed in a color image, and the brightness of the region corresponding to the red, green, and blue filter segments was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Further, the brightness displayed in white is obtained from the brightness.

Further, for the regions corresponding to the red, green, and blue color filter segments, a contrast ratio was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and black-and-white display was obtained from the contrast ratios. The contrast ratio at the time. In addition, the contrast ratio in black-and-white display is practically required to be 7600 or more, and 7600 or more is preferable. The evaluation results of the color filters are shown in Table 12.

The blue resist materials used in Comparative Examples 9B, 10B, and 12B did not contain: blue pigment [A1] and A coloring agent (A) of the dye [A2], and a copper indigo amine compound (C). In Examples 27B to 35B and 38B to 41B, the contrast ratio at the time of black-and-white display was higher than that of Comparative Examples 9B, 10B, and 12B, and practical performance was achieved. The reason why the performance achieved in Comparative Examples 9B and 10B was low was that the blue resist materials used in Comparative Examples 9B and 10B did not contain the copper indigo amine compound (C), and thus The fluorescent component of the dye acts as light leakage, and as a result, the luminance at the time of black display is improved. Further, from the results of Comparative Example 12B, it was confirmed that if a fine pigment (CI Pigment Violet 23) was used instead of the Rose Bengal dye or If the dye is dyed, the brightness will become lower.

As described above, by using a blue pigment [A1] together with The coloring agent (A) of the dye [A2] and the copper azurin compound (C) can obtain a blue coloring composition for color filters and a color filter excellent in color characteristics (lightness), heat resistance, and contrast ratio. Light film.

○3rd aspect

Next, the third aspect will be described.

The blue coloring composition of the color filter of the third aspect contains a binder resin and a coloring agent. The colorant contains a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group. In this aspect, an amine is used as a compound having a cationic group. The amine is selected from at least one of the group consisting of a primary amine, a secondary amine, and a tertiary amine.

When a color filter is produced using the blue coloring composition of the third aspect, a high brightness and a wide color reproduction area can be achieved, and since the dye is in the form of a salt-forming product, heat resistance, light resistance, and solvent resistance are achieved. Sex can also achieve excellent performance.

Also, the conventional combination of copper enamel blue pigment and two The color filter of a color filter such as a pigment has a breakthrough spectrum of a blue coloring composition, and the peak position is present at around 450 nm, and the transmittance is rapidly lowered on the short wavelength side of 450 nm or less.

In contrast, when the color filter of the present aspect is colored with a blue color, it is compared with the use of the copper phthalocyanine blue pigment and the second When the pigment is combined, a high transmittance is achieved on the short wavelength side of 450 nm or less. Further, the luminescence spectrum of many backlights such as a cold cathode tube has, for example, a peak wavelength in or near a wavelength range of 425 to 500 nm. The filter segment obtained by using the blue coloring composition of the color filter of the present aspect can achieve high brightness.

<colorant>

The color filter of the present aspect is a coloring agent for a blue coloring composition, comprising: And an acid dye and a salt-forming product (A) and a blue pigment selected from at least one selected from the group consisting of a primary amine, a secondary amine and a tertiary amine.

By using the salt-forming product (A) in combination with the blue pigment, as described above, a high transmittance can be achieved in the wavelength range of 425 to 500 nm or in the vicinity thereof. Yes, compared to the combination of copper phthalocyanine pigments and two A well-known color filter for pigments achieves high brightness and wide color reproducibility. Further, the salt formation of the acid dye can achieve high solvent solubility in addition to high heat resistance, light resistance and solvent resistance.

(salt-forming product (A))

The salt-forming product (A) will be described below. by An acid dye, used in a salt forming product (A) composed of a cationic component of a primary amine, a secondary amine or a tertiary amine The acid dye is red or purple and has the form of a dye.

Red or purple It is an acid dye and belongs to acid dyes such as CI acid red and CI acid purple, or direct dyes such as CI direct red and CI direct purple. Here, the direct dye has a form of an acid dye in this aspect because it has a sulfonic acid group.

Salt-forming product (A) It is a salt-forming dye which is formed by acid dyes (also including direct dyes) with the opposite component amines which produce relative ions, and which are modified as needed. In the salt formation reaction, the amine compound exists as an ammonium ion in an aqueous solution and reacts with an acid dye dissolved in the aqueous solution. It is preferred here to use an aqueous acetic acid solution.

[ Acid dye]

Following instructions It is an acid dye. The acid dye can be used in the same manner as in the first aspect.

Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, or C.I. Acid Red 388 is preferably used.

[amine compound]

Next, the description is generated It is a relative ion of an acid dye, that is, an amine of a cationic component. Since an amine has an amine group, its ion is used as a relative ion of an acid dye.

The amine which is the relative component of the salt-forming product (A) is preferably colorless or white.

Here, colorless or white means a state of being transparent, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. That is, the above-mentioned amine must not interfere with the color development of the dye component and does not cause a change in color thereof.

The amine may be a primary amine, a secondary amine or a tertiary amine. Among them, from the viewpoint of excellent heat resistance and light resistance, it is preferred to use a secondary amine or a tertiary amine. Primary amines are generally inferior in performance compared to secondary amines and tertiary amines, but can be preferred materials by optimizing the number of carbon atoms such as alkyl groups.

The molecular weight of the amine is preferably in the range of from 129 to 591, more preferably in the range of from 255 to 591. When the molecular weight is less than 129, light resistance and heat resistance are lowered, and solubility in a solvent is lowered. Further, when the molecular weight is more than 591, the ratio of the chromonic component in the molecule is lowered, and as a result, the color developability is lowered and the brightness is also lowered. Here, the molecular weight is determined according to the structural formula. The atomic weight of C is set to 12, the atomic weight of H is set to 1, and the atomic weight of N is set to 14.

Further, preferred molecular weights of the primary amine, the secondary amine and the tertiary amine are as follows.

The molecular weight of the primary amine is, for example, in the range of 129 to 297, preferably in the range of 255 to 297. When the molecular weight is less than 129, light resistance and heat resistance are lowered, and solubility in a solvent may be lowered. Moreover, when the molecular weight is more than 297, the ratio of the chromonic component in the molecule is lowered, and the color developability is lowered, and the brightness tends to be lowered.

The molecular weight of the secondary amine is, for example, in the range of 241 to 577, preferably in the range of 353 to 577. When the molecular weight is less than 241, light resistance and heat resistance are lowered, and solubility in a solvent may be lowered. Moreover, when the molecular weight is more than 577, the ratio of the chromonic component in the molecule is lowered, and the color developability is lowered, and the brightness is also lowered.

The molecular weight of the tertiary amine is, for example, in the range of from 255 to 591, preferably in the range of from 311 to 591. When the molecular weight is less than 255, the light resistance and heat resistance are lowered, and the solubility in a solvent may be lowered. Moreover, when the molecular weight is more than 591, the ratio of the chromonic component in the molecule is lowered, and the color developability is lowered, and the brightness is also lowered.

The secondary amine and the tertiary amine are preferably represented by the following formula (13).

General formula (13):

R ₁ R ₂ R ₃ N

[In the general formula (13), two of R ₁ to R ₃ each independently represent an alkyl group or a benzyl group having 8 to 22 carbon atoms, and one of them represents a hydrogen atom or has 1 to 22 carbon atoms. Alkyl or benzyl. ]

Among R ₁ to R ₃ , when two or more of them are an alkyl group or a benzyl group having 8 to 22 carbon atoms, the solubility in a solvent can be improved. More preferably, two or more of R ₁ to R _{3 are} an alkyl group or a benzyl group having 12 to 22 carbon atoms. When there are two alkyl groups having a carbon number of less than 8, the solubility in a solvent is deteriorated, and a coating film foreign matter is likely to occur. Further, when an alkyl group having more than 22 carbon atoms is present, the coloration property of the salt-forming product (A) is impaired. Solvent solubility is remarkably good by the presence of two groups having 8 to 22 carbon atoms.

(primary amine)

The primary amine is represented by the following formula (14).

General formula (14):

RNH ₂

Here, R is, for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The primary amine may have an oxygen atom or the like between R and a nitrogen atom.

The aforementioned substituent of an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, for example, an alkyl group, an aryl group, an alkylamino group, an aryloxy group, a decylamino group, a halogen atom, a decylamino group, an anthracene group Base, alkylthio, arylthio, hydroxy, cyano, alkylaminocarbonyl, arylaminocarbonyl, substituted amine carbamoyl, substituted sulfamoyl, nitro, substituted amine, alkyl sulfonium a arylsulfonyl group, a substituted alkylsulfonylamino group, and a substituted arylsulfonylamino group.

Primary amines such as: methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine, dodecylamine (lauramide), ten Aliphatic unsaturated primary amines such as triamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocamine, tallow alkylamine, hardened tallow alkylamine, allylamine , aniline, and benzylamine.

The number of carbon atoms of the alkyl group constituting the primary amine is preferably in the range of 8 to 24. When the number of carbon atoms is less than 8, it is hardly soluble in an organic solvent, and high heat resistance and light resistance cannot be achieved. Further, when the number of carbon atoms is more than 24, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 10 to 20, more preferably in the range of 14 to 20.

A preferred primary amine is one having a carbon number of octylamine or more. Such primary amines are typically present as a mixture of compounds having different numbers of carbon atoms. That is, such a primary amine has a distribution of carbon numbers.

Specifically, for example, octylamine (in the range of 8 to 10 carbon atoms, 8 in a ratio of 98%), laurylamine (in the range of 10 to 14 carbon atoms, 12 in the range) The ratio is 98%), myristylamine (in the range of 12 to 16 carbon atoms, 14 in a ratio of 96%), and stearylamine (having a carbon number of 14 to 20) Within, 18% of the ratio is 93%), cocamine, tallow amine (in the range of 12 to 20 carbon atoms, and 64% in number of cases), hardened tallow An alkylamine (in the range of 12 to 20 carbon atoms, 18 in a number ratio of 65%), and oleylamine (in the range of 14 to 20 carbon atoms, 18 in number ratio) 82%). Among them, it is preferred to use tallow alkylamine, hardened tallow alkylamine, oleylamine, or stearylamine.

Specifically, commercially available primary amines such as ARMEEN 8D (octylamine), ARMEEN 12D (lauramide), ARMEEN 14D (myristylamine), ARMEEN 18D (stearylamine), and ARMEEN TD (made by LION Corporation) can be used. Tallow alkylamine), ARMEEN HTD (hardened tallow alkylamine) and ARMEEN OD (oleylamine), and FARMEEN CS (coconutamine), FARMEEN 08D (octylamine), FARMEEN 20D (laurylamine), FARMEEN 80 Stearylamine), FARMEEN 86T (stearylamine), FARMEEN O (oleylamine) and FARMEEN T (tallowamine).

(secondary amine)

The secondary amine is represented by the following formula (15).

General formula (15):

R ₁ R ₂ NH

Here, R ₁ and R _{2 are} , for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The secondary amine may have an oxygen atom or the like between R ₁ or R ₂ and a nitrogen atom.

Examples of the substituent of the aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent include an alkyl group, an aryl group, an alkylamino group, an aryloxy group, a decylamino group, a halogen atom, and a decylamine. Base, mercapto group, alkylthio group, arylthio group, hydroxyl group, cyano group, alkylaminocarbonyl group, arylaminocarbonyl group, substituted amine methyl group, substituted amine sulfonyl group, nitro group, substituted amine group, alkyl sulfonyl group An arylsulfonyl group, a substituted alkylsulfonylamino group, and a substituted arylsulfonylamino group.

The secondary amine may, for example, be an aliphatic unsaturated secondary amine such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine or diallylamine, methylaniline or ethyl. Aniline, dibenzylamine, diphenylamine, dicoconamine, dihardened tallow alkylamine, and distearylamine.

Among the above formula (15), those in which R ₁ and R ₂ are an alkyl group having 8 to 22 carbon atoms or a benzyl group are preferred. The secondary amine having 8 or more carbon atoms is usually present as a mixture of a compound having a small number of carbon atoms and a compound having a large number of carbon atoms. That is, such secondary amines generally have a distribution of carbon numbers.

The number of carbon atoms constituting the alkyl group of the secondary amine is preferably in the range of 8 to 22. If the number of carbon atoms is less than 8, it is insoluble in an organic solvent, and heat resistance and light resistance are inferior. Further, when the number of carbon atoms is more than 22, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 12 to 18, more preferably in the range of 14 to 18.

A secondary amine, using dicoconamine (with a carbon number of 8 to 18, 12 in a ratio of 60%), a dihardened tallow alkylamine (having a carbon number of 12 to 20) It is preferable that the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of the ratio of

Specifically, commercially available secondary amines such as ARMEEN 2C and ARMEEN 2HT manufactured by LION Corporation and FARMEEN D86 manufactured by Kao Corporation are available.

(tribasic amine)

The tertiary amine is represented by the following formula (16).

General formula (16):

R ₁ R ₂ R ₃ N

Here, R ₁ to R _{3 are} , for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The tertiary amine may have an oxygen atom or the like between each of R ₁ to R ₃ and a nitrogen atom.

Examples of the substituent of the aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent include an alkyl group, an aryl group, an alkylamino group, an arylamino group, a decylamino group, a halogen atom, and a decylamine. Base, fluorenyl, alkylthio, arylthio, hydroxy, cyano, alkylaminocarbonyl, aryloxycarbonyl, substituted aminemethanyl, substituted amine sulfonyl, nitro, substituted amine, alkyl sulfonium Base, arylsulfonyl, substituted alkylsulfonylamino, and substituted arylsulfonylamino

As the tertiary amine, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, or tribenzylamine can be used. As the tertiary amine, for example, a tertiary amine represented by the following formula (17) or (18) can be used.

General formula (17):

RN(CH ₃ ) ₂

Here, R is an alkyl group or a benzyl group having 8 to 22 carbon atoms.

General formula (18):

R ₁ R ₂ NCH ₃

Here, R ₁ and R ₂ are an alkyl group or a benzyl group having 8 to 22 carbon atoms.

A tertiary amine having 8 or more carbon atoms is usually present as a mixture of a smaller number of carbon atoms and a larger number of carbon atoms. That is, such tertiary amines generally have a distribution of carbon numbers.

The number of carbon atoms of the tertiary amine, particularly the alkyl group constituting the tertiary amine represented by the general formula (17), is preferably in the range of 8 to 22. If the number of carbon atoms is less than 8, it is insoluble in an organic solvent, and heat resistance and light resistance are inferior. Further, when the number of carbon atoms is more than 22, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 12 to 18, more preferably in the range of 14 to 18.

A tertiary amine represented by the formula (17), for example, N-methyldodecylamine (in the range of 8 to 12 carbon atoms, 10 in a number ratio of 98%), N-methyl group Dicocylamine (in the range of 8 to 18 carbon atoms, 12 in number of ratios of 60% and 14 in number of ratios of 22%), N-methyl dihardened taurine Methylamine (in the range of 12 to 20 carbon atoms, 64 in number of ratios of 64% and 16 in number of ratios of 30%), N-methyldioleylmethylamine ( The number of carbon atoms is in the range of 14 to 20, the ratio of 18 is 84% by number, and the amount of dilauryl monomethylamine (the number of carbon atoms is 10 to 14 and the ratio of 12 is Counted as 98%).

a tertiary amine represented by the formula (18), for example, N,N-dimethyllaurylamine (in the range of 10 to 14 carbon atoms, 12 in a ratio of 98%), N, N-dimethyl myristylamine (in the range of 12 to 16 carbon atoms, 14 in a ratio of 96%), N,N-dimethyl palmitamine (having 14 to 18 carbon atoms) Within the range of 16, 96% by number of N, N-dimethylstearylamine (in the range of 14 to 20 carbon atoms, and 94% in number of cases) ), N,N-dimethyl behenylamine (in the range of 22 to 24 carbon atoms, 22 in number of ratios of 92%), N,N-dimethylcocoamine (in the range of 12 to 16 carbon atoms, 12 in the range of 12% by number), N,N-dimethyltallowamine (in the range of 12 to 16 carbon atoms, 18 65%), N,N-dimethyl hardened tallow alkylamine (in the range of 12 to 16 carbon atoms, 18 in a number ratio of 80%), and N, N - dimethyl oleylamine (the number of carbon atoms is in the range of 16 to 20, and the ratio of 18 is 93% in number).

Commercially available tertiary amines represented by the general formula (17), such as ARMEEN DM12D, DM14D, DM16D, DM18D, DM22D, DMCD, DMTD, DMMHTD and DMOD manufactured by LION Corporation, and FARMEENDM series manufactured by Kao Corporation. A commercially available tertiary amine represented by the formula (18), for example, ARMEEN M210D, M2C, M2HT and M20 manufactured by LION Corporation, and FARMEEN M2-2095 and T-08 manufactured by Kao Corporation.

In the present aspect, the tertiary amine represented by the formula (18) is preferred because it is excellent in the effect of suppressing the coating film foreign matter of the colored composition.

[salt treatment]

by The salt-forming product (A) composed of an acid dye and an amine compound (any one selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine) can be synthesized by a conventionally known method.

For example, after the amine compound is dissolved in water, it is added to the aqueous solution. It is an acid dye and can be stirred. The method of dissolving the amine compound in water, for example, adding the amine compound to water together with acetic acid, is preferably dissolved in water in the form of an acetate. The dissolved amine compound has the form of an ammonium ion. A sulfonic acid group (-SO3H or -SO3Na) in an acid dye is bonded to an ammonium group (NH4 ⁺ ) of an amine compound to obtain a salt-forming product (A). In the case of solvents, it is also possible to use methanol or ethanol instead of water.

Especially by The salt-forming product (A) of the dye CI red acid 289 and the amine compound having a molecular weight of 269 to 591 is excellent in solvent solubility, and when used in combination with a blue pigment, excellent heat resistance, light resistance and solvent resistance can be achieved. The reason why the salt-forming product (A) and the blue pigment are used together to achieve good performance is that the salt-forming product (A) is dissolved or dispersed in a solvent and adsorbed to the blue pigment.

(blue pigment)

As the blue pigment, for example, an indigo pigment and/or a triarylmethane-based lake pigment can be used in the same manner as in the first aspect. The indigo pigment is preferably a copper phthalocyanine blue pigment.

[Micronization of pigments]

The blue pigment used in the blue coloring composition of the present aspect and the other pigment which can be used arbitrarily can be subjected to a salt milling treatment in the same manner as in the first aspect to be fine. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of good dispersion in the colorant carrier. Further, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly preferred range is 25 to 85 nm. In addition, the primary particle diameter of the pigment is measured by a method of directly measuring the size of the primary particles by an electron microscope photograph taken by a TEM (transmission electron microscope) of the pigment, similarly to the first aspect.

(other coloring agents)

In the blue colored composition of the present aspect, as in the first aspect, other organic pigments may be added as long as the effects obtained are not impaired.

When the total mass of the coloring agent of the blue coloring composition is 100 parts by mass, the content of the pigment other than the blue pigment is preferably 20 parts by mass or less. If it is more than 20 parts by mass, it is difficult to satisfy the desired hue which is blue.

<Resin>

The resin is such that the colorant is especially dispersed as a salt product, or the salt forming product is dyed or impregnated. The resin may, for example, be a thermoplastic resin or a thermosetting resin, and may be used in the same manner as in the first aspect.

<solvent>

In the same manner as in the first aspect, the blue coloring composition of the present invention is applied to a substrate such as a glass substrate in order to facilitate the dispersion or dissolution of the coloring agent in the colorant carrier, so that the dried film thickness is 0.2 to 5 μm to form a filter. The sheet section may contain a solvent.

The solvent can be used in the same manner as in the first aspect.

Among them, from the viewpoints of good dispersibility and solubility of the pigment and the salt-forming product (A), ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monomethyl ether B are used. A diol acetate such as an acid ester or an ethylene glycol monoethyl ether acetate, an aromatic alcohol such as benzyl alcohol or a ketone such as cyclohexanone is preferred. Among them, cyclohexanone is preferably used.

<Method for Producing Colored Composition>

The blue coloring composition of this aspect can be made by a salt-forming product (A) composed of an acid dye and an amine compound (a cationic component thereof), and optionally a coloring agent composed of a solvent such as a blue pigment, dissolved or dispersed in a solvent composed of the above-mentioned resin and optionally used solvent Made in the middle. When the above material is dispersed in a colorant carrier, the blue coloring composition is preferably used together with a dispersing aid such as a dye derivative or a resin type dispersing agent, and is used in a three-roll mill or a two-roll mill. It is produced by dispersion treatment of various dispersing tools such as a sand mill, a kneader, and an attritor. Further, the blue coloring composition of the present aspect may be produced by dissolving or dispersing a salt-forming product (A) and other coloring agents such as a blue pigment in a colorant carrier, and then mixing them.

(dispersion aid)

When the coloring agent is dispersed in the coloring agent carrier, a dispersing aid such as a dye derivative, a resin type dispersing agent, or a surfactant can be suitably used in the same manner as in the first aspect.

In this aspect, a pigment derivative represented by the following formula (19) among the dye derivatives is preferred.

General formula (19):

PL _m

[Here, P is an organic pigment residue, an anthracene residue, an acridone residue or three The residue, L is a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent, and m is an integer of 1 to 4. ]

Examples of the organic pigment constituting the organic pigment residue include a diketopyrrolopyrrole pigment; an azo pigment such as azo, disazo, and polyazo; copper indigo, halogenated copper indigo, and none. Indigo pigments such as metal indigo; amine guanidine, diamino dioxime, pyrimidine, flavonthrone, anthanthrone, indanthrone, pyranthrone ) and anthraquinone pigments such as Violathrone; quinacridone pigments; Pigment; perinone pigment; lanthanide pigment; thioindigo pigment; isoporphyrin pigment; isoindolinone pigment; quinophthalone pigment; reduction (Threne) Pigments; and metal complex pigments.

In the blue coloring composition of the present aspect, a pigment derivative which is preferably used is a copper indigo amine compound. The copper azurin compound refers to a basic compound (copper indigo sulfonate phthalamide compound) in which P is a copper indigo residue, L is a basic substituent, and P is copper indigo. a residue, L is a salt forming product of an acidic compound and an quaternary ammonium salt (copper phthalocyanine ammonium salt compound), or P is a copper indigo residue, and L is introduced or may have a substituent. a compound of phthalic acid imine methyl. The most preferred pigment derivative which can be used is a copper phthalocyanine decylamine compound.

In the blue coloring composition of the present aspect, a photopolymerizable compound and/or a photopolymerization initiator may be further added and used as a coloring composition for a color filter.

<Photopolymerizable compound>

In the present aspect, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

In the color filter of the present aspect, the blue coloring composition is used, and when the filter segment is formed by photolithography which is cured by irradiation with ultraviolet rays, the photopolymerization can be added in the same manner as in the first aspect. The initiator or the like is prepared in the form of a solvent developing type or an alkali developing type colored resist.

<sensitizer>

Further, in the blue coloring composition of the color filter of the present aspect, the sensitizer may be contained in the same manner as in the first aspect.

<leveling agent>

In the coloring composition of the present aspect, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent in the same manner as in the first aspect.

<hardener, hardening accelerator>

In the coloring composition of the present aspect, in order to assist the hardening of the thermosetting resin, a curing agent, a curing accelerator, or the like may be contained as needed in the same manner as in the first aspect.

<Other additive ingredients>

In the blue coloring composition of the present aspect, in order to keep the viscosity of the composition for a long period of time, the storage stabilizer can be contained in the same manner as in the first aspect. Further, in order to improve the adhesion to the transparent substrate, an adhesion enhancer such as a decane coupling agent may be contained in the same manner as in the first aspect.

<antioxidant>

In the coloring composition of this aspect, in order to increase the transmittance of the coating film, it is preferable to contain an antioxidant similarly to the first aspect.

<Removal of large particles>

It is preferable to remove the large particles and the dust to be mixed in the coloring composition of the present aspect as in the first aspect.

<Color Filter>

The color filter of this aspect is formed in the same manner as the first aspect except that the color filter of the present aspect is colored with a blue coloring composition.

The red filter segment can be formed using a general red colored composition containing a red pigment and a colorant carrier, similarly to the first aspect.

In the red coloring composition, an orange pigment and/or a yellow pigment may be used in combination as in the first aspect.

The green filter segment can be formed using a general green coloring composition containing a green pigment and a colorant carrier, similarly to the first aspect.

In the green coloring composition, a yellow pigment can be used in combination as in the first aspect.

<Method of Manufacturing Color Filter>

The color filter of this aspect can be produced by a printing method or a photolithography method in the same manner as the first aspect.

[Example C]

The present invention will be described below based on the examples, but the present invention is not limited to these. In addition, "parts" means "parts by mass" unless otherwise specified. Further, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. Further, tetrahydrofuran (THF) was used as a developing solvent.

First, the acrylic resin solution, the fine pigment, and the salt-forming product (A) used in the examples and the comparative examples, a compound, a pigment dispersion, a resin solution containing a salt-forming product, and a A method of producing a resin solution of a compound, a red resist material, and a green resist material will be described.

<Method for Producing Acrylic Resin Solution 1C to 4C> (Preparation of Acrylic Resin Solution 1C)

An acrylic resin solution 1C was prepared by the same method as the method described for the acrylic resin solution 1A except that propylene glycol monomethyl ether acetate (PGMAC) was used instead of cyclohexanone. The acrylic resin contained in the resin solution 1C had a weight average molecular weight (Mw) of 26,000.

(Preparation of Acrylic Resin Solution 2C)

The acrylic resin solution 2C was prepared in the same manner as described for the acrylic resin solution 2A. The acrylic resin contained in the resin solution 2C had a weight average molecular weight (Mw) of 18,000.

(Preparation of Acrylic Resin Solution 3C)

The acrylic resin solution 3C was prepared in the same manner as described for the acrylic resin solution 3A. The acrylic resin contained in the resin solution 3C had a weight average molecular weight (Mw) of 19,000.

(Preparation of Acrylic Resin Solution 4C)

The acrylic resin solution 4C was obtained in the same manner as described for the acrylic resin solution 4A. The acrylic resin contained in the resin solution 4C had a weight average molecular weight (Mw) of 19,000.

<Method for Producing Micronized Pigment> (Production of blue fine pigment 1C)

Indigo blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Co., Ltd., specific surface area 60 m ² /g) 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol It was placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of blue fine pigment 1C. The blue fine pigment 1C had a specific surface area of 80 m ² /g.

(Production of blue fine pigment 2C)

200 parts of triphenylmethane-based blue pigment CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of blue fine pigment 2C. The blue fine pigment 2C had a specific surface area of 65 m ² /g.

(Production of purple fine pigment 1C)

Will be two 200 parts of purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.) The mixture was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of purple fine pigment 1C. The purple fine pigment 1C has a specific surface area of 95 m ² /g.

(Production of red fine pigment 1C)

200 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of red fine pigment 1C. The red fine pigment 1C has a specific surface area of 70 m ² /g.

(Production of yellow fine pigment 1C)

500 parts of isoporphyrin yellow pigment CI Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 120 ° C for 8 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 80 ° C for one day and night to obtain 490 parts of yellow fine pigment 1C. The yellow fine pigment 1C has a specific surface area of 70 m ² /g.

(Production of green fine pigment 1C)

200 parts of indigo green pigment CI Pigment Green 36 ("Leonol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was prepared and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of green fine pigment 1C. The green fine pigment 1C had a specific surface area of 75 m ² /g.

(Production of yellow fine pigment 2C)

200 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by Lanxess Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.). ), kneading was carried out at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of yellow fine pigment 2C. The yellow fine pigment 2C has a specific surface area of 65 m ² /g.

<Method for Producing Salt-Forming Product (A)> (salt-forming product (A-1C))

A salt-forming product (A-1C) composed of C.I. Acid Red 289 and stearylamine (FARMEEN 80) (molecular weight 269) was produced by the following procedure.

Stearic acid was added to 10 to 20% aqueous acetic acid, and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and stearylamine, that is, a salt-forming product (A-1C).

(salt-forming product (A-2C))

A salt-forming product (A-2C) composed of C.I. Acid Red 289 and distearylamine (FARMEEN D80 manufactured by Kao) (having a molecular weight of 521) was produced by the following procedure.

The distearylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and distearylamine, that is, a salt-forming product (A-2C).

(salt-forming product (A-3C))

A salt-forming product (A-3C) consisting of C.I. Acid Red 289 and dicoconamine (molecular weight 353) was produced by the following procedure.

Dicoconamine was added to 10 to 20% aqueous acetic acid and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and dicocylamine, that is, a salt-forming product (A-3C).

(salt-forming product (A-4C))

A salt-forming product (A-4C) composed of C.I. Acid Red 289 and N-methyldiamine (having a molecular weight of 311) was produced by the following procedure.

N-methyldiamine was added to 10 to 20% aqueous acetic acid, and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to allow sufficient reaction. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and N-methyldiamine, a salt-forming product (A-4C).

(salt-forming product (A-5C))

A salt-forming product (A-5C) composed of C.I. Acid Red 289 and N-methyldisulfase tallow alkylmethylamine (having a molecular weight of 367 to 591) was produced by the following procedure.

N-methyldi hardened tallow alkylmethylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and N-methyldi-cursified tallow alkylmethylamine, that is, a salt-forming product (A-5C).

(salt-forming product (A-6C))

A salt-forming product (A-6C) composed of C.I. Acid Red 289 and N-butyldimethylamine (molecular weight 101) was produced by the following procedure.

N-butyldimethylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and N-butyldimethylamine, that is, a salt-forming product (A-6C).

(salt-forming product (A-7C))

A salt-forming product (A-7C) composed of C.I. Acid Red 52 and distearylamine (FARMEEN D80 manufactured by Kao) (having a molecular weight of 521) was produced by the following procedure.

The distearylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 52 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 52. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 52 and distearylamine, that is, a salt-forming product (A-7C).

(salt-forming product (A-8C))

A salt-forming product (A-8C) composed of C.I. Acid Red 87 and distearylamine (FARMEEN D80 manufactured by Kao) (having a molecular weight of 521) was produced by the following procedure.

The distearylamine was added to a 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 87 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 87. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 87 and distearylamine, that is, a salt-forming product (A-8C).

(salt-forming product (A-9C))

A salt-forming product (A-9C) composed of C.I. Acid Red 92 and distearylamine (FARMEEN D80, Kao) (having a molecular weight of 521) was produced by the following procedure.

The distearylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 92 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 92. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 92 and distearylamine, that is, a salt-forming product (A-9C).

(salt-forming product (A-10C))

A salt-forming product (A-10C) composed of C.I. Acid Red 388 and distearylamine (FARMEEN D80, Kao) (having a molecular weight of 521) was produced by the following procedure.

The distearylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 388 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 388. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 388 and distearylamine, that is, a salt-forming product (A-10C).

(salt-forming product (A-11C))

A salt-forming product (A-11C) composed of C.I. Acid Red 289 and dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (having a molecular weight of 101) was produced by the following procedure.

Dipropylamine was added to 10 to 20% aqueous acetic acid solution and the solution was thoroughly stirred. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and dipropylamine, that is, a salt-forming product (A-11C).

(salt-forming product (A-12C))

A salt-forming product (A-12C) composed of C.I. Acid Red 289 and di-docosylmethylamine (molecular weight 647) was produced by the following procedure.

Di-docosylmethylamine was added to 10 to 20% aqueous acetic acid and the solution was stirred for 10 minutes. After the solution was heated to 60 ° C, C.I. Acid Red 289 was added dropwise in small portions. An aqueous solution can also be used for C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and di-docosylmethylamine, that is, a salt-forming product (A-12C).

< Method for producing a compound > ( Compounds (C-1C) and (C-2C))

on Compounds (C-1A) and (C-2A) were prepared separately by the same method as above. Compounds (C-1C) and (C-2C).

<Method for Producing Pigment Dispersion> (Production of Pigment Dispersion (DP-1C))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and Eigermil ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.) was used for dispersion treatment for 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DP-1C).

Blue fine pigment 1C (C.I. Pigment Blue 15:6): 9.5 parts

Pigment derivative 1C (copper indigo sulfonate amide compound): 1.5 parts

Surfactant 1C ("Tohol N-120" (coconut oil fatty acid monoethanol amide) manufactured by Toho Chemical Co., Ltd.): 0.2 parts

Acrylic resin solution 1C: 39.8 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.): 1.0 part

Further, the pigment derivative 1C (copper indigo sulfonate decylamine compound) contains m = 2 among the compounds represented by the following structural formula in a mass ratio of 65:35 and m=2 among the compounds represented by the following structural formula: a mixture of people.

(Production of Pigment Dispersion (DP-2C))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and Eigermil ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.) was used for dispersion treatment for 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DP-2C).

Blue fine pigment 2C (C.I. Pigment Blue 1): 11.0 parts

Acrylic resin solution 1C: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.): 1.0 part

(Preparation of pigment dispersions (DP-3C) to (DP-7C))

A pigment dispersion (DP-3C) to (DP-7C) was prepared in the same manner as the above pigment dispersion (DP-2C) except that the blue fine pigment 1C was changed to the pigment shown in Table 13.

<Resin solution containing salt-forming product and containing Method for producing resin solution of compound> (Preparation of resin solution (DA-1C) containing salt-forming product)

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and Eigermil ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.) was used for dispersion treatment for 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DA-1C).

Salt-forming product (A-1C): 11.0 parts

Acrylic resin solution 1C: 40.0 parts

Cyclohexanone: 49.0 parts

(Resin solution containing salt-forming product (DA-2C) to (DA-12C) and containing Preparation of resin solutions (DC-1C) and (DC-2C)

The salt-forming product (A-1C) is changed to the salt-forming product (A) shown in Table 14 or In addition to the above-mentioned resin solution (DA-1C) containing a salt-forming product, a resin solution (DA-2C) to (DA-12C) containing a salt-forming product and containing the compound are prepared. A resin solution (DC-1C) and (DC-2C) of the compound.

<Method of Manufacturing Red and Green Resist Material> (Preparation of red resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a red resist.

Pigment dispersion (DP-4C): 50.0 parts

Pigment dispersion (DP-5C): 10.0 parts

Acrylic resin solution 1C: 11.0 parts

Trimethylolpropane triacrylate ("NK E STER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.: 0.4 parts)

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Preparation of green resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a green resist.

Pigment dispersion (DP-6C): 45.0 parts

Pigment dispersion (DP-7C): 15.0 parts

Acrylic resin solution 1C : 11.0 parts

Trimethylolpropane triacrylate ("NK E STER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 1C to 12C and Comparative Examples 1C and 2C] (Example 1C: Colored composition (DB-1C))

The mixture was stirred well, and then filtered through a 5.0 μm filter to obtain a mixed coloring composition.

Resin solution containing salt-forming product (DA-1C): 2.2 parts

Pigment dispersion (DP-1C): 8.8 parts

Acrylic resin solution 1C: 40.0 parts

Cyclohexanone: 49.0 parts

(Examples 2C to 12C and Comparative Examples 1C and 2C: Colored Compositions (DB-2C) to (DB-14C))

The resin solution (DA-1C) containing the salt-forming product was changed to a resin solution containing a salt-forming product as shown in Table 15 or contained. In the same manner as the coloring composition (DB-1C), a coloring composition (DB-2C) to (DB-14C) was prepared, except that the resin solution of the compound was used.

(Test method for foreign matter in coating film)

With respect to the above colored composition, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, the colored composition was applied onto a transparent substrate to a dry film thickness of about 2.0 μm, and this was heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated in any five fields of view, and the total number of particles is obtained. The results are shown in Table 15.

In Table 15, the symbols in the "coated foreign matter" column have the following meanings.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

When the total number of particles is less than 20, coating unevenness due to foreign matter hardly occurs. In addition, when the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. In addition, when the total number of particles is 100 or more, coating unevenness (speckle) due to foreign matter occurs.

The coating film obtained from the coloring composition containing the salt-forming product (A) of this aspect and the blue pigment has less foreign matter (undissolved foreign matter). On the other hand, by containing The coating film obtained by the coloring composition of the compound (C-1C) and (C-2C) has a large amount of foreign matter. That is, When a dye is formed into a salt with a primary, secondary or tertiary amine, In the case of a functional group of a dye, more excellent properties can be achieved.

In Examples 6C and 11C, the cationic portion of the salt-forming product had a molecular weight of 101, which was smaller than Examples 1C to 10C. Therefore, in Examples 6C and 11C, there were many foreign materials in the coating film as compared with Examples 1C to 10C. However, in Examples 6C and 11C, the amount of the membrane foreign matter was at a practical level.

In addition, Example 1C uses a primary amine and a salt-forming product of dyes, and the use of secondary amines in Examples 2C and 3C a salt-forming product of the dye, and examples 4C to 6C use a tertiary amine and A salt-forming product of a dye. Since these amines each contain an alkyl chain having 8 or more carbon atoms, the evaluation results of the coating film foreign bodies of Examples 1C to 6C were good. In particular, the case of the secondary amine can give more excellent results than the case of the primary amine, and the case of the tertiary amine can give even more excellent results.

[Examples 13C to 32C and Comparative Examples 3C to 5C] (Example 13C: Resist material (R-1C))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-1C).

Resin solution containing salt-forming product (DA-1C): 12.0 parts

Pigment dispersion (DP-1C): 48.0 parts

Acrylic resin solution 1C : 11.0 parts

Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Cyclohexanone: 23.2 parts

(Examples 14C to 32C and Comparative Examples 3C to 5C: Resist materials (R-2C) to (R-23C))

The type of the resin solution and the pigment dispersion containing the colorant and the blending amount and the type of the acrylic resin solution were changed to those shown in Table 16, and the alkali material was obtained in the same manner as the resist material (R-1C). Type resist (R-2C) to (R-23C).

(evaluation of resist material)

A coating film was formed from the resist materials (R-1C) to (R-23C), and the chromaticity, the amount of foreign matter, heat resistance, light resistance, and solvent resistance were examined for each of the coating films by the following methods. The test results are shown in Table 17.

(coating film foreign body test)

With respect to the above-mentioned resist material, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, a resist material was applied onto a transparent substrate to have a dry film thickness of about 2.5 μm, and the coating film was entirely exposed to ultraviolet light. Thereafter, the mixture was heated at 230 ° C for 20 minutes in the oven, and then allowed to cool to obtain an evaluation substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Then, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is calculated. The results are shown in Table 17.

In addition, in Table 17, the meaning of the symbol shown in the "coating foreign matter" column is as follows.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

(Evaluation of color characteristics)

A resist material is coated on the glass substrate. Specifically, the resist material was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.060. The substrate was heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). Table 17 shows the results.

(coating film heat resistance test)

The resist material was applied onto the transparent substrate to a dry film thickness of about 2.5 μm, and the coating film was exposed to ultraviolet light through a mask having a predetermined pattern. The alkali developer is sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, it was heated in an oven at 230 ° C for 20 minutes. After cooling, the color of the obtained coating film under a C light source was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1), b*( 1)). Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the chromaticity 2 (L*(2), a*(2), b*(2)) under a C light source was measured.

Using these chromaticities, the color difference ΔEab* is calculated according to the following calculation formula. Further, the heat resistance of the coating film was evaluated in the following five stages based on the color difference ΔEab*.

◎◎: ΔEab* is less than 0.5

◎: ΔEab* is 0.5 or more and less than 1.5

○: ΔEab* is 1.5 or more and less than 2.5

△: ΔEab* is 2.5 or more and less than 5.0

×: ΔEab* is 5.0 or more

The results are shown in Table 17.

(coating film light resistance test)

The test substrate was prepared in the same manner as the coating film heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a* (1), b*(1)). Thereafter, the substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI Co., Ltd.), and left for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using these chromaticities, the color difference ΔEab* was calculated in the same manner as the coating film heat resistance test, and the light resistance of the coating film was evaluated on the same basis as the heat resistance. Table 17 shows the results.

(film resistance test)

The test substrate was produced in the same procedure as the heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1) ), b*(1)). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the chromaticity was measured in the same manner as the coating film heat resistance test to calculate the color difference. ΔEab*, the solvent resistance of the coating film was evaluated on the same basis as the heat resistance. Table 17 shows the results.

Contained by A coloring layer obtained by using a blue coloring composition of a color filter composed of an acid dye and a primary, secondary or tertiary amine salt product (A) and a blue pigment, which is excellent in lightness and resistance, and has no display coating. Excellent results for membrane foreign matter.

Since the resist materials (R-13C) and (R-18C) contain two Since the purple pigment is used, the brightness of the colored layer obtained from the resist materials (R-13C) and (R-18C) is somewhat low, but it is above the practical level. Moreover, the coloring layer obtained from the resist materials (R-13C) and (R-18C) is excellent in heat resistance, light resistance, and solvent resistance, in particular.

The coloring layer obtained from the resist materials (R-14C) and (R-19C) is excellent in color characteristics. Further, the coloring layers obtained from the resist materials (R-14C) and (R-19C) are somewhat low in heat resistance, light resistance, and solvent resistance, but are used at a level where there is no problem in the color filter.

The resist materials (R-6C) and (R-11C) contain an amine compound having a molecular weight of 101 and It is a salt-forming product of a dye, and thus the coating film foreign matter of the coloring layer obtained from the above is somewhat. On the other hand, the resist (R-12C) contains an amine compound having a molecular weight of 647 and It is a salt-forming product of the dye, so the transmittance of the colored layer obtained by the above is somewhat low, and the brightness is somewhat low. But all are satisfied with the practical level.

On the other hand, the coloring layer obtained from the resist materials (R-21C) and (R-22C) has many foreign matters. Further, the coloring layer obtained from the resist material (R-23C) has a lower brightness (Y) than the coloring layer obtained from the resist materials (R-1C) to (R-20C).

Further, from the results obtained for the resist materials (R-15C) to (R-17C) and (R-20C), it is understood that the coating film foreign matter is reduced and the solvent is resistant by using an active energy ray-curable resin having a vinyl bond. Sexual improvement.

[Examples 33C to 52C and Comparative Example 6C] (Example 31C: Color filter (CF-1C))

A black matrix of a light-shielding pattern was formed on the glass substrate, and then a red resist was applied using a spin coater. The red resist material was applied such that the chromaticity under the C light source was a film thickness of x=0.640 and y=0.330. For the coating film, ultraviolet rays were irradiated through a photomask using an ultrahigh pressure mercury lamp at an exposure amount of 300 mJ/cm ² . Next, the coating film was supplied to a spray developing using an alkali developing solution composed of a 0.2% by mass aqueous sodium carbonate solution, the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

Next, a green resist material was applied on the substrate by the same method as described above. The green resist material was applied so that the chromaticity under the C light source became a film thickness of x=0.300 and y=0.600. The coating film was exposed, developed, washed, and fired in the same manner as described above to form a green filter segment.

Further, a blue resist (R-1A) was applied onto the substrate in the same manner as described above. The blue resist (R-1A) was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.06. The coating film was subjected to the same exposure, development, cleaning, and firing as described above for the red filter segment to form a blue filter segment. As described above, a color filter (CF-1C) was obtained.

(production of liquid crystal display)

An electrode made of ITO was formed on a color filter (CF-1C), and a polyimide polyimide alignment layer was formed thereon. Further, a TFT array and a pixel electrode were formed on one surface of the separately prepared glass substrate, and an alignment layer made of polyimide was formed thereon.

Next, on the surface of the glass substrate on which the electrode is provided, a sealant is used to form a frame-like pattern having a passage connecting the inside and the outside of the frame. Then, the substrates are bonded to each other with the spacer beads interposed therebetween so that the electrodes face each other.

Next, in the internal space of the unit cell obtained in this manner, the liquid crystal composition was injected from the previous passage. After the via was sealed, a polarizing plate was attached to both sides of the unit cell to obtain a liquid crystal display panel.

Thereafter, the liquid crystal display panel is combined with a backlight unit including a three-wavelength CCFL to complete the liquid crystal display.

(Examples 34C to 52C and Comparative Example 6C)

A color filter (CF-2C) was produced in the same manner as the color filter (CF-1C) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 18. (CF-21C) and liquid crystal display. Further, since the coloring layer obtained from the blue resist materials (R-21C) and (R-22C) has a large amount of coating foreign matter, the color filters using these are not produced.

(Evaluation of color filters (CF-1C) to (CF-21C))

The liquid crystal display was displayed in a color image, and the brightness of the region corresponding to the red, green, and blue filter segments was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Further, the brightness displayed in white is obtained from the brightness. The results are shown in Table 18.

The blue colored layer of the color filter (CF-1C) to (CF-20C) is formed of a resist material containing a blue pigment and a salt-forming product (A). On the other hand, the blue colored layer of the color filter (CF-21C) is composed of a copper indigo pigment and two It is formed by a pigment resist. As shown in Table 18, a liquid crystal display including a color filter (CF-1C) to (CF-20C) can display a white image with higher brightness than a liquid crystal display including a color filter (CF-21C). .

○4th aspect

Next, the fourth aspect will be explained.

The color filter of the fourth aspect is a blue coloring composition containing a binder resin and a coloring agent. A coloring agent containing a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group. In this aspect, a resin having a cationic group in a side chain is used as a compound having a cationic group.

When the blue coloring composition of the fourth aspect is used for the production of a color filter, high brightness and a wide color reproduction area can be realized, and since the dye is in the form of a salt-forming product, heat resistance, light resistance, and resistance are obtained. Excellent performance is achieved in terms of solvent.

Also, the conventional combination of copper enamel blue pigment and two The color filter of a color filter such as a pigment has a transmittance spectrum of a blue coloring composition, and the peak position exists in the vicinity of 450 nm and the transmittance on the short wavelength side of 450 nm or less sharply decreases.

In contrast, when using the color filter of the present aspect, the blue coloring composition is used as compared with the use of the copper phthalocyanine blue pigment and the second In the case of a combination of pigments, a high transmittance on the short-wavelength side of 450 nm or less is achieved. Further, the luminescence spectrum of many backlights such as a cold cathode tube has a peak wavelength in or near a wavelength range of, for example, 425 to 500 nm. Therefore, the filter segment obtained by using the blue coloring composition of the color filter of the present aspect can achieve high definition.

<salt formation product (A)> (resin having a cationic group in the side chain)

The resin having a cationic group in the side chain for obtaining the salt-forming product (A) used in this aspect will be described below. The resin is not particularly limited as long as it has at least one onium salt base in the side chain. The onium salt structure is preferably an ammonium salt, a barium salt, a barium salt, a diazonium salt or a barium salt from the viewpoint of availability, etc., in consideration of preservation stability (thermal stability), an ammonium salt, a barium salt or a barium salt. Preferably. More preferably, it is an ammonium salt.

When a blue coloring composition containing a salt-forming product (A) is prepared and exhibited as a color filter, bonding with a blue coloring composition constituting a color filter is used. The resin is preferably the same resin. In this aspect, the acrylic resin is preferably used as the binder resin for the coloring composition of the color filter. Therefore, the resin having a cationic group in the side chain for obtaining the salt-forming product (A) is preferably an acrylic resin. .

In the aspect of the resin having a cationic group in the side chain, an acrylic resin containing a structural unit represented by the following formula (20) can be used.

General formula (20):

[In the formula (20), R ₁ represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R ₂ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group, and _{two of} R ₂ to R ₄ may be bonded to each other. Knot to form a ring. Q represents an alkylene group, an extended aryl group, -CONH-R ₅ -, -COO-R ₅ -, and R ₅ represents an alkylene group. Y ^- represents an inorganic or organic anion. ]

In the formula (20), R ₁ represents a hydrogen atom, or a substituted or unsubstituted alkyl group. The alkyl group in R ₁ may, for example, be a methyl group, an ethyl group, a propyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-hexyl group or a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ₁ has a substituent, the substituent may, for example, be a hydroxyl group or an alkoxy group.

Among the above, R ₁ is preferably a hydrogen atom or a methyl group.

In the formula (20), R ₂ to R ₄ each independently may, for example, be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Here, the alkyl group in R ₂ to R ₄ may, for example, be a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dec. Dibasic, n-tetradecyl, n-hexadecanyl and n-octadecyl, etc., branched alkyl (isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl) , a third amyl group, an isohexyl group, a 2-ethylhexyl group, a 1,1,3,3-tetramethylbutyl group, etc.), a cycloalkyl group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.) And crosslinking of a cyclic alkyl group (norbornyl group, adamantyl group, fluorenyl group, etc.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

The alkenyl group in R2 to R4 may, for example, be a linear or branched alkenyl group (vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.) Base (2-cyclohexenyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R2 to R4 include a monocyclic aryl group (such as a phenyl group) and a condensed polycyclic aryl group (naphthyl group, anthracenyl group, phenanthryl group, anthracenyl group, anthracenyl group, and naphthylquinone group. And an aromatic heterocyclic hydrocarbon group (thienyl group (a group derived from thiophene), a furyl group (a group derived from furan), a pipenyl group (a group derived from a piper group), a pyridyl group (a group derived from a pyridine), 9-sideoxy Keto group A ketone-derived group) and a 9-side aminothioxanthone group (a group derived from a thioxanthone) and the like.

When the alkyl group, the alkenyl group or the aryl group represented by R2 to R4 has a substituent, the substituent may, for example, be selected from a halogen atom, a hydroxyl group, an alkylamino group, an aryloxy group, an alkenyl group, a decyl group or an alkylaminocarbonyl group. a substituent such as a carboxyl group or a phenyl group. Among these substituents, a halogen atom, a hydroxyl group, an alkylamino group, and a phenyl group are particularly preferable.

From the viewpoint of stability, R ₂ to R ₄ are preferably a substituted or unsubstituted alkyl group, and an unsubstituted alkyl group is more preferable.

Further, _{two of} R ₂ to R ₄ may be bonded to each other to form a ring.

In the formula (20), the component of Q in which the acryl-based moiety is bonded to the ammonium salt group represents an alkylene group, an extended aryl group, -CONH-R ₅ -, -COO-R ₅ -, and R ₅ represents an alkylene group. . Among them, -CONH-R ₅ -, -COO-R ₅ - is preferred because of the polymerizability and ease of availability. Further, R ₅ is preferably a methylene group, an ethyl group, a propyl group or a butyl group, and a ethyl group is particularly preferred.

The Y-component in the formula (20) constituting the relative anion of the resin may be an inorganic or organic anion. The counter anion can be used without any limitation, and specific examples thereof include hydroxide ions; halide ions such as chloride ions, bromide ions, and iodide ions; and carboxylate ions such as formate ions and acetate ions. Carbonate ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and, for example, hexacyanoferrate (III) acid ion The complex ion and so on. From the viewpoint of synthetic suitability or stability, a halogen ion and a carboxylate ion are preferred, and a halogen ion is preferred. When the relative anion is an organic acid ion such as a carboxylic acid ion, an organic acid ion may be covalently bonded to the resin to form an intramolecular salt.

A preferred embodiment of the acrylic resin comprising the structural unit represented by the formula (20) can be copolymerized by using, for example, an ethylenically unsaturated monomer having an ammonium salt group as a monomer component. Obtained by the method. Alternatively, the acrylic resin can be copolymerized by using an ethylenically unsaturated monomer having an amine group as a monomer component, thereby obtaining an acrylic resin having an amine group, and then reacting the hydrazine salting agent with Obtained by the method of ammonium salting.

Specific examples of the ethylenically unsaturated monomer which can be used in order to obtain an acrylic resin having a structural unit represented by the general formula (20) are shown below.

The ethylenically unsaturated monomer having a quaternary ammonium salt group may, for example, be (meth)acryloxyethyltrimethylammonium chloride or (meth)acryloylaminoethyltriethylammonium chloride. , (meth) propylene oxiranyl ethyl dimethyl benzyl ammonium chloride, and (meth) propylene oxime aminoethyl methyl N- Alkyl (meth) acrylate-based quaternary ammonium compound such as morphyl ammonium chloride, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidoethyltriethyl Alkyl (methyl) propylene decyl amide amine quaternary ammonium compound such as ammonium chloride and (meth) acrylamidoethyl dimethyl benzyl ammonium chloride, dimethyl propylene dimethacrylate Alkyl ammonium, and trimethylvinylphenyl ammonium chloride.

The ethylenically unsaturated monomer having an amine group may, for example, be dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or dipropylaminoethyl (meth)acrylate. , diisopropylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, diisobutylaminoethyl (meth)acrylate, di-tert-butylamino (meth)acrylate Ester, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl ( Methyl) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide and di-tert-butylaminopropyl (meth) propylene hydride a (meth) acrylate or a (meth) acrylamide having a dialkylamino group such as an amine; a styrene having a dialkylamine group such as dimethylaminostyrene or dimethylaminomethylstyrene; a diallylamine compound such as allylmethylamine or diallylamine; and an aromatic vinyl-based monomer containing an amine group such as N-vinylpyrrolidine, N-vinylpyrrolidone or N-vinylcarbazole.

Examples of the hydrazine salting agent include alkylsulfuric acid such as dimethylsulfuric acid, diethylsulfonic acid and dipropylsulfuric acid, sulfonic acid esters such as methyl p-toluenesulfonate and methyl benzenesulfonate, methyl chloride and chlorine chloride. Chloroalkanes such as alkane, chloropropane and chlorooctane, bromoethanes such as methyl bromide, ethyl bromide, bromopropane and octyl chlorobromide, and chlorotoluene and bromine toluene.

The reaction of the ethylenically unsaturated monomer having an amine group with the hydrazine salting agent can be usually carried out by adding a hydrazine salting agent having an amine group to the same molar amount to the ethylenically unsaturated monomer having an amine group. The solution is carried out. The temperature at the time of the ammonium salting reaction is about 90 ° C or lower. In particular, when the vinyl monomer is ammonium-salted, it is preferably about 30 ° C or less, and the reaction time is about 1 to 4 hours.

As the hydrazine salting agent, an alkylaminocarbonylalkyl halide can also be used. The alkylaminocarbonylalkyl halide is represented by the following formula (21).

General formula (21):

ZR ₆ -COOR ₇

[In the formula (21), Z is a halogen such as chlorine or bromine, preferably bromine, and R6 is an alkylene group having 1 to 6, preferably 1 to 5, more preferably 1 to 3, R 7 It is a lower alkyl group having 1 to 6, preferably 1 to 3 carbon atoms. ]

The reaction of the ethylenically unsaturated monomer having an amine group with the alkoxycarbonylalkyl halide can be carried out by using an alkylaminocarbonylalkyl halide having an amine group of less than the molar amount and the above-described hydrazine salting agent. After the reaction, -COOR _{7 is} hydrolyzed to obtain a carboxylate ion (-COO ^- ). Thereby, an ethylenically unsaturated monomer having an ammonium salt group having a carboxybetaine structure represented by the formula (21) can be obtained.

Other ethylenically unsaturated monomers other than the structural unit represented by the formula (20), such as (meth) acrylates, crotonates, vinyl esters, maleic acid diesters, fumaric acid II Esters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, and the like are preferred.

Specific examples of such a vinyl monomer include the following compounds.

Examples of (meth) acrylates, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl) N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Cyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (meth)acrylic acid Ethyloxyethyl ester, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2-(2-methoxyethylamino)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Diethylene glycol monomethyl ether, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl (meth)acrylate, (meth)acrylic acid Polyethylene glycol monomethyl ether, (meth)acrylic acid polyethylene glycol single Ether, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Cyclopentenylaminoethyl ester, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Tribromophenyl methacrylate, and tribromophenylaminoethyl (meth) acrylate.

Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl carbamate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the itaconic acid diesters include, for example, dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of the (meth) acrylamide may, for example, be (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl. Base (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl acrylate (methyl) decylamine, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-(2-methylaminoethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-di Ethyl hydrazine (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene sulfhydryl Porphyrin, and diacetone acrylamide and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, and hydroxystyrene. Methoxystyrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, groups deprotected by available acidic materials (eg t-Boc, etc.) protected hydroxystyrene, methyl benzoate, and α-methylstyrene.

Other ethylenically unsaturated monomers which may be used other than the structural unit represented by the formula (20) may further contain a copolymerization unit derived from a monomer having an acid group.

Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, and itaconic acid; Acidic, itaconic anhydride, citraconic acid, citraconic anhydride, and unsaturated dicarboxylic acids such as mesaconic acid or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof; succinic acid mono(2-propene) Ethyloxyethyl ester), succinic acid mono(2-methylpropenyloxyethyl ester), phthalic acid mono(2-propenyloxyethyl ester), and phthalic acid mono(2-methylpropene oxime) Mono[(meth)acryloxyalkylene] ester of a polyvalent carboxylic acid having two or more esters; ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate A mono(meth)acrylate such as an ester or the like having a terminal carboxyl group polymer.

A method of obtaining an acrylic resin containing a structural unit represented by the formula (20) can be carried out by a known method such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, or living radical polymerization. Among these, it is preferred to use free radical polymerization or living radical polymerization.

In the case of the free radical polymerization method, it is preferred to use a polymerization initiator. As the polymerization initiator, for example, an azo compound or an organic peroxide can be used. Examples of the azo compound, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1) -carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methylaminovaleronitrile), Dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxyl) Methylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides, such as benzammonium peroxide, tertiary butyl peroxybenzoate, hydroperoxide , diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, tertiary butyl peroxy neodecanoate, peroxypivalic acid The third butyl ester, peroxidized (3,5,5-trimethylhexyl), dipropyl fluorenyl peroxide, or diethyl sulfoxide. These polymerization initiators may be used singly or in combination of two or more. The reaction temperature is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C. The reaction time is preferably from 3 to 30 hours, more preferably from 5 to 20 hours.

The living radical polymerization method can suppress side reactions occurring in general radical polymerization, and can uniformly grow polymerization. Therefore, a block polymer or a resin having a uniform molecular weight can be easily synthesized.

Among them, the use of an organic halide or a halogenated sulfonyl compound as a starting agent, and the use of a transition metal complex as a catalyst for atomic mobile radical polymerization, can be adapted to a wide range of monomers and can be used From the standpoint of the polymerization temperature to which the existing equipment is applicable, it is preferred. The atomic mobile radical polymerization method can be carried out by the methods described in the following References 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329

(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921

(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614

(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866

(Reference 5) WO96/030421

(Reference 6) WO97/018247

(Reference 7) Japanese Patent Laid-Open No. 9-208616

(Reference 8) Japanese Patent Laid-Open No. 8-41117

It is preferred to use an organic solvent for the above polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol can be used. Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate. These solvents may be used in combination of two or more kinds.

The amount of the cationic group present in the resin having a cationic group in the side chain is not particularly limited, but the cationic salt value of the resin is preferably from 10 to 200 mgKOH/g, more preferably from 20 to 130 mgKOH/g. The cation salt price is expressed by the valence of the sulfonium salt, the quaternary ammonium compound, and the amine salt. The amount of the ammonium salt group and the amine salt group present in the acrylic resin containing the structural unit represented by the formula (20) is preferably from 10 to 200 mgKOH/g, and from 20 to 130 mgKOH, based on the ammonium salt value and the amine salt value of the resin. /g is better.

If it is less than 10mgKOH/g, it comes from The concentration of the dye of the acid dye is low, and the resin component is increased, so that it does not function as a colorant component. Moreover, when it is larger than 200 mgKOH/g, the dye component will increase and the solvent solubility will fall.

The molecular weight of the acrylic resin containing the structural unit represented by the general formula (20) is not particularly limited. The converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably from 1,000 to 500,000, more preferably from 3,000 to 15,000.

The acrylic resin containing the structural unit represented by the general formula (20) is preferably one having a property of being dissolved in a solvent widely used for a coloring composition for a color filter. Thereby, a coating film which does not generate foreign matter can be obtained. In particular, it is more preferred to dissolve in propylene glycol monomethyl ether acetate.

In the resin having a cationic group in the side chain, the total content of the structural unit represented by the above formula (20) is not particularly limited, but the total structural unit contained in the resin having a cationic group in the side chain is set to 100. In the case of a part by mass, the total content of the structural unit represented by the above formula (20) is preferably 5 parts by mass or more, more preferably 10 to 50 parts by mass, from the viewpoints of solvent solubility and coloring ability of the salt-forming product. .

( Acid dye)

Used to obtain the salt-forming product (A) It is an acid dye and can be used similarly to the first aspect.

(salt formation)

The salt-forming product (A) used in this aspect can be obtained by using a resin having a cationic group in a side chain. An aqueous solution of an acid dye is stirred or vibrated, or an aqueous solution of a resin having a cationic group in a side chain An aqueous solution of an acid dye is easily obtained by mixing under stirring or shaking. In aqueous solution, the cationic group of the resin The anionic group of the acid dye is ionized, and these are ion-bonded, and the ionic bond portion is water-insoluble and precipitates. On the contrary, due to the relative anion of the resin The salt of the relative cation which is an acid dye is water-soluble, and therefore it can be removed by washing with water or the like. a resin having a cationic group in a side chain and The acid dyes may be used alone or in a plurality of different configurations.

a resin having a cationic group dissolved in a side chain when the salt is formed It is an acid dye, and a mixed solution of water and a water-soluble organic solvent can be used. The water-soluble organic solvent may, for example, be methanol, ethanol, n-propanol, isopropanol, 1-methylamino-2-propanol, 1-ethoxy-2-propanol, n-butanol or isobutanol. 2-(methoxymethoxy)ethanol, 2-butylaminoethanol, 2-(isopentylamino)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol single Dibutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate Ester, methyl ethyl ketone, N, N-dimethylformamide, dimethyl hydrazine, tetrahydrofuran (THF), two Alkane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, tetradecyl alcohol, and 4 -Methoxy-4methylpentanone. When the total mass of the aqueous solution is 100 parts by mass, the amount of 5 to 50 parts by mass is preferably used, and the amount of 5 to 20 parts by mass is most preferably used.

From the salt-forming product (A) The content of the dye component of the acid dye is preferably in the range of 10 to 60 parts by mass based on 100 parts by mass of the salt-forming product (A), and particularly preferably in the range of 15 to 55 parts by mass. By controlling in this range, the salt-forming product (A) excellent in solvent solubility can be obtained.

Salt-containing product (A) The amount of the effective dye component (after removing the relative ions of the alkali metal ions or the like) in the acid dye can be adjusted to the same concentration of the salt-forming product (A) solution by measurement and The spectral spectrum of the acid dye solution is calculated by calculating the spectral intensity ratio of the maximum absorption wavelength.

For example, it can be used to fully dissolve the salt-forming product (A) with a solvent (N-methyl-2-pyrrolidone, etc.) which is an acid dye, and is prepared into a salt product (A) solution and a salt forming product (A) solution obtained by using an acid dye solution at a certain concentration and measuring the absorbance The absorbance in the maximum absorption wavelength of the acid dye solution is defined as Xa and Xb. Most of the acid dyes may contain relative ions such as alkali metal ions. In this case, if the number of relative ions present in one molecule is Na, the atomic amount of the relative ions is determined to be Ma. The molecular weight of the acid dye is set to Mb, then The mass % of the effective pigment component in the acid dye can be provided by the following formula.

(1-Ma×Na/Mb)×100 [% by mass]

Then, using this formula, the salt product (A) can be calculated from the following formula. It is the mass % of the effective pigment component in the acid dye.

(Xa/Xb) × (1-Ma × Na / Mb) × 100 [% by mass]

(blue pigment)

As the blue pigment constituting the coloring agent used in the present aspect, as the first aspect, a cordier pigment and/or a triarylmethane-based lake pigment or the like can be used. The indigo pigment is preferably a copper phthalocyanine blue pigment.

Among these, in terms of excellent heat resistance and color developability, the blue pigment is preferably C.I. Pigment Blue 15:6 or C.I. Pigment Blue 1.

[Micronization of pigments]

The blue pigment used in the blue coloring composition of the present aspect and the pigment which can be used arbitrarily can be subjected to salt milling treatment in the same manner as in the second aspect to be fine.

In addition, the primary particle diameter of the pigment can be obtained by directly measuring the size of the primary particles by using an electron micrograph of the pigment imaged by TEM (transmission electron microscope) in the same manner as the second aspect.

The salt-forming product (A) is preferably used in an amount of from 1 to 800 parts by mass based on 100 parts by mass of the blue pigment. The amount of the salt-forming product (A) is more preferably from 5 to 400 parts by mass. When the amount of the salt-forming product (A) to be added is less than 1 part by mass, the reproducible chromaticity region is narrowed, and if it exceeds 800 parts by mass, the hue changes.

If the conversion is made in consideration of the color composition, the salt-forming product (A) The effective dye component of the acid dye is preferably from 1 to 400 parts by mass based on 100 parts by mass of the blue pigment. The effective dye component of the dye is more preferably in the range of 5 to 300 parts by mass based on 100 parts by mass of the blue pigment.

Salt-forming product (A), especially When CI acid red 289 or CI acid red 52 is used as the acid dye, excellent solvent solubility is exhibited, and when used together with the blue pigment, excellent heat resistance, light resistance, and solvent resistance can be achieved.

The reason why the salt-forming product (A) and the blue pigment are used in combination to achieve good performance is that the salt-forming product is adsorbed to the blue pigment in a state of being dissolved or dispersed in a solvent.

(other coloring agents)

In the blue colored composition of the present aspect, in addition to the component of the coloring agent, other organic pigments may be added as long as the effect of the obtained color is not impaired as in the first aspect.

<Binder resin>

The binder resin is used to disperse the colorant, especially the salt-forming product, or to dye or impregnate the salt-forming product. A binder resin such as a thermoplastic resin or a thermosetting resin can be used in the same manner as the "resin" in the first aspect.

<organic solvent>

The blue colored composition of this aspect may contain an organic solvent similarly to the first aspect.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate are used from the viewpoint of dispersion or dissolution of the pigment and the salt-forming product (A). Further, diol acetates such as ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferred. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety sanitary surface and low viscosity.

These organic solvents may be used singly or in combination of two or more. In the case of a mixed solvent of two or more kinds, the preferred organic solvent is preferably 65 to 95% by mass based on the total amount of the organic solvent (100% by mass). In particular, propylene glycol monomethyl ether acetate is preferred as the main component, and the proportion of the organic solvent is preferably from 65 to 100% by mass.

The organic solvent is used in an amount of 800 to 4000 parts by mass when the total mass of the colorant is set to 100 parts by mass in order to adjust the coloring composition to a suitable viscosity to form a filter segment of a uniform film thickness. good.

<scatter>

The blue coloring composition can be obtained by using a blue pigment and a salt-forming product, and the resin having a cationic group in the side chain The coloring agent of the salt-forming product (A) obtained by the reaction of the acid dye is preferably used together with a dispersing aid such as a pigment derivative in a coloring agent carrier composed of a binder resin and a solvent to be used as needed. It is manufactured by treatment of various dispersing tools such as a grinder, a two-roll mill, a sand mill, a kneader, and an attritor. Further, the blue coloring composition may be produced by dispersing a blue pigment, a salt-forming product (A), and other coloring agents, respectively, in a colorant carrier, and mixing the same.

(dispersion aid)

When the colorant is dispersed in the colorant carrier, a dispersing aid such as a dye derivative, a resin type dispersant, or a surfactant can be suitably used.

In the case of the blue coloring composition of the present aspect, the pigment derivative is preferably a basic compound using copper phthalocyanine having a basic substituent introduced into the indigo pigment, similarly to the second aspect. The basic compound of copper phthalocyanine is preferably a copper indigo amine compound, and examples thereof include a copper sulfonium sulfonate ammonium salt compound, a copper phthalocyanine tertiary amine, and a copper phthalocyanine sulfonamide compound.

In the blue coloring composition of the present aspect, the mass ratio of the copper indigo amine compound to the salt-forming product (A) (the copper indigo amine compound/salt product (A)) is preferably from 0.3 to 1.5.

When the mass ratio is within this range, the dispersibility of the blue pigment can be impaired, and the fluorescence generated by the salt-forming product (A) can be suppressed. As a result, a color filter having a high brightness and a high contrast ratio can be achieved.

When the mass ratio is less than 0.3, since the fluorescence suppression and the dispersibility of the copper indigo amine compound are insufficient, the contrast is lowered. On the other hand, if the mass ratio exceeds 1.5, the color characteristics are affected, and sometimes the brightness is low. The preferred mass ratio (copper indigo amine compound / salt forming product (A)) is from 0.4 to 1.2, and the optimum mass ratio (copper indigo amine compound / salt forming product (A)) is from 0.5 to 1.1.

In the blue coloring composition of the present aspect, a photopolymerizable compound and/or a photopolymerization initiator may be further added, and the color filter may be used as a coloring composition for a color filter.

<Photopolymerizable compound>

In the present aspect, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

In the color filter of the present aspect, a blue coloring composition is used, and when a filter segment is formed by photolithography including a step of curing the composition by ultraviolet irradiation, photopolymerization can be added in the same manner as in the first aspect. The initiator or the like is prepared in the form of a solvent developing type or an alkali developing type colored resist.

<sensitizer>

Further, in the blue colored composition of the color filter of the present aspect, the sensitizer can be contained in the same manner as in the first aspect.

<leveling agent>

In the blue colored composition of the present aspect, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent in the same manner as in the first aspect.

<hardener and hardening accelerator>

In the blue colored composition of the present aspect, in order to assist the hardening of the thermosetting resin, a curing agent, a curing accelerator, or the like may be contained as needed in the same manner as in the first aspect.

<Other additive ingredients>

In the blue coloring composition of the present aspect, in order to keep the viscosity of the composition for a long period of time, the storage stabilizer can be contained in the same manner as in the first aspect. Further, in order to improve the adhesion to the transparent substrate, an adhesion enhancer such as a decane coupling agent may be contained in the same manner as in the first aspect.

<antioxidant>

In the coloring composition of this aspect, in order to increase the transmittance of the coating film, it is preferable to contain an antioxidant similarly to the first aspect.

<Removal of large particles>

In the same manner as in the first aspect, the coloring composition of this aspect preferably removes large particles and dust mixed therein.

<Color Filter>

The color filter of this aspect is formed in the same manner as the first aspect except that the color filter of the present aspect is colored with a blue coloring composition.

The red filter segment can be formed using a usual red coloring composition containing a red pigment and a colorant carrier, similarly to the first aspect.

In the red colored composition, an orange pigment and/or a yellow pigment may be used in combination in the same manner as in the first aspect.

The green filter segment can be formed using a usual green coloring composition containing a green pigment and a colorant carrier, similarly to the first aspect.

In the green coloring composition, a yellow pigment can be used in combination as in the first aspect.

As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminum boron borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. A transparent electrode made of indium oxide or tin oxide can be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the panelization.

<Method of Manufacturing Color Filter>

The color filter of this aspect can be produced by a printing method or a photolithography method in the same manner as the first aspect.

[Example D]

The present invention will be described below based on the examples, but the present invention is not limited to these. In addition, "parts" means "parts by mass" unless otherwise specified. Further, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. The solvent was developed using THF. Further, the measurement of the specific surface area was carried out in accordance with the BET method using nitrogen adsorption using an automatic vapor adsorption amount measuring device ("BELSORP18" manufactured by Nippon BEL Co., Ltd.).

First, the acrylic resin solution (binder resin component) used in the examples and the comparative examples, the fine pigment, the resin having a cationic group in the side chain, the salt-forming product (A), a compound, a pigment derivative, a pigment dispersion, a resin solution containing a salt-forming product, and a The resin solution of the compound, the red resist material, and the method for producing the green resist material will be described.

<Method for Producing Acrylic Resin Solution> (Preparation of acrylic resin solution 1D)

The acrylic resin solution 1D was prepared in the same manner as described for the acrylic resin solution 1A.

(Preparation of acrylic resin solution 2D)

The acrylic resin solution 2D was prepared in the same manner as described for the acrylic resin solution 2A.

(Preparation of acrylic resin solution 3D)

An acrylic resin solution 3D was prepared in the same manner as described for the acrylic resin solution 3A.

(Preparation of acrylic resin solution 4D)

The acrylic resin solution 4D was prepared in the same manner as described for the acrylic resin solution 4A.

<Method for Producing Micronized Pigment> (Production of blue fine pigment 1D)

The blue fine pigment 1D was prepared in the same manner as described for the blue fine pigment 1A.

(Production of blue fine pigment 2D)

The blue fine pigment 2D was prepared in the same manner as described for the blue fine pigment 2A.

(Production of purple fine pigment 1D)

The purple fine pigment 1D was prepared in the same manner as described for the purple fine pigment 1A.

(Production of red fine pigment 1D)

The red fine pigment 1D was prepared in the same manner as described for the red fine pigment 1A.

(Production of yellow fine pigment 1D)

The yellow fine pigment 1D was prepared in the same manner as described for the yellow fine pigment 1A.

(Production of green fine pigment 1D)

The green fine pigment 1D was prepared in the same manner as described for the green fine pigment 1A.

(Production of yellow fine pigment 2D)

The yellow fine pigment 2D was prepared in the same manner as described for the yellow fine pigment 2A.

<Preparation method of resin having a cationic group in a side chain> (Production of Resin 1D having a cationic group in a side chain)

Into a separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'- 6.5 parts of azobis(2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were uniformly mixed, and the mixture was placed in a dropping funnel. Then, the dropping funnel was attached to a 4-port separable flask, and the mixture was added dropwise to the reaction vessel over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed from the obtained solid component that a resin having a polymerization yield of 98% or more and a weight average molecular weight (Mw) of 6830 was obtained. Next, the liquid containing the solid component was cooled to 50 ° C, and 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and further reacted at 50 ° C for 2 hours. Thereafter, the temperature was raised to 80 ° C for 1 hour, and further reacted for 2 hours. In this manner, the resin 1D having a cationic group in the side chain was obtained in the form of a resin solution having a resin component of 47% by mass. The obtained resin had an ammonium salt value of 34 mgKOH/g.

Further, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Further, the ammonium salt value of the resin having a cationic group in the side chain is obtained by using a 5% potassium chromate aqueous solution as an indicator and converting the value obtained by titrating with a 0.1 N aqueous silver nitrate solution into an equivalent amount of potassium hydroxide. The value represents the ammonium salt value of the solid component.

(Production of Resin 2D having a cationic group in a side chain)

6 parts of isopropyl alcohol was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacrylamidopropyltrimethylammonium chloride, and 2,2' were further added. 5.7 parts of azobis(2,4-dimethylvaleronitrile) and 15.6 parts of methyl ethyl ketone were uniformly mixed, and the mixture was placed in a dropping funnel. The dropping funnel was then attached to a 4-port separable flask, and the mixed droplets were added to the reaction vessel for 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content formed, and the weight average molecular weight (Mw) was 7,420. Then, the liquid containing the solid component was cooled to 50 ° C, and 72 parts of isopropyl alcohol was added thereto, and a resin 2D having a cationic group in the side chain was obtained in the form of a resin solution having a resin component of 40% by mass. The obtained resin had an ammonium salt value of 45 mgKOH/g.

(Production of Resin 3D having a cationic group in a side chain)

Into a separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 27.5 parts of isopropyl methacrylate, 25.0 parts of benzyl methacrylate, 27.5 parts of 2-ethylhexyl acrylate, 20.0 parts of N,N-dimethylaminomethylstyrene, 2,2' 6.7 parts of azobis(2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were uniformly mixed, and the mixture was placed in a dropping funnel. Further, the dropping funnel was attached to a 4-port separable flask, and the mixed droplets were added to the reaction vessel for 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content formed, and the weight average molecular weight (Mw) was 6,770. Next, the liquid containing the solid component was cooled to 50 ° C, and 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was further reacted at 50 ° C for 2 hours. Thereafter, the temperature was raised to 80 ° C over 1 hour, and the reaction was further carried out for 2 hours. Thus, a resin solution having a resin component of 50% by mass was obtained as the resin 3D having a cationic group in the side chain. The obtained resin had an ammonium salt value of 60 mgKOH/g.

(Production of Resin 4D having a cationic group in a side chain)

6 parts of isopropyl alcohol was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 25.0 parts of methyl methacrylate, 25.0 parts of stearyl methacrylate, 20.0 parts of cyclohexyl methacrylate, and 15.0 parts of BLEMMER PE90 (manufactured by Nippon Oil Co., Ltd., diethylene glycol monomethacrylate) were added. 20.0 parts of N-vinylpyrrolidone, 4.7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 15.6 parts of isopropanol were uniformly mixed, and the mixture was added dropwise. funnel. Then, the dropping funnel was attached to a 4-port separable flask, and the mixed droplets were added to the reaction vessel for 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content formed, and the weight average molecular weight (Mw) was 7,550. Next, the liquid containing the solid component was cooled to 50 ° C, and 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added thereto, and the mixture was further reacted at 50 ° C for 2 hours. Then, the temperature was raised to 80 ° C over 1 hour, and the reaction was further carried out for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to the solution, and a resin 4D having a cationic group in a side chain was obtained in the form of a resin solution having a resin component of 44% by mass. The obtained resin had an ammonium salt value of 92 mgKOH/g.

(Production of Resin 5D having a cationic group in a side chain)

To a separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 82.0 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. Further, 23.5 parts of ethyl methacrylate, 26.0 parts of butyl methacrylate, 25.0 parts of lauryl methacrylate, and KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd., ε-caprolactone 1 mol) 10.0 parts of 2-hydroxyethyl acrylate phosphate, 17.5 parts of diethylaminopropyl methacrylate, 6.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and methyl ethyl ketone 25.6 parts were uniformly mixed, and the mixture was placed in a dropping funnel. Further, the dropping funnel was attached to a 4-port separable flask, and the mixed droplets were added to the reaction vessel for 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content formed, and the weight average molecular weight (Mw) was 7010. The liquid containing the solid component was then cooled to 50 °C. In this manner, the resin 5D having a cationic group in the side chain was obtained in the form of a resin solution having a resin component of 48% by mass. The obtained amine salt of the resin had a valence of 49 mgKOH/g.

Further, the amine valence of the resin having a cationic group in the side chain is obtained by converting the value measured by the potentiometric titration method into the equivalent of potassium hydroxide using a 0.1 N aqueous hydrochloric acid solution.

<Method for Producing Salt-Forming Product (A)> (salt-forming product (A-1D))

A salt-forming product (A-1D) composed of C.I. Acid Red 289 and a resin 1D having a cationic group in a side chain was produced by the following procedure.

To the 2000 parts of water, 51 parts of a resin 1D having a cationic group in a side chain was added, and the mixture was thoroughly stirred, and then heated to 60 °C. To the resin solution, an aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 289 in 90 parts of water was added dropwise in small portions. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-1D) of 32 parts of C.I. Acid Red 289 and a resin 1D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-1D) was 29% by mass.

(salt-forming product (A-2))

A salt-forming product (A-2D) composed of C.I. Acid Red 289 and a resin 2D having a cationic group in a side chain was produced by the following procedure.

To a solution of 2000 parts of a 10% aqueous methanol solution, 88 parts of a resin 2D having a cationic group in a side chain was added, and the mixture was thoroughly stirred, followed by heating to 60 °C. A small amount of the resin solution was added dropwise to 90 parts of water to dissolve 10 parts of an aqueous solution of C.I. Acid Red 289. After completion of the dropwise addition, the solution was stirred at 60 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-2D) of 43 parts of C.I. Acid Red 289 and a resin 2D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-2D) was 22% by mass.

(salt-forming product (A-3D))

A salt-forming product (A-3D) composed of C.I. Acid Red 289 and a resin 3D having a cationic group in a side chain was produced by the following procedure.

To 2000 parts of a 10% N,N-dimethylformamide aqueous solution, 46.7 parts of a resin 3D having a cationic group in a side chain was added, and the mixture was thoroughly stirred, followed by heating to 70 °C. An aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 289 in 90 parts of water was successively added dropwise to the resin solution. After completion of the dropwise addition, the mixture was stirred at 70 ° C for 120 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After stirring to cool to room temperature, the mixture was subjected to suction filtration and washed with water, and the salt-forming product remaining on the filter paper was removed by using a dryer to obtain 29 parts of CI Acid Red 289 and having a cationic group in the side chain. Salt-forming product of resin 3D (A-3D). The content of the effective dye component derived from C.I. Acid Red 289 in the salt-forming product (A-3D) was 30% by mass.

(salt-forming product (A-4D))

A salt-forming product (A-4D) composed of C.I. Acid Red 289 and a resin 4D having a cationic group in a side chain was produced by the following procedure.

A solution obtained by dissolving 20.0 parts of a resin 4D having a cationic group in a side chain in 1000 parts of water was prepared, and the mixture was thoroughly stirred, and then heated to 70 °C. A small amount of the resin solution was added dropwise to 90 parts of water to dissolve 10 parts of an aqueous solution of C.I. Acid Red 289. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain 19 parts of a salt-forming product (A-4D) of C.I. Acid Red 289 and a resin 4D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-4D) was 53% by mass.

(salt-forming product (A-5D))

A salt-forming product (A-5D) composed of C.I. Acid Red 289 and a resin 5D having a cationic group in a side chain was produced by the following procedure.

63.2 parts of a resin 5D having a cationic group in a side chain was added to 20 parts of 20% acetic acid, and the mixture was thoroughly stirred, and then heated to 60 °C. Thereby, the tertiary amine ammonium of the side chain is salted. To the resin solution, an aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 289 in 90 parts of water was added dropwise in small portions. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain 38 parts of a salt-forming product (A-5D) of C.I. Acid Red 289 and a resin 5D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-5D) was 23% by mass.

(salt-forming product (A-6D))

A salt-forming product (A-6D) composed of C.I. Acid Red 289 and Disperbyk-2000 (modified acrylic-based block copolymer, ammonium salt price: 61 mgKOH/g) manufactured by C.I. Acid Red 289 was prepared by the following procedure.

50.9 parts of Disperbyk-2000 was added to 2000 parts of water and the mixture was thoroughly stirred, and then heated to 60 °C. An aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 289 in 90 parts of water was added dropwise in this resin solution in small portions. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain 31 parts of a salt-forming product (A-6D) of C.I. Acid Red 289 and Disperbyk-2000. The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-6D) was 33% by mass.

(salt-forming product (A-7D))

A salt-forming product (A-7D) composed of C.I. Acid Red 52 and a resin 1D having a cationic group in a side chain was produced by the following procedure.

To 2000 parts of water, 51 parts of a resin 1D having a cationic group in a side chain was added and the mixture was thoroughly stirred, followed by heating to 60 °C. An aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water was added dropwise in small portions to the resin solution. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-7D) of 32 parts of C.I. Acid Red 52 and a resin 1D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 52 in the salt-forming product (A-7D) was 30% by mass.

(salt-forming product (A-8D))

A salt-forming product (A-8D) composed of C.I. Acid Red 87 and a resin 1D having a cationic group in a side chain was produced by the following procedure.

To 2000 parts of water, 51 parts of a resin 1D having a cationic group in a side chain was added and the mixture was thoroughly stirred, followed by heating to 60 °C. A small amount of an aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 87 in 90 parts of water was successively added dropwise to the resin solution. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-8D) of 32 parts of C.I. Acid Red 87 and a resin 1D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 87 in the salt-forming product (A-8D) was 28% by mass.

(salt-forming product (A-9D))

A salt-forming product (A-9D) composed of C.I. Acid Red 92 and a resin 1D having a cationic group in a side chain was produced by the following procedure.

To the 2000 parts of water, 51 parts of a resin 1D having a cationic group in a side chain was added, and the mixture was thoroughly stirred, followed by heating to 60 °C. An aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 92 in 90 parts of water was added dropwise to the resin solution. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-9D) of 32 parts of C.I. Acid Red 92 and a resin 1D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 92 in the salt-forming product (A-9D) was 29% by mass.

(salt-forming product (A-10D))

A salt-forming product (A-10D) composed of C.I. Acid Red 388 and a resin 1D having a cationic group in a side chain was produced by the following procedure.

To 2000 parts of water, 51 parts of a resin 1D having a cationic group in a side chain was added and the mixture was thoroughly stirred, followed by heating to 60 °C. A small amount of the resin solution was dropwise added to 90 parts of water to dissolve 10 parts of C.I. Acid Red 388. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product (A-10D) of 32 parts of C.I. Acid Red 388 and a resin 1D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 388 in the salt-forming product (A-10D) was 30% by mass.

(salt-forming product (A-11D))

A salt-forming product (A-11D) composed of C.I. Acid Red 52 and a resin 5D having a cationic group in a side chain was produced by the following procedure.

To 2,200 parts of acetic acid, 63.2 parts of a resin 5D having a cationic group in a side chain was added and the mixture was thoroughly stirred, followed by heating to 60 °C. Thereby, the tertiary amine ammonium of the side chain is salted. To the resin solution, an aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water was added dropwise in small portions. After completion of the dropwise addition, in order to sufficiently react, the mixture was stirred at 60 ° C for 120 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain 38 parts of a salt-forming product (A-11D) of C.I. Acid Red 52 and a resin 5D having a cationic group in a side chain. The content of the effective pigment component derived from C.I. Acid Red 52 in the salt-forming product (A-11D) was 22% by mass.

< Method for producing a compound > ( Compounds (C-1D) and (C-2D))

The first aspect Compounds (C-1A) and (C-2A), respectively The compounds (C-1D) and (C-2D) are used.

<Method for Producing Pigment Derivative> (Production of pigment derivative 1D (basic compound of copper indigo))

30 parts of copper indigo was added to 300 parts of chlorosulfonic acid to completely dissolve it. Next, 24 parts of sulfinium chloride was added to the solution, and the temperature was gradually raised, and the reaction was carried out at 101 ° C for 3 hours. Next, the reaction liquid was poured into 9000 parts of ice water, stirred, filtered, and washed with water. The obtained press cake was dispersed in 300 parts of water to make a slurry, and 15 parts of N,N-dimethylaminopropylamine was added to the slurry, and the mixture was stirred at room temperature for 3 hours, followed by stirring at 60 ° C for 2 hours. . Thereafter, the mixture was filtered, washed with water and dried to obtain 36 parts of a copper phthalic acid sulfonamide compound. The obtained copper indigo sulfonate decylamine compound was subjected to composition analysis by a liquid chromatography mass spectrometer platform LCZ manufactured by Waters Co., Ltd., and as a result, it did not contain three or more substituents, and had one of the following formulas (22). A mixture of a substituent of the copper phthalocyanine decylamine compound and a copper phthalocyanine sulfonamide compound having two substituents of the following formula (22) in a mass ratio of 85:15. This copper indolinium sulfonamide compound was used as the pigment derivative 1D.

CuPc: copper indigo residue

<Method for Producing Pigment Dispersion> (Preparation of pigment dispersion (DP-1D))

After the following mixture was uniformly stirred, zirconia beads having a diameter of 0.5 mm were used, and Eigermil ("Minimodel M-250 MKII" manufactured by Eiger Japan Co., Ltd.) was used for dispersion treatment for 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DP-1).

Blue fine pigment 1D (C.I. Pigment Blue 15:6): 11.0 parts

Pigment Derivative 1D: 1.0 part

Acrylic resin solution 1D: 39.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.): 1.0 part

(Preparation of pigment dispersions (DP-2D) to (DP-7D))

A pigment dispersion (DP-2D) to (DP-7D)) was prepared in the same manner as in the above pigment dispersion (DP-1D) except that the blue fine pigment 1D was changed to the pigment shown in Table 19. Further, in the case where the pigment derivative 1D was not contained, the acrylic resin solution was determined to be 40 parts.

<Resin solution containing salt-forming product and containing Method for producing resin solution of compound> (Preparation of resin solution (DA-1D) containing salt-forming product)

The following mixture was stirred uniformly, and then filtered through a 5.0 μm filter to obtain a resin solution (DA-1D) containing a salt-forming product.

(Preparation of resin solution (DA-1D) containing salt-forming product)

The salt-forming product (A-1D) is changed to the salt-forming product (A) shown in Table 20 or In addition to the above-mentioned resin solution (DA-1D) containing a salt-forming product, a resin solution (DA-2D) to (DA-11D) containing a salt-forming product and containing the same are prepared. A resin solution (DC-1D) and (DC-2D) of the compound. The content of the pigment component is shown in Table 20. In addition, the pigment content A indicates a salt-forming product (A) or The content (% by mass) of the effective pigment component in the compound. Further, the pigment content B indicates the content (% by mass) of the effective dye component in the resin solution containing the colorant.

*1 Pigment component content A: salt-forming product (A) or Effective pigment component content of the compound (% by weight)

*2 Pigment component content B: Content of effective pigment component (% by weight) in resin solution containing colorant

<Method of Manufacturing Red and Green Resist Material> (Preparation of red resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a red resist.

Pigment dispersion (DP-4D): 50.0 parts

Pigment dispersion (DP-5D): 10.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred uniformly, and then filtered through a 1.0 μm filter to obtain a green resist.

Pigment dispersion (DP-6D): 45.0 parts

Pigment dispersion (DP-7D): 15.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK E STER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1D to 14D, Comparative Examples 1D to 4D] (Example 1D: Colored composition (DB-1D))

The mixture was stirred well, and then filtered through a 5.0 μm filter to obtain a mixed coloring composition.

Resin solution containing colorant (DA-1D): 2.2 parts

Pigment dispersion (DP-1D): 8.8 parts

Acrylic resin solution 1D : 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Examples 2D to 14D, Comparative Examples 1D to 4D: Colored Compositions (DB-2D) to (DB-18D))

The coloring composition (DB-2D) was prepared in the same manner as the coloring composition (DB-1D) except that the resin solution (DA-1D) containing the coloring agent and the blending amount thereof were changed as shown in Table 21. DB-18D).

(Evaluation of color characteristics)

A coloring composition is applied to the glass substrate. Specifically, the color compositions of Examples 1D to 11D and Comparative Examples 1D to 3D were applied so that the chromaticity under the C light source became a film thickness of x=0.150 and y=0.060. Further, the color compositions of Examples 12D to 14D and Comparative Example 4D were applied such that the chromaticity under the C light source was a film thickness of x=0.190 and y=0.060. The substrates were then heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness (Y) of the substrate on which the colored layer was formed was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). Table 22 shows the results.

(Test method for foreign matter in coating film)

With respect to the above colored composition, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, the colored composition was applied onto a transparent substrate to a dry film thickness of about 2.0 μm, and this was heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is obtained. The results are shown in Table 22.

In Table 22, the symbols in the "coated foreign matter" column have the following meanings.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

When the total number of particles is less than 20, coating unevenness due to foreign matter hardly occurs. In addition, when the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. In addition, when the total number of particles is 100 or more, coating unevenness (speckle) due to foreign matter occurs.

The coating film obtained from the colored composition containing the blue pigment and the salt-forming product (A) has less foreign matter (undissolved foreign matter). On the other hand, by containing The coating film obtained by the coloring composition of the compound (C-1D) and (C-2D) has a large amount of foreign matter. That is, when a salt-forming product of a resin having a cationic group in a side chain is used, it is compared with the use of a substituted functional group. When dyes are used, more excellent performance can be achieved.

Further, a coating film obtained by using a coloring composition containing a blue pigment and a salt-forming product (A) has a high brightness. Further, the coating film of the comparative example was lower in brightness than the coating film of the example.

[Examples 15D to 27D and Comparative Examples 5D to 7D]

(Example 15D: Resist material (R-1D))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-1D).

Resin solution containing colorant (DA-1D): 12.0 parts

Pigment dispersion (DP-1D): 48.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Examples 16D to 27D and Comparative Examples 5D to 7D: Resist materials (R-2D) to (R-16D))

The alkali developing type anti-corrosion was obtained in the same manner as in the resist material (R-1D) except that the resin solution containing the coloring agent, the colorant dispersion, and the blending amount were changed as shown in Table 23. Etched materials (R-2D) to (R-16D).

(Examples 28D to 33D: Resist materials (R-17D) to (R-22D))

The alkali-developing resist material (R-17D) and (R) were obtained in the same manner as the resist material (R-5D) except that the acrylic resin solution 1D was changed to the acrylic resin solutions 2D, 3D, and 4D. -18D) and (R-19D). In addition, the alkali-developing resist material (R-20D) was obtained in the same manner as the resist material (R-11D) except that the acrylic resin solution 1D was changed to the acrylic resin solutions 2D, 3D, and 4D. , (R-21D) and (R-22D).

(evaluation of resist material)

A coating film is formed from the resist materials (R-1D) to (R-22D), and the chromaticity, the amount of foreign matter, heat resistance, light resistance, solvent resistance, and contrast ratio are examined for the coating films by the following methods, respectively. . The test results are shown in Table 24.

(Test method for foreign matter in coating film)

With respect to the above-mentioned resist material, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, a resist material was applied onto a transparent substrate to have a dry film thickness of about 2.5 μm, and the coating film was entirely exposed to ultraviolet light. Thereafter, it was heated in an oven at 230 ° C for 20 minutes, and then allowed to cool to obtain an evaluation substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is obtained. The results are shown in Table 24.

In addition, in Table 24, the meaning of the mark in the "coating foreign matter" column is as follows.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

(Evaluation of color characteristics)

A resist material is coated on the glass substrate. Specifically, the resist material was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.060. The substrates were heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). Table 24 shows the results.

(Method of coating film heat resistance test)

The resist material was applied onto the transparent substrate to a dry film thickness of about 2.5 μm, and the coating film was exposed to ultraviolet light through a mask having a predetermined pattern. The alkali developer is sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, this was equal to heating in an oven at 230 ° C for 20 minutes. After cooling, the color of the obtained coating film under a C light source was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1), b*( 1)). Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the chromaticity 2 (L*(2), a*(2), b*(2)) under a C light source was measured.

Using these chromaticities, the color difference ΔEab* is calculated according to the following calculation formula. Then, based on the color difference ΔEab*, the heat resistance of the coating film was evaluated in the following four stages.

◎: ΔEab* is less than 1..5

○: ΔEab* is 1.5 or more and less than 2.5

△: ΔEab* is 2.5 or more and less than 5.0

×: ΔEab* is 5.0 or more

Table 24 shows the results.

(Method of coating film light resistance test)

The test substrate was prepared in the same manner as the coating film heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a* (1), b*(1)). Thereafter, the substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI Co., Ltd.), and left for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using these chromaticities, the color difference ΔEab* was calculated in the same manner as the coating film heat resistance test, and the light resistance of the coating film was evaluated on the same basis as the heat resistance. Table 24 shows the results.

(Method of film resistance test)

The test substrate was produced in the same procedure as the heat resistance test, and the chromaticity 1 under the C light source was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1) ), b*(1)). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the chromaticity was used in the same manner as the coating film heat resistance test. The color difference ΔEab* was calculated, and the solvent resistance of the coating film was evaluated on the same basis as the heat resistance. Table 24 shows the results.

(contrast ratio evaluation)

For the coloring layer formed in the evaluation of the color characteristics, the contrast ratio was measured in the following manner. The results are shown in Table 24.

(Measurement method of coating film contrast ratio)

The light emitted from the liquid crystal display backlight unit is incident on the first polarizing plate, and the linear polarized light that has penetrated the first polarizing plate passes through the dried coating film of the coloring composition, and is incident on the second polarizing plate. Further, the luminance of the second polarizing plate is measured such that the transmission axes of the first and second polarizing plates are parallel to each other (corresponding to white display) and the transmission axes of the first and second polarizing plates are orthogonal to each other. The situation (equivalent to black display) both. The contrast ratio is a ratio of the luminance when the transmission axes of the first and second polarizing plates are parallel, and the luminance when the transmission axes are orthogonal to each other.

Here, the luminance meter is a color luminance meter ("BM-5A" manufactured by TOPCON Co., Ltd.), and the first and second polarizing plates are "NPF-G1220DUN" manufactured by Nitto Denko Corporation. Further, in order to shield the luminance, a black mask having a hole of 1 cm square was superposed on the second polarizing plate, and the region corresponding to the hole was performed.

Further, when the linear polarized light penetrates the dried coating film of the colored composition, it is scattered by the pigment particles to become elliptically polarized light. As a result, when the transmission axes of the first and second polarizing plates are parallel, the amount of light that penetrates the second polarizing plate is reduced, that is, when the pigment in the coating film is scattered, the luminance when the transmission axis is parallel is lowered. When the transmission axis is orthogonal, the luminance increases, so the contrast ratio becomes lower.

The coating films obtained from the resist materials (R-1D) to (R-12D) and (R-14D) to (R-19D) achieve good performance for contrast ratio, lightness, and light resistance. In addition, the coating film obtained from the resist material (R-13D) is somewhat low in heat resistance, light resistance, and solvent resistance, but is excellent in color characteristics when it is used at a level where the color filter is not problematic. On the other hand, the coating film obtained from the resist materials (R-14D) and (R-15D) has a large amount of foreign matter and a low contrast ratio.

The coating film obtained from the resist material (R-16D) of Comparative Example 7D had a lower brightness (Y) than the coating films of Examples 15D to 33D.

Further, as a result of the resist materials (R-17D) to (R-22D), it is understood that the coating film foreign matter can be further reduced by using an active energy ray-curable resin having a vinyl bond.

[Example 34D] (Color Filter (CF-1D))

A black matrix of a light-shielding pattern was formed on the glass substrate, and then a red resist was applied using a spin coater. The red resist material was applied such that the chromaticity under the C light source was a film thickness of x=0.640 and y=0.330. For the coating film, ultraviolet rays were irradiated through a photomask using an ultrahigh pressure mercury lamp at an exposure amount of 300 mJ/cm ² . Next, the coating film was subjected to spray development using an alkali developing solution composed of a 0.2% by mass aqueous sodium carbonate solution, and the exposed portion was removed and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

Next, a green resist material was applied on the substrate by the same method as described above. The green resist material was applied so as to have a film thickness of x=0.300 and y=0.600 under the C light source. The coating film was subjected to the same exposure, development, cleaning, and firing as the red filter segment to form a green filter segment.

Further, a blue resist (R-1D) was applied on the substrate in the same manner as described above. The blue resist (R-1D) was applied so that the chromaticity under the C light source was a film thickness of x=0.150 and y=0.060. The coating film was subjected to the same exposure, development, cleaning, and firing as the red filter segment to form a blue filter segment. The color filter (CF-1D) was obtained in the above manner.

(production of liquid crystal display)

An electrode made of ITO was formed on a color filter (CF-1D), and an alignment layer made of polyimide was formed thereon. Further, a TFT array and a pixel electrode were formed on one surface of a separately prepared glass substrate, and an alignment layer made of polyimide was formed thereon.

Next, on the surface of the glass substrate on which the electrode is provided, a sealant is used to form a frame-like pattern having a passage connecting the inside and the outside of the frame. Then, the substrates are bonded to each other with the spacer beads interposed therebetween so that the electrodes face each other.

Next, in the internal space of the unit cell obtained in this manner, the liquid crystal composition was injected from the previous passage. After the via was sealed, a polarizing plate was attached to both sides of the unit cell to obtain a liquid crystal display panel.

Thereafter, the liquid crystal display panel is combined with a backlight unit including a three-wavelength CCFL to complete the liquid crystal display.

[Examples 35D to 52D and Comparative Examples 8D to 10D] (Color Filter (CF-2D) to (CF-22D))

A color filter (CF-2D) was produced in the same manner as the color filter (CF-1D) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 25. (CF-22D) and liquid crystal display.

The liquid crystal display was displayed in a color image, and the brightness of the region corresponding to the red, green, and blue filter segments was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Then, the brightness of the white display is obtained from the brightness. The results are shown in Table 25.

The color filters (CF-1D) to (CF-13D) and (CF-17D) to (CF-22D) are formed of a resist material containing a blue pigment and a salt-forming product (A). On the other hand, the color filter (CF-16D) is composed of a copper indigo pigment and two A pigment-based resist material former. From the comparison of the data obtained, the liquid crystal display including the color filters (CF-1D) to (CF-13D) and (CF-17D) to (CF-22D) is compared with the color filter. The film (CF-16D) liquid crystal display can display white images with higher brightness. Further, although the color filters (CF-14D) and (CF-15D) have high brightness, as described above, foreign matter is large and therefore it is not practical.

The techniques explained in the first to fourth aspects can be combined with each other. For example, a compound having a cationic group may be used in combination of two or more kinds of a quaternary ammonium salt, an amine, and a resin having a cationic group. Further, the blue colored composition of the first, third, and fourth aspects may contain the copper phthalocyanine described in the second aspect.

(Example 61D)

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-61D).

Resin solution containing salt-forming product (DA-1D): 12.0 parts

Pigment dispersion (DP-1D): 48.0 parts

Acrylic resin solution 1D: 10.5 parts

Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Antioxidant [neopentitol-肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]: 0.5 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

The same evaluation as that for the resist material (R-1D) was carried out except that the resist material (R-61D) was used. As a result, the lightness (Y) was 6.9, and the contrast ratio was 9,600. Further, all of the evaluations of the coating film foreign matter, heat resistance, light resistance, and solvent resistance were excellent (◎). As compared with the results obtained for the resist materials (R-61D) and (R-1D), the brightness and contrast ratio can be improved by using an antioxidant.

o fifth aspect

Next, the fifth aspect will be explained.

Since the past, the blue filter segment has been manufactured using two The blue coloring composition of the pigment is used as a purple pigment. In order to obtain a blue filter segment which is thin and excellent in color purity from such a blue colored composition, the pigment content in the blue filter segment has been increased so far.

However, in order to increase the color difference from the green filter segment, the blue filter segment formed so that the spectral transmittance of the region near the wavelength of 570 nm becomes 3% or less, and the spectroscopic region in the region near the wavelength of 450 nm The maximum penetration rate is low, and the color reproducibility of blue is low. As described above, it is difficult to obtain a blue filter segment which exhibits high transmittance in the blue wavelength region and sufficiently reduces the transmittance in the green and red wavelength regions.

The color filter for the fifth aspect of the color filter contains a binder resin and a coloring agent. The colorant contains a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group. If the blue coloring composition is used, a blue filter segment having desired optical characteristics can be easily realized.

That is, the coating film formed by the blue coloring composition of the present aspect so as to have a spectral transmittance of 570 nm of 570 nm has the following spectral characteristics: a wavelength of 50% of the spectral transmittance is 490 to 490 In the range of 510 nm, the spectral transmittance at a wavelength of 450 nm is 85% or more, and the spectral transmittance at a wavelength of 540 nm is 11% or less. Such a film is compared to the use of two The pigment CI Pigment Violet 23 replaces the blue coloring composition of the salt product to form a coating film having a spectral transmittance of 3% at a wavelength of 570 nm, and exhibits a high spectral transmittance at a wavelength of around 450 nm, and is near a wavelength of 650 nm. The area shows low spectroscopic transmittance. As described above, the blue filter segment formed of the blue colored composition of the present aspect has a high maximum value of the spectral transmittance in the vicinity of the wavelength of 450 nm. Therefore, the blue filter segment is excellent in color reproducibility in the blue region.

That is, in order to sufficiently reduce the transmittance of the wavelength region below the green color, the blue coloring component of the present aspect forms a blue filter segment such that the transmittance in the region around the wavelength of 570 nm becomes about 3%. Such a blue filter segment can also have a low transmittance in a region near a wavelength of 650 nm.

Alternatively, in order to sufficiently reduce the transmittance of the wavelength region lower than green, the blue coloring component of the present aspect forms a blue filter segment such that the transmittance in the region near the wavelength of 540 nm becomes about 10%. The blue filter segment can have a high transmittance in a region near the wavelength of 450 nm.

Thus, according to this aspect, a blue filter segment which exhibits high transmittance in the blue wavelength region and sufficiently reduces the transmittance in the green and red wavelength regions can be obtained.

<salt formation product (A)> (Compound (a) having a cationic group)

The compound having a cationic group is not particularly limited as long as it has at least one onium salt group. The compound having a phosphonium salt group is preferably an ammonium salt compound, a phosphonium salt compound, a phosphonium salt compound, a diazonium salt compound, or a phosphonium salt compound.

The compound having a cationic group is preferably a resin (a1) having a cationic group in a side chain or a quaternary ammonium compound (a2) represented by the formula (23).

A preferred embodiment of the compound (a) having a cationic group is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance in the entire wavelength region of 400 to 700 nm in the visible light region is 95% or more, preferably 98% or more. That is, the compound (a) having a cationic group is preferably one which does not interfere with the color development of the dye component and does not cause color change.

[Resin (a1) having a cationic group in a side chain]

In the resin (a1) having a cationic group in the side chain, the resin (a1) having a cationic group in the side chain in the fourth aspect can be similarly used.

[Quaternary ammonium compound (a2) represented by the general formula (23)]

The quaternary ammonium compound (a2) represented by the formula (23) can be similarly used in the quaternary ammonium compound of the first aspect.

[In the formula (23), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y- represents an inorganic or organic anion. ]

Wherein the quaternary ammonium compound (a2) represented by the formula (23) is preferably such that R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least 2 carbon atoms The number is 5 to 20.

( Acid dye)

For obtaining a salt-forming product (A) Acid dye, the same can be used in the first aspect. It is an acid dye.

(salt treatment) [Resin (a1) having a cationic group in a side chain and Salt formation of acid dyes]

a resin (a1) having a cationic group in a side chain and The salt-forming product of the acid dye can be obtained in the same manner as described in the column of "(salt formation)" in the fourth aspect.

a resin (a1) having a cationic group in a side chain and The ratio of the acid dye to the total cation unit of the resin is determined from the viewpoint of preferably preparing the salt-forming product (A) of the present aspect. The molar ratio of the total anionic group of the acid dye is preferably in the range of from 10/1 to 1/4, and more preferably in the range of from 2/1 to 1/2.

[Quaternary ammonium compound (a2) and Salt formation of acid dyes]

The salt-forming product of the acid dye and the quaternary ammonium compound (a2) can be obtained by the same method as described in the first aspect.

(content of effective pigment component contained in salt-forming product (A))

From the salt-forming product (A) The content of the effective dye component of the acid dye is the same as that of the fourth aspect.

<blue pigment>

As the blue pigment constituting the coloring agent, as the first aspect, a phthalocyanine pigment and/or a triarylmethane-based lake pigment or the like can be used. For the indigo pigment, it is preferred to use a copper phthalocyanine pigment.

Among them, the blue pigment is preferably C.I. Pigment Blue 15:6 or C.I. Pigment Blue 1.

(fineness of pigment)

The blue pigment used in the blue coloring composition of this aspect and the other pigment which can be used arbitrarily can be subjected to salt milling treatment in the same manner as in the second aspect to be fine.

In addition, the primary particle diameter of the pigment is measured by directly measuring the size of the primary particles by an electron micrograph taken by a TEM (transmission electron microscope) of the pigment, similarly to the second aspect.

The salt-forming product (A) is preferably used in an amount of from 1 to 800 parts by mass, more preferably from 5 to 400 parts by mass, per 100 parts by mass of the blue pigment. When the amount of the salt-forming product (A) to be added is less than 1 part by mass, the reproducible chromaticity region is narrowed. Moreover, when the amount added exceeds 800 parts by mass, the hue changes.

When the color configuration is considered, the content of the effective dye component in the salt-forming product (A) is preferably in the range of 1 to 400 parts by mass based on 100 parts by mass of the blue pigment. The mass of the effective dye component in the salt-forming product (A) is more preferably in the range of 5 to 300 parts by mass based on 100 parts by mass of the blue pigment, and particularly preferably in the range of 17 to 300 parts by mass.

In particular, use CI Acid Red 289 or CI Acid Red 52 as The salt-forming product (A) of an acid dye is excellent in solvent solubility, and when used in combination with a blue pigment, excellent heat resistance, light resistance, and solvent resistance can be achieved. Further, the reason why the salt-forming product (A) and the blue pigment are used in combination to achieve good performance is that the salt-forming product (A) is adsorbed to the blue pigment in a state of being dissolved or dispersed in a solvent.

<Other coloring agents>

In the blue coloring composition of the present aspect, in addition to the components of the coloring agent, in addition to the first aspect, other organic pigments may be added as long as the effects are not impaired for the purpose of coloring.

<Binder resin>

The binder resin is used to disperse the colorant, especially the salt-forming product, or to dye or impregnate the salt-forming product. The binder resin may, for example, be a thermoplastic resin or a thermosetting resin, and the "resin" of the first aspect may be used in the same manner.

<organic solvent>

In the same manner as in the first aspect, the coloring agent is applied to a substrate such as a glass substrate to form a dry film thickness of 0.2 to 5 μm in order to facilitate the coloring agent to be sufficiently dispersed or dissolved in the colorant carrier. The filter section may contain a solvent.

As the organic solvent, the solvent of the first aspect can be used in the same manner.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether B are used from the viewpoint of good dispersibility or solubility of the pigment and the salt-forming product (A). A glycol diol such as an acid ester or ethylene glycol monoethyl ether acetate, an aromatic alcohol such as benzyl alcohol, or a ketone such as cyclohexanone is preferred. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety sanitary surface and low viscosity.

These organic solvents may be used alone or in combination of two or more. When two or more solvents are mixed, the above preferred organic solvent is preferably 65 to 95% by mass.

The organic solvent is used in an amount of 800 to 4000 parts by mass when the coloring agent is adjusted to have a suitable viscosity and a filter segment having a uniform film thickness for the purpose of the coloring agent is 100 parts by mass. The amount is better.

<scatter>

The blue coloring composition of the present aspect can be obtained by using a resin containing a blue pigment and having a cationic group in a side chain. The coloring agent of the salt-forming product (A) obtained by the reaction of the acid dye is preferably used together with a dispersing aid such as a pigment derivative in a coloring agent carrier composed of a binder resin and a solvent to be used as needed. It is manufactured by treatment of various dispersing tools such as a grinder, a two-roll mill, a sand mill, a kneader, and an attritor. Further, in the blue coloring composition of the present aspect, the blue pigment, the salt-forming product (A), and other coloring agents may be separately dispersed in the colorant carrier, and these may be mixed and manufactured.

(dispersion aid)

When the coloring agent is dispersed in the coloring agent carrier, a dispersing aid such as a dye derivative, a resin type dispersing agent, or a surfactant can be suitably used in the same manner as in the fourth aspect.

As the dye derivative, the pigment derivative of the fourth aspect can also be used in the same manner.

As the resin type dispersant, the resin type dispersant of the first aspect can also be used in the same manner.

As the surfactant, the surfactant of the first aspect can also be used in the same manner.

In the blue coloring composition of the present aspect, a photopolymerizable compound and/or a photopolymerization initiator may be further added, and the color filter may be used as a coloring composition for a color filter.

<Photopolymerizable compound>

In this aspect, the photopolymerizable compound of the first aspect can also be used in the same manner.

<Photopolymerization initiator>

In the color filter of the present aspect, a blue coloring composition is used, and when a filter segment is formed by photolithography including a step of hardening the composition by ultraviolet irradiation, photopolymerization can be added in the same manner as in the first aspect. The initiator or the like is prepared in the form of a solvent developing type or an alkali developing type colored resist.

<sensitizer>

Further, in the blue coloring composition of the color filter of the present aspect, the sensitizer can be contained in the same manner as in the first aspect.

<leveling agent>

In the blue colored composition of the present aspect, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent in the same manner as in the first aspect.

<hardener, hardening accelerator>

In the blue colored composition of the present aspect, in order to assist the hardening of the thermosetting resin, a curing agent, a curing accelerator, and the like may be contained in the same manner as in the first aspect.

<Other additive ingredients>

In the blue coloring composition of the present aspect, in order to keep the viscosity of the composition for a long period of time, the storage stabilizer can be contained in the same manner as in the first aspect. Further, in order to improve the adhesion to the transparent substrate, the adhesion enhancer may be contained in the same manner as in the first aspect.

<antioxidant>

In the coloring composition of this aspect, in order to increase the transmittance of the coating film, it is preferable to contain an antioxidant similarly to the first aspect.

<Method for Producing Colored Composition for Color Filter>

The color filter of the present aspect is a blue coloring composition, and a step of kneading a mixture containing a binder resin, a colorant, and any of the above components by a two-roll mill to form a sheet by repeating a plurality of times, for example, The sheet is pulverized, and the thus obtained chips are added to an organic solvent and stirred, and then obtained by dispersion treatment using a medium disperser such as a bead mill. Alternatively, the color filter of the present aspect may be a blue coloring composition, and the mixture may be subjected to dispersion treatment using a media disperser such as a bead mill to prepare a blue coloring composition, and a photopolymerizable compound may be blended therein. It is obtained by a photopolymerization initiator, an organic solvent, or the like.

It is preferable to remove large particles of 5 μm or more from the colored composition by a method such as centrifugation, sinter filtration, or membrane filtration, and it is preferably a large particle of 1 μm or more, more preferably a large particle of 0.5 μm or more, and dust mixed therein.

<Color Filter>

Next, the color filter of this aspect will be described.

The color filter of this aspect comprises, for example, a plurality of filter segments having different absorption spectra and typically regularly arranged. A color filter comprising: at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter of this aspect, for example, the blue filter segment is formed of the coloring composition for the color filter described above.

The red filter segment can be formed using a general red coloring composition containing a red pigment and a pigment carrier, similarly to the first aspect. Further, in the red colored composition, an orange pigment and/or a yellow pigment may be used in combination in the same manner as in the first aspect.

The green filter segment can be formed using a general green coloring composition containing a green pigment and a pigment carrier in the same manner as in the first aspect. Further, in the green coloring composition, a yellow pigment may be used in combination in the same manner as in the first aspect.

As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminum boron borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. A transparent electrode made of indium oxide or tin oxide can be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the panelization.

<Method of Manufacturing Color Filter>

The color filter of this aspect can be produced by a printing method or a photolithography method in the same manner as the first aspect.

[Example E]

The present invention will be described below based on the examples, but the present invention is not limited to these. In addition, "parts" means "parts by mass" unless otherwise specified. Further, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. The solvent was developed using THF.

In addition, the weight average molecular weight (Mw) of the acrylic resin was measured by using a TSKgel column (manufactured by Tosoh Corporation), GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and using THF as a developing solvent. The weight average molecular weight (Mw) in terms of styrene.

First, the acrylic resin solution, the fine pigment, the resin having a cationic group in the side chain, the salt-forming product (A), and the salt-forming product (A) used in the examples and the comparative examples. a compound, a pigment dispersion, a resin solution containing a salt-forming product, and a The resin solution of the compound, the red resist material, and the method for producing the green resist material will be described.

<Method for Producing Acrylic Resin Solution> (Preparation of Acrylic Resin Solution 1E)

The acrylic resin solution 1E was prepared in the same manner as described for the acrylic resin solution 1A.

(Preparation of Acrylic Resin Solution 2E)

The acrylic resin solution 2E was prepared in the same manner as described for the acrylic resin solution 2A.

(Preparation of Acrylic Resin Solution 3E)

The acrylic resin solution 3E was prepared in the same manner as described for the acrylic resin solution 3A.

(Preparation of Acrylic Resin Solution 4E)

The acrylic resin solution 4E was prepared in the same manner as described for the acrylic resin solution 4A.

<Method for Producing Micronized Pigment> (production of blue fine pigment 1E)

The blue fine pigment 1E was prepared in the same manner as described for the blue fine pigment 1A.

(Production of blue fine pigment 2E)

The blue fine pigment 2E was prepared in the same manner as described for the blue fine pigment 2A.

(Production of purple fine pigment 1E)

The purple fine pigment 1E was prepared in the same manner as described for the purple fine pigment 1A.

<Preparation method of resin (a1) having a cationic group in a side chain> (Preparation of Resin 1E having a cationic group in a side chain)

Resin 1E having a cationic group in a side chain was prepared in the same manner as described for the resin 1D.

(Preparation of Resin 2E having a cationic group in a side chain)

Resin 2E having a cationic group in a side chain was prepared in the same manner as described for Resin 2D.

(Preparation of Resin 3E having a cationic group in a side chain)

Resin 3E having a cationic group in the side chain was prepared in the same manner as described for the resin 3D.

(Preparation of Resin 4E having a cationic group in a side chain)

Resin 4E having a cationic group in a side chain was prepared in the same manner as described for Resin 4D.

(Preparation of Resin 5E having a cationic group in a side chain)

Resin 5E having a cationic group in the side chain was prepared in the same manner as described for the resin 5D.

<Method for producing salt-forming product> (salt-forming product (A-1E))

The salt-forming product (A-1E) was prepared in the same manner as described for the salt-forming product (A-1D).

(salt-forming product (A-2E))

The salt-forming product (A-2E) was prepared in the same manner as described for the salt-forming product (A-2D).

(salt-forming product (A-3E))

The salt-forming product (A-3E) was prepared in the same manner as described for the salt-forming product (A-3D).

(salt-forming product (A-4E))

The salt-forming product (A-4E) was prepared in the same manner as described for the salt-forming product (A-4D).

(salt-forming product (A-5E))

The salt-forming product (A-5E) was prepared in the same manner as described for the salt-forming product (A-5D).

(salt-forming product (A-6E))

The salt-forming product (A-6E) was prepared in the same manner as described for the salt-forming product (A-6D).

(salt-forming product (A-7E))

The salt-forming product (A-7E) was prepared in the same manner as described for the salt-forming product (A-7D).

(salt-forming product (A-8E))

The salt-forming product (A-8E) was prepared in the same manner as described for the salt-forming product (A-8D).

(salt-forming product (A-9E))

The salt-forming product (A-9E) was prepared in the same manner as described for the salt-forming product (A-9D).

(salt-forming product (A-10E))

The salt-forming product (A-10E) was prepared in the same manner as described for the salt-forming product (A-10D).

(salt-forming product (A-11E))

The salt-forming product (A-11E) was prepared in the same manner as described for the salt-forming product (A-11D).

(salt-forming product (A-12E))

A salt-forming product (A-12E) composed of C.I. Acid Red 289 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

The C.1. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.1. Acid Red 289 and distearyldimethylammonium chloride, that is, a salt-forming product (A-12E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-12E) was 54% by mass.

(salt-forming product (A-13E))

A salt-forming product (A-13E) composed of C.I. Acid Red 289 and dilauryldimethylammonium chloride (having a molecular weight of 382 in the cationic portion) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, dilauryl dimethyl ammonium chloride was added dropwise in small portions. An aqueous solution can also be used for dilauryl dimethyl ammonium chloride. After the dropwise addition of dilauryldimethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and dilauryldimethylammonium chloride, that is, a salt-forming product (A-13E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-13E) was 63% by mass.

(salt-forming product (A-14E))

A salt-forming product (A-14E) consisting of C.I. Acid Red 289 and tristearate monomethylammonium chloride (molecular weight of the cationic moiety of 788) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, tristearate monomethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for tristearate monomethylammonium chloride. After the dropwise addition of tristearate monomethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and tristearate monomethylammonium chloride, that is, a salt-forming product (A-14E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-14E) was 45% by mass.

(salt-forming product (A-15E))

A salt-forming product (A-15E) composed of C.I. Acid Red 52 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

The C.I. Acid Red 52 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 52 and distearyldimethylammonium chloride, that is, a salt-forming product (A-15E). The content of the effective pigment component derived from C.I. Acid Red 52 in the salt-forming product (A-15E) was 50% by mass.

(salt-forming product (A-16E))

A salt-forming product (A-16E) composed of C.I. Acid Red 87 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 in the cationic moiety) was produced by the following procedure.

The C.I. Acid Red 87 was dissolved in 7 to 15 mol% of a sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 87 and distearyldimethylammonium chloride, that is, a salt-forming product (A-16E). The content of the effective pigment component derived from C.I. Acid Red 87 in the salt-forming product (A-16E) was 55 mass%.

(salt-forming product (A-17E))

A salt-forming product (A-17E) composed of C.I. Acid Red 92 and trilaurylbenzylammonium chloride (having a molecular weight of the cationic moiety of 612) was produced by the following procedure.

The C.I. Acid Red 92 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, trisodium lauryl benzyl ammonium chloride was added dropwise in small portions. An aqueous solution can also be used for trilaurylbenzylammonium chloride. After the dropwise addition of trilaurylbenzylammonium chloride was completed, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 92 and trilaurylbenzylammonium chloride, that is, a salt-forming product (A-17E). The content of the effective pigment component derived from C.I. Acid Red 92 in the salt-forming product (A-17E) was 57% by mass.

(salt-forming product (A-18E))

A salt-forming product (A-18E) composed of C.I. Acid Red 388 and distearyldimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 of a cationic moiety) was produced by the following procedure.

The C.I. Acid Red 388 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After heating the solution to 70 to 90 ° C, QUARTAMIN D86P was added dropwise in small portions. An aqueous solution can also be used with the QUARTAMIN D86P. After the completion of the dropwise addition of QUARTAMIN D86P, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 388 and distearyl dimethylammonium chloride, that is, a salt-forming product (A-18E). The content of the effective pigment component derived from C.I. Acid Red 388 in the salt-forming product (A-18E) was 51% by mass.

(salt-forming product (A-19E))

A composition consisting of CI Acid Red 289 and a dialkyl (alkyl group having 14 to 18 carbon atoms) dimethylammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 of a cationic moiety) was produced by the following procedure. Salt product (A-19E).

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Arquad 2HT-75 was added dropwise in small portions. Aqueous solutions can also be used with Arquad 2HT-75. After the completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of CI acid red 289 and a dialkyl group (having an alkyl group having 14 to 18 carbon atoms) of dimethyl ammonium chloride. Salt product (A-19E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-19E) was 57% by mass.

(salt-forming product (A-20E))

A salt formed from CI Acid Red 52 and a dialkyl (14 to 18 atomic number of alkyl group) dimethylammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 of a cationic moiety) was produced by the following procedure. Product (A-20E).

The C.I. Acid Red 52 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Arquad 2HT-75 was added dropwise in small portions. Aqueous solutions can also be used with Arquad 2HT-75. After the completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of CI acid red 52 and a dialkyl group (having an alkyl group having 14 to 18 carbon atoms) of dimethyl ammonium chloride. Salt product (A-20E). The content of the effective pigment component derived from C.I. Acid Red 52 in the salt-forming product (A-20E) was 53% by mass.

(salt-forming product (A-21E))

A salt-forming product (A-21E) composed of C.I. Acid Red 289 and monolauryl trimethylammonium chloride (having a molecular weight of 228 of a cationic moiety) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, monolauryl trimethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for monolauryl trimethylammonium chloride. After completion of the dropwise addition of monolauryl trimethylammonium chloride, the solution was stirred at 70 to 90 ° C for 60 minutes in order to sufficiently react. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and monolauryltrimethylammonium chloride, that is, a salt-forming product (A-21E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-21E) was 74% by mass.

(salt-forming product (A-22E))

A salt-forming product (A-22E) composed of C.I. Acid Red 289 and tetraethylammonium chloride (having a molecular weight of the cationic moiety of 122) was produced by the following procedure.

The C.I. Acid Red 289 was dissolved in 7 to 15 mol% sodium hydroxide solution, and the solution was thoroughly stirred. After the solution was heated to 70 to 90 ° C, tetraethylammonium chloride was added dropwise in small portions. An aqueous solution can also be used for tetraethylammonium chloride. After the dropwise addition of tetraethylammonium chloride was completed, the solution was stirred at 70 to 90 ° C for 60 minutes. The reaction end point was defined as the time point at which the reaction liquid was dropped on the filter paper without bleeding. That is, when the exudation disappears, it is judged that the salt-forming product has been obtained. After cooling to room temperature while stirring, the mixture was filtered and washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of C.I. Acid Red 289 and tetraethylammonium chloride, that is, a salt-forming product (A-22E). The content of the effective pigment component derived from C.I. Acid Red 289 in the salt-forming product (A-22E) was 84% by mass.

< Method for producing a compound > ( Compounds (C-1E) and (C-2E))

Use and for Prepare the same method as described in the compounds (C-1A) and (C-2A) separately Compounds (C-1E) and (C-2E).

<Method for Producing Pigment Dispersion> (Preparation of blue pigment dispersion (DP-1E))

After the following mixture was stirred uniformly, zirconia beads having a diameter of 0.5 mm were used, and Eigermil ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.) was used for dispersion treatment for 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to obtain a pigment dispersion (DP-1E).

Blue fine pigment 1E (C.I. Pigment Blue 15:6): 11.0 parts

Acrylic resin solution 1E: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.): 1.0 part

(Preparation of blue pigment dispersions (DP-2E) and (DP-3E))

Pigment dispersions (DP-2E) and (DP-3E) were prepared in the same manner as in the above pigment dispersion (DP-1E) except that the pigment was changed as shown in Table 26.

<Method for Producing Resin Solution Containing Salt-Forming Product> (Preparation of resin solution (DA-1E) containing salt-forming product)

The mixture was stirred well, and then filtered through a 5.0 μm filter to obtain a resin solution (DA-1E) containing a salt-forming product.

Salt-forming product (A-1E): 11.0 parts

Acrylic resin solution 1E: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Resin solution containing salt-forming products (DA-2E) to (DA-11E) and containing Preparation of resin solutions (DC-1E) and (DC-2E)

The salt-forming product (A-1E) was changed to the salt-forming product (A) as shown in Table 27 or In addition to the above-mentioned resin solution (DA-1E) containing a salt-forming product, a resin solution (DA-2E) to (DA-11E) containing a salt-forming product and containing the same are prepared. A resin solution (DC-1E) and (DC-2E) of the compound. The content of the pigment component is shown in Table 27. In addition, the pigment content A represents a salt forming product (A) or The content (% by mass) of the effective pigment component in the compound. Further, the dye content B represents the content (% by mass) of the effective dye component in the resin solution containing the colorant.

*1 Pigment component content A: salt-forming product (A) or Effective pigment component content of the compound (% by weight)

*2 Pigment content B: Effective pigment component content (% by weight) in the resin solution containing the colorant

[Example 1E] (resist material (R-1E))

A resist material prepared by the above method and a salt-forming product containing a tree solution or the like were prepared and evaluated. First, a method of preparing a resist agent will be described.

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (R-1E).

Resin solution containing salt-forming product (DA-1E): 21.0 parts

Pigment dispersion (DP-1E): 39.0 parts

Acrylic resin solution 1E: 11.0 parts

Trimethylolpropane triacrylate ("NK E STER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 2E to 25E and Comparative Examples 1E to 3E] (resist material (R-2E) to (R-28E))

The alkali-developing type resist was obtained in the same manner as the resist material (R-1E) except that the resin solution containing the colorant and the pigment dispersion and the blending amount thereof were changed as shown in Table 28. Reagents (R-2E) to (R-28E).

[Examples 26E to 31E] (resist material (R-29E) to (R-34E))

In the same manner as the resist material (R-5E), the alkali-developing resist material (R-29E) and (respectively, the acrylic resin solution 1E were changed to the acrylic resin solutions 2E, 3E, and 4E, respectively) R-30E) and (R-31E). In the same manner as the resist material (R-10E), the alkali-developing resist material (R-32E) was obtained, and the acrylic resin solution 1E was changed to the acrylic resin solutions 2E, 3E, and 4E, respectively. R-33E) and (R-34E).

(evaluation of resist material)

A coating film was formed from the resist materials (R-1E) to (R-34E), and the color reproducibility and the amount of foreign matter were examined for each of the coating films by the following methods.

(resist evaluation method)

The resist material was coated on a transparent substrate by a spin coater. The resist material was applied such that the transmittance of the colored layer to light having a wavelength of 570 nm was 3%. The coating film was dried at 80 ° C for 30 minutes using a hot air oven, and the film thickness and spectral transmittance of the coloring layer thus obtained were measured. The spectral transmittance was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). Next, the value T ₁ is obtained by accumulating the transmittance from 5 nm to 480 nm every 5 nm. Further, the spectral transmittance was measured in the same manner for the transparent substrate on which the colored layer was not formed, and the value T ₂ was obtained by accumulating the transmittance from 5 nm to 480 nm every 5 nm. Further, the color reproducibility is judged based on the ratio T ₁ /T _{2 of the} value T ₁ and the value T ₂ . The results are shown in Table 29.

In addition, the meaning of the mark in the column of "color reproducibility" in Table 29 is as follows.

○: T ₁ /T ₂ is 0.765 or more

×: T ₁ /T _{2 is} less than 0.765

(Test method for foreign matter in coating film)

With respect to the above-mentioned resist material, the ease of occurrence of coating unevenness due to foreign matter was evaluated. Specifically, first, a resist material was applied onto a transparent substrate to have a dry film thickness of about 2.5 μm, and the coating film was entirely exposed to ultraviolet light. Thereafter, it was heated in an oven at 230 ° C for 20 minutes, and then allowed to cool to obtain an evaluation substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is obtained. The results are shown in Table 29.

In addition, in Table 29, the meaning of the mark in the "coating foreign matter" column is as follows.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

When the total number of particles is less than 20, coating unevenness due to foreign matter hardly occurs. In addition, when the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. In addition, when the total number of particles is 100 or more, coating unevenness due to foreign matter may occur.

The resist materials (R-1E) to (R-25E) and (R-29E) to (R-34E) used in Examples 1E to 31E contained a blue pigment and a salt-forming product (A). On the other hand, the resist material (R-26E) of Comparative Example 1E contains copper indigo pigment and two It is a pigment. If these are compared, the coloring layer obtained from the resist materials (R-1E) to (R-25E) and (R-29E) to (R-34E) is compared with the resist material (R-26E). The obtained coloring layer showed better transmittance characteristics and was excellent in color reproducibility. Further, from the results of Examples 26E to 31E, it was found that the coating film foreign matter was reduced by using the active energy ray-curable resin having a vinyl bond.

The coloring layer obtained from the resist materials (R-27E) and (R-28E), although exhibiting good transmittance characteristics, produces many foreign matters.

○ sixth aspect

The sixth aspect is a color filter for an organic EL display which is preferably used in a color display using a white light-emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as "organic electroluminescence element"), and A color display including the color filter and the organic electroluminescence element. In addition, "white" contains pseudo-white.

A color display using a color filter may, for example, be (i) a backlight including a light source, a liquid crystal layer as a light valve, and a color adjustment function (color conversion function, color separation function, color correction function, etc.). A liquid crystal display in which a combination of color filters is used, or a white light source including one or more organic electroluminescence elements, and a color adjustment function (color conversion function, color separation function, color correction function, etc.) A combined organic EL display of color filters.

Liquid crystal displays are generally referred to as low power consumption. However, in the liquid crystal display, the backlight unit continues to emit light similarly to the white display even when it is displayed in black. That is, the liquid crystal display wastes energy.

The organic EL display is provided with a light source for each pixel, and can control the on/off of each light source by means of a TFT (Thin Film Transistor) or the like. Therefore, the organic EL display can perform black display by stopping the supply of current to the light source. Further, in the organic EL display, the liquid crystal layer and the polarizing plate are not required, and energy loss due to light absorption by the polarizing plate is not caused. Therefore, the organic EL display is advantageous in terms of power consumption. Further, in the organic EL display, since the black display is performed by stopping the supply of current to the light source, darker black can be displayed than the liquid crystal display. Therefore, the organic EL display is also advantageous in terms of the contrast ratio.

In addition, an organic EL display is disclosed in, for example, Japanese Laid-Open Patent Publication No. 2005-100921, and an organic EL display capable of displaying color images is available.

Further, an organic EL display capable of displaying a color image generally has a structure in which an organic electroluminescence device that emits red light, an organic electroluminescence device that emits green light, and an organic electroluminescence device that emits blue light are disposed. In the production of such an organic EL display, it is necessary to form a pattern of a light-emitting layer of an organic electroluminescence element that emits red light, a pattern of a light-emitting layer of a green-emitting organic electroluminescence element, and a pattern of vapor deposition using a mask. A pattern of a light-emitting layer of an organic electroluminescent element that emits blue light. Therefore, such an organic EL display has complicated construction and manufacturing steps, and requires high-precision mask alignment for manufacturing. Therefore, the above-described organic EL display is difficult to manufacture at low cost, high definition, and large screen. In order to solve such problems, it has been proposed that a white light-emitting layer to be described later is used for the light-emitting layer, and the white light-emitting layer and the color filter are combined (refer to Japanese Patent Laid-Open No. 2004-47469, JP-A-2008-518400, and JP-A-07 -220871).

Color reproducibility is valued in displays that can display color images. For example, the color reproducibility of a color liquid crystal display is determined by the color of light emitted from the red, green, and blue filter segments, and is evaluated in the following manner. That is, the chromaticity coordinates (xR, yR), (xG, yG), and (xB, yB) of the red, green, and blue filter segments are plotted on the x, y chromaticity diagram, and the The area of the triangle surrounded by 3 points. In addition, the chromaticity coordinates (0.67, 0.33), (0.21, 0.71), and (0.14, 0.08) of the three primary colors according to the standard method prescribed by the National Television System Committee (NTSC) of the United States are plotted on the x, y chromaticity diagram. Take the area of the triangle surrounded by these 3 points. The color reproducibility is evaluated based on the ratio of the area of the former to the area of the latter (unit is %. Hereinafter referred to as NTSC ratio). In addition, the value is generally 40 to 100% in the case of a notebook computer, 50 to 100% in the case of a monitor of a desktop computer, and 70 to 100 in the case of an LCD TV. % is ideal.

The backlight of the liquid crystal display, for example, a backlight including a cold cathode tube as a light source, and a backlight including a light-emitting diode or an organic electroluminescence element made of an inorganic material as a light source, for example, a two-wavelength luminescence spectrum having two peaks A shape-like white backlight or a 3-wavelength backlight with three peaks in the luminescence spectrum. The backlight including the light source other than the organic electroluminescence element is based on the display performance of the liquid crystal display, specifically, the color reproducibility achievable with the color filter, and the durability of the backlight. Design the glow spectrum.

An organic electroluminescence device used as a white light source in an organic EL display or a backlight includes, for example, a two-wavelength light source having two peaks in an emission spectrum, a three-wavelength light source having three peaks in an emission spectrum, or an emission spectrum. A light source with multiple peaks. A white light source comprising a white light-emitting layer composed of a mixture of a plurality of organic EL materials emitting different color lights, or a laminate comprising a plurality of light-emitting layers emitting different color lights as a white light-emitting layer.

An organic electroluminescence device which is a white light source has a different light emission spectrum from a light-emitting diode composed of a cold cathode tube and an inorganic material used as a white light source. For example, a light-emitting diode composed of a cold cathode tube or an inorganic material which is a white light source has a peak at 420 to 430 nm or in the vicinity thereof. On the other hand, the luminescence spectrum of the organic electroluminescence device which is a white light source generally has no peak at or near 420 to 430 nm due to material properties, and has a peak at about 460 nm. Further, the luminescence spectrum of the organic electroluminescence device which is a white light source is wider than the luminescence spectrum of the luminescent diode formed of a cold cathode tube or an inorganic material which is a white light source. Specifically, the former has a higher luminous intensity in a wavelength range of about 460 nm to about 500 _n m than the latter. For these reasons, a display including an organic electroluminescence element as a white light source cannot directly use the color filter currently used. Therefore, it is necessary to select and develop a color filter material which exhibits an optimum hue and transmittance characteristics when combined with an organic electroluminescence element which is a white light source.

In order to increase the NTSC ratio in, for example, an organic EL display including an organic electroluminescence device as a white light source and a color filter, it is necessary to increase the color purity of each filter segment. However, if the color purity is increased, the utilization efficiency of the light emitted by the light source (corresponding to the brightness Y) is reduced, so that the power consumption is increased.

For example, mobile devices mainly use battery-driven products and pay attention to power consumption, so the NTSC ratio of color liquid crystal displays loaded with such products is as low as 30 to 50%. However, recently, as the number of opportunities for viewing photos or animations using mobile devices has increased, the demand for an NTSC ratio increase for displays of mobile devices has also increased. Therefore, in the above organic EL display, it is preferable that the color purity and the brightness Y of each of the filter segments are high.

Conventionally, the blue filter segment of an organic EL display is generally formed of a coloring composition containing an indigo pigment excellent in resistance and color tone. The indigo pigment is known to have various central metals such as copper, zinc, nickel, cobalt, and aluminum. Among them, copper phthalocyanine is widely used because it can display vivid colors, and compounds other than copper phthalocyanine, such as metal-free indigo, zinc indigo, and cobalt indigo have also been put into practical use. The indigo pigment has various crystal forms such as α-type, β-type, δ-type, and ε-type, and is suitable as a color filter for color filters because it has excellent properties such as excellent chroma and coloring power. In conventional color filters, by using such copper indigo pigments It is a combination of pigment CI Pigment Violet 23 and the like, and a wide range of color display areas can be achieved.

Further, a coloring agent using a pigment and a dye in combination is also used in the color filter. For example, it has been proposed to use a copper indigo pigment, an oil-soluble dye, a disperse dye or a basic dye as a blue filter segment. (For example, refer to Japanese Patent Laid-Open No. Hei 11-242109 and JP-A No. 2001-124915).

Furthermore, it has also been proposed to use in color filters. It is known that the dye is used together with acid rose red (CI acid red 52), a polyimide resin or a photosensitive acrylic resin, and a color filter excellent in heat resistance can be obtained (for example, see Japanese Patent Laid-Open No. Hei 6-59114 Bulletin).

However, even if these techniques are applied to the above-described organic EL display, it is difficult to achieve sufficiently high color purity and brightness.

The color filter of the sixth aspect has a green filter segment, a red filter segment, and a blue filter segment. The blue filter segment is formed of a blue colored composition containing a binder resin and a coloring agent. The colorant contains a blue pigment and a salt forming product. Salt-forming product It is formed by an acid dye and a compound having a cationic group.

The blue filter section of the color filter of the sixth aspect can have high brightness and a wide color reproduction area. Further, since the dye is in the form of a salt-forming product, the blue filter segment of the color filter of the present aspect can have excellent performance against heat resistance, light resistance, and solvent resistance.

Further, by combining the blue filter segment with the red and green filter segments each containing a specific pigment, a color filter capable of achieving high whiteness (Y) and NTSC ratio can be obtained. Therefore, by combining the light-emitting devices included in the color filter as a light source of the white light-emitting organic electroluminescence device, a color display having a high whiteness (Y) and a high NTSC ratio can be obtained.

When the content of the blue pigment is 100 parts by mass, when the amount of the effective dye component in the salt-forming product is in the range of 5 to 150 parts by mass, particularly excellent performance can be achieved.

<<Blue coloring composition>>

The blue coloring composition used in this aspect comprises: a compound (a) having a cationic group and It is a salt-forming product (A) obtained by reacting an acid dye; a blue pigment; and a binder resin. The blue coloring composition may be contained in an organic solvent, a dispersing aid, a photopolymerizable compound, a photopolymerization initiator, and other additives as described later, if necessary.

In this aspect, the colorant is composed of a pigment component and a salt-forming product (A).

<salt formation product (A)>

a salt-forming product (A) which is a compound having a cationic group (a) A salt-forming product obtained by reacting an acid dye.

(Compound (a) having a cationic group)

The compound having a cationic group is not particularly limited as long as it is a compound having at least one onium salt group. The compound having a phosphonium salt group is preferably an ammonium salt compound, a phosphonium salt compound, a phosphonium salt compound, a diazonium salt compound or a phosphonium salt compound.

Among the preferred compounds having a cationic group, the resin (a1) having a cationic group in a side chain or the quaternary ammonium compound (a2) represented by the following formula (24).

[In the formula (24), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion. ]

The preferred form of the compound (a) having a cationic group is colorless or white. The term "colorless or white" as used herein means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. That is, the compound (a) having a cationic group is preferably one which does not inhibit the color development of the dye component and does not cause a color change.

[Resin (a1) having a cationic group in a side chain]

In the resin (a1) having a cationic group in the side chain, the resin (a1) having a cationic group in the side chain in the fourth aspect can be similarly used.

[Quaternary ammonium compound (a2) represented by the general formula (24)]

The quaternary ammonium compound (a2) represented by the formula (24) can be similarly used in the quaternary ammonium compound of the first aspect.

[In the formula (24), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y- represents an inorganic or organic anion. ]

Wherein the quaternary ammonium compound (a2) represented by the formula (24), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least 2 of the carbon atoms are 5 to 20 Preferably.

( Acid dye)

For obtaining a salt-forming product (A) Acid dye, the same can be used in the first aspect. It is an acid dye.

(salt treatment) [Resin (a1) having a cationic group in a side chain and Salt formation of acid dyes]

a resin (a1) having a cationic group in a side chain and The salt-forming product of the acid dye can be obtained by the same method as described in the column of "(salt formation)" in the fourth aspect. a resin (a1) having a cationic group in a side chain and The ratio of the acid dye is preferably the same as that described in the fifth aspect.

[Quaternary ammonium compound (a2) and Salt formation of acid dyes]

The salt-forming product of the acid dye and the quaternary ammonium compound (a2) can be obtained by the same method as that described in the first aspect.

(content of effective pigment component contained in salt-forming product (A))

From the salt-forming product (A) The content of the effective dye component of the acid dye is the same as that of the fourth aspect.

<blue pigment>

As the blue pigment constituting the coloring agent, an indigo pigment can be used in the same manner as in the first aspect. The indigo pigment is preferably a copper phthalocyanine pigment.

Among these, the blue pigment is preferably C.I. Pigment Blue 15:6.

(fineness of pigment)

The blue pigment used in the color filter of this aspect and the other pigments used arbitrarily can be subjected to salt milling treatment in the same manner as in the first aspect to be fine. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of dispersibility in the colorant carrier. Further, from the viewpoint of forming a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferred range is 25 to 85 nm.

Further, the primary particle diameter of the pigment was determined from an electron microscope photograph of a TEM (transmissive electron microscope) of the pigment. Specifically, first, the pigment particles were sampled on a grid to prepare a sample for TEM observation. Next, the sample was observed by TEM, and the short axis diameter and the major axis diameter of the primary particles were measured for 100 or more pigment particles. And the average of these is regarded as the primary particle diameter of the pigment particle.

The salt-forming product (A) is preferably used in an amount of from 1 to 800 parts by mass, more preferably from 5 to 400 parts by mass, per 100 parts by mass of the blue pigment. When the amount of the salt-forming product (A) to be added is less than 1 part by mass, the reproducible chromaticity region is narrowed. Further, if the amount added exceeds 800 parts by mass, the hue changes.

When the color constitution is considered, the content of the effective dye component in the salt-forming product (A) is preferably in the range of 1 to 400 parts by mass based on 100 parts by mass of the blue pigment. The mass of the effective dye component in the salt-forming product (A) is more preferably in the range of 5 to 150 parts by mass based on 100 parts by mass of the blue pigment.

In particular, use CI Acid Red 289 or CI Acid Red 52 as The salt-forming product (A) which is an acid dye is excellent in solvent solubility, and when used together with a blue pigment, it is excellent in heat resistance, light resistance, and solvent resistance. Further, the reason why the salt-forming product (A) and the blue pigment are used in combination can achieve good performance in that the salt-forming product (A) is adsorbed to the blue pigment in a state of being dissolved or dispersed in a solvent.

<Other coloring agents>

In the blue coloring composition of the present aspect, in addition to the components of the coloring agent, other organic pigments may be added for the purpose of coloring as long as the effect is not impaired, similarly to the first aspect.

<Binder resin>

The binder resin is used to disperse the colorant, especially the salt-forming product, or to dye or impregnate the salt-forming product. The binder resin may, for example, be a thermoplastic resin or a thermosetting resin, and the "resin" in the first aspect may be used in the same manner.

<organic solvent>

In the same manner as in the first aspect, the blue coloring composition of the present aspect is applied to a substrate such as a glass substrate in order to sufficiently disperse or dissolve the coloring agent in the colorant carrier to have a dry film thickness of 0.2 to 5 μm to form a filter. The sheet segments are easy to carry and may contain a solvent.

As the organic solvent, the solvent of the first or fifth aspect can be used similarly.

<scatter>

In the color filter of this aspect, a resin containing a blue pigment and having a cationic group in a side chain can be used. The coloring agent of the salt-forming product (A) obtained by the reaction of the acid dye is preferably used together with a dispersing aid such as a pigment derivative in a coloring agent carrier composed of a binder resin and an organic solvent to be used as needed. A colored composition produced by treatment of various dispersing tools such as a roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. Further, in the color filter of the present aspect, a coloring composition obtained by dispersing a blue pigment, a salt-forming product (A), and other coloring agents, respectively, in a colorant carrier, and mixing the same may be used. .

(dispersion aid)

When the coloring agent is dispersed in the coloring agent carrier, a dispersing aid such as a dye derivative, a resin type dispersing agent, or a surfactant can be suitably used in the same manner as in the fourth aspect.

As the dye derivative, the pigment derivative of the fourth aspect can be used in the same manner.

The pigment derivative is preferably a basic compound using copper indigo which has a basic substituent introduced into the indigo pigment. The basic compound of copper phthalocyanine is preferably a copper indigo amine compound such as a copper sulfonium sulfonate ammonium salt compound, a copper phthalocyanine tertiary amine or a copper phthalocyanine sulfonamide compound.

A blue filter segment having a high brightness and a high contrast ratio can be realized by using a copper phthalocyanine basic compound, particularly a copper phthalocyanine compound. The reason is that the basic compound of copper phthalocyanine inhibits the dispersibility of the blue pigment while suppressing Fluorescence is produced by acid dyes. Especially, have It is of great significance that the salt-forming product (A) of the acid dye and the basic compound of copper indigo coexist in the blue coloring composition.

The basic compound of the copper phthalocyanine may be used singly or in combination of two or more. The basic compound of the copper phthalocyanine is preferably used in an amount of from 0.01 to 200 parts by mass, more preferably from 1 to 100 parts by mass, per 100 parts by mass of the total amount of the blue pigment.

Further, the ratio of the mass of the basic compound of the copper phthalocyanine to the mass of the salt-forming product (A) (the basic compound of the copper phthalocyanine / the salt-forming product (A)) is preferably from 0.3 to 1.5. In this case, the fluorescence generated by the salt-forming product (A) can be suppressed while the dispersion of the blue pigment is increased, and as a result, a blue coloring composition capable of realizing a color filter of high definition and high contrast ratio can be obtained. .

When the amount is less than 0.3, the suppression of fluorescence and the dispersibility of the copper indigo amine compound are insufficient, so that the contrast is low, and if it exceeds 1.5, the color characteristics are affected, and the brightness may be lowered. A better mass ratio is from 0.4 to 1.2, and an optimum mass ratio is from 0.5 to 1.1.

As the resin type dispersant, the resin type dispersant of the first aspect can be used in the same manner.

As the surfactant, the surfactant of the first aspect can be used in the same manner.

When the amount of the resin-type dispersant and/or the surfactant is added, the amount is preferably from 0.1 to 55 parts by mass, more preferably from 0.1 to 45 parts by mass, based on 100 parts by mass of the total amount of the colorant. . When the blending amount is less than 0.1 part by mass, it is difficult to obtain the effect of the resin type dispersant and/or the surfactant. If the blending amount is more than 55 parts by mass, the dispersion may be affected by the excessive dispersant.

<Photopolymerizable compound>

The blue coloring composition used for the production of the color filter of the present aspect may further contain a photopolymerizable compound and/or a photopolymerization initiator, and may be used as a color filter for a photosensitive blue coloring composition. . As the photopolymerizable compound, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

In the present aspect, the photopolymerization initiator of the first aspect can be used similarly.

<sensitizer>

The blue coloring composition used for the production of the color filter of the present aspect may further contain a sensitizer in the same manner as in the first aspect.

<leveling agent>

In the blue colored composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent in the same manner as in the first aspect.

<hardener, hardening accelerator>

In the blue colored composition used in the aspect, in order to assist the hardening of the thermosetting resin, a curing agent, a curing accelerator, or the like may be contained in the same manner as in the first aspect.

<Other additive ingredients>

In the blue coloring composition used in this aspect, in order to keep the viscosity of the composition long, the storage stabilizer can be contained in the same manner as in the first aspect. Further, in order to improve the adhesion to the transparent substrate, an adhesion enhancer such as a decane coupling agent may be contained in the same manner as in the first aspect.

<antioxidant>

In the colored composition used in this aspect, in order to increase the transmittance of the coating film, it is preferable to contain an antioxidant similarly to the first aspect.

<Removal of large particles>

From the blue coloring composition used for the production of the color filter of the present aspect, large particles of 5 μm or more, preferably large particles of 1 μm or more, are preferably removed by a method such as centrifugal separation, sintering filtration, or membrane filtration, and more preferably Large particles of 0.5 μm or more and dust mixed therein are preferred.

<<Color filter>>

The color filter of this aspect contains, for example, a plurality of filter segments which are different in absorption spectrum and are typically regularly arranged. A color filter of the form comprising: at least one red filter segment; at least one green filter segment; and at least one blue filter segment. In the color filter of this aspect, for example, the blue filter segment is formed of the coloring composition for the color filter described above.

The red filter segment can be formed using a general red coloring composition containing a red pigment and a pigment carrier, similarly to the first aspect. Further, in the red colored composition, an orange pigment and/or a yellow pigment may be used in combination in the same manner as in the first aspect.

From the viewpoint of achieving high brightness and a wide color display area, if the penetration spectrum of the red filter segment is matched with the luminescence spectrum of the white organic electroluminescent element, the red filter segment is selected It is preferred that at least one red pigment is selected from the group consisting of CI Pigment Red 177 and CI Pigment Red 179. Among the preferred reasons for using these pigments in the red filter segment, it is considered that the high coloring power of the pigments is effective for exhibiting a wide range of color display regions.

The green filter segment can be formed using a general green coloring composition containing a green pigment and a pigment carrier in the same manner as in the first aspect. Further, in the green coloring composition, a yellow pigment may be used in combination in the same manner as in the first aspect.

From the viewpoint of realizing high brightness and a wide color display area, if the matching between the breakthrough spectrum of the green filter segment and the emission spectrum of the white organic electroluminescent element is considered, the green filter segment is included At least one green pigment selected from the group consisting of CI Pigment Green 7 and CI Pigment Green 36 and at least one yellow selected from the group consisting of CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185 The pigment is preferred. In the green filter segment, the reason why the combination of the pigments is preferable is that the high coloring power of the pigments is effective for exhibiting a wide color display region.

As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminum boron borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. A transparent electrode made of indium oxide or tin oxide can be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the panelization.

<Method of Manufacturing Color Filter>

The color filter of this aspect can be produced, for example, by a printing method, a photolithography method, an electrodeposition method, a transfer method, or an inkjet method. Any of the methods can be utilized for the coloring composition used in this aspect.

By the printing method, the patterned filter segments can be formed by printing and drying only the coloring composition prepared as a printing ink repeatedly. Therefore, the printing method is low in cost and excellent in mass productivity. Moreover, due to the development of printing technology, it is possible to form a fine pattern having high dimensional accuracy and smoothness by printing.

The ink used for printing preferably has a composition that does not dry and cure on the printed plate or blanket. Further, in the printing method, it is also important to control the fluidity of the ink on the printing press. The fluidity of the ink can be controlled by adjusting the viscosity of the ink by using a dispersant or an extender pigment.

According to photolithography, a color filter can be manufactured with higher precision than a printing method.

When a filter segment is formed by photolithography, a coloring composition which is a solvent developing type or an alkali developing type coloring resist is prepared, and is applied by a coating method such as spray coating, spin coating, slit coating, or roll coating. On the transparent substrate, the dry film thickness is made into a range of, for example, 0.2 to 5 μm. The coating film is dried as needed, and the coating film is exposed to ultraviolet rays by a mask having a predetermined pattern which is provided in contact or non-contact with the coating film. Thereafter, the coating film is immersed in a solvent or an alkali developing solution or a coating film spray solvent or an alkali developing solution to remove the uncured portion from the coating film. Thereby, a film pattern corresponding to a filter segment of a certain color can be obtained. The coloring composition for the color filter segments of the other colors was used, and the same operation as described above was repeated to form a film pattern corresponding to the remaining filter segments. Thereafter, the film patterns are fired as needed, thereby obtaining a color filter. Further, firing may be performed each time a film pattern is formed.

At the time of development, an alkali solution such as sodium carbonate or sodium hydroxide is used as the alkali developer. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.

Further, in order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied onto the colored resist film obtained by applying and drying the colored resist. The coating film was dried, followed by ultraviolet exposure. A coating film composed of a water-soluble or alkali-soluble resin prevents polymerization in the colored resist film from being hindered by oxygen.

In the manufacture of a color filter using an electrodeposition method, a substrate having a transparent conductive film on one of the main faces is prepared, and the transparent conductive film is used as an electrode to cause colloidal particles to be electrophoresed on the transparent conductive film. A filter segment is formed.

Further, in the manufacture of a color filter using a transfer method, a filter segment is formed in advance on a main surface of a transfer substrate in which one of the main faces has a release property, and the filter is formed. The light sheet section is transferred from the transfer substrate to the substrate.

On the transparent substrate, a black matrix that is a light-shielding pattern may be formed before the filter segments are formed. For the black matrix, for example, a metal film such as a chromium film, a multilayer film such as a chromium/chromium oxide film, an inorganic compound film such as a titanium nitride film, or a resin film obtained by dispersing a light shielding material in a resin can be used.

In the transparent substrate, before forming the color filter, a circuit such as an active matrix circuit including a thin film transistor (TFT) may be formed. Further, other layers such as an overcoat film and a transparent conductive film may be formed on the color filter as needed. By forming the filter segments on the TFT substrate, the aperture ratio of the display panel can be increased and the luminance can be improved.

<<Color display>>

In this aspect, the color display comprises: a color filter having a compound (a) containing a cationic group; a blue filter segment formed by a salt-forming product (A) obtained by reacting an acid dye and a blue pigment, and a blue coloring composition of the binder resin; and a white light-emitting organic light as a light source A light-emitting element (hereinafter referred to as an organic electroluminescence element).

(Organic Electroluminescent Element (White Light Emitting Organic Electroluminescent Element))

The organic electroluminescence device which can be used in this aspect has an emission spectrum having two or more maximum values in a wavelength range of 400 nm to 700 nm, and has a luminous intensity in a wavelength range of 430 nm to 485 nm and a wavelength range of 580 nm to 620 nm. The maximum peak wavelengths λ1 and λ2, the ratio I2/I1 between the luminous intensity I2 of the wavelength λ2 and the luminous intensity I1 of the wavelength λ1, is preferably 0.4 to 0.9, more preferably 0.5 to 0.8, and particularly preferably 0.5 to 0.7.

The luminescence spectrum of the organic electroluminescence device is preferably a maximum value or a shoulder portion having a luminescence intensity in a wavelength range of 530 nm to 650 nm.

The peak wavelength λ1 is in the wavelength range of 430 nm to 485 nm, and it is advantageous for the color display including the color filter to exhibit blue color with high color reproducibility. The peak wavelength λ1 is more preferably in the range of 430 nm to 475 nm.

By using the organic electroluminescence element having the above configuration and the color filter described above, a color display having a wide color reproduction area, high definition, and high contrast ratio can be obtained.

The organic electroluminescence device is composed of an element in which one or more organic layers are formed between an anode and a cathode. Here, the one-layer type organic electroluminescence element means an element having only a light-emitting layer between the anode and the cathode. On the other hand, the multilayer organic electroluminescence device means that, in addition to the light-emitting layer, in order to facilitate the injection of holes or electrons into the light-emitting layer or to recombine the holes and electrons in the light-emitting layer, the laminate can be smoothly performed. Hole injection layer, hole transport layer, hole stop layer, electron injection layer, and the like. Representative element configurations of the multilayer organic electroluminescence device include (1) anode/hole injection layer/light-emitting layer/cathode, (2) anode/hole injection layer/hole transport layer/light-emitting layer/cathode (3) anode/hole injection layer/light-emitting layer/electron injection layer/cathode, (4) anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode, (5) anode/electric Hole injection layer/light-emitting layer/hole stop layer/electron injection layer/cathode, (6) anode/hole injection layer/hole transport layer/light-emitting layer/hole stop layer/electron injection layer/cathode, (7) Anode/light-emitting layer/hole stop layer/electron injection layer/cathode, and (8) anode/light-emitting layer/electron injection layer/cathode, and the like. However, the constitution of the organic electroluminescence element used in this aspect is not limited to these.

Further, each of the above organic layers may have a laminated structure of two or more layers. In this case, a plurality of layers can be repeatedly laminated. In such an example, in recent years, in order to improve the light extraction efficiency, a layer of a plurality of layers of the multilayer organic electroluminescence device is referred to as a "multi‧photon‧emission" element. An example of such a component structure is an organic electroluminescence device comprising a glass substrate/anode/hole transport layer/electron transport light-emitting layer/electron injection layer/charge generation layer/light-emitting unit/cathode. A structure in which a plurality of layers of the charge generating layer and the light emitting unit are laminated.

The materials that can be used for the layers are specifically exemplified below. However, the materials that can be used in this aspect are not limited to these.

The material which can be used for the hole injection layer is preferably a phthalocyanine compound. Examples of the indigo compound include copper indigo (CuPc) and vanadyl indigo (VOPc). Further, a material which is chemically doped with a conductive polymer compound can be used, and examples of such a material include a material doped with polystyrenesulfonic acid (PSS) in polyethylene diaminothiophene (PEDOT). Also, polyaniline (PANI) can also be used. Further, the hole injection layer may also be used molybdenum oxide (MoO _x), vanadium oxide film (VO _x) and nickel oxide (NiO _x) and inorganic semiconductors composed of, or aluminum oxide (Al ₂ O ₃₎ of an inorganic insulator Ultra-thin film. Also, 4,4',4"-para (N,N-diphenyl-amino)-triphenylamine (TDATA), 4,4',4"-para [N-(3-methyl) can also be used. Phenyl)-N-phenyl-amino]-triphenylamine (MTDATA), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl -4,4'-diamine (TPD), 4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]-biphenyl (α-NTPD) and 4,4'- An aromatic amine compound such as bis[N-(4-(N,N-di-m-tolyl)amino)phenyl-N-anilino]biphenyl (DNTPD). Among the aromatic amine-based compounds, a substance exhibiting an acceptor property may be added. For example, it can also be used for the addition of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) to VOPc as acceptor, or to add to α-NPD. Sub MoO _X.

The material of the hole transport layer is preferably an aromatic amine compound, and examples thereof include TDATA, MTDATA, TPD, α-NPD, and DNTPD described in the hole injection material.

The material of the electron transport layer, such as ginseng (8-hydroxyquinoline) aluminum (Alq3), ginseng (4-methyl-8-hydroxyquinoline) aluminum (Almq ₃ ), bis(10-hydroxybenzo[h]- Quinoline)BeBq ₂ , bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum (BAlq), bis[2-(2-hydroxyphenyl)benzo A metal complex such as azole]zinc (Zn(BOX) ₂ ) or bis[2-(2-hydroxyphenyl)benzothiazole]zinc (Zn(BTZ) ₂ ). Also, 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4- can also be used. Diazole (PBD) and 1,3-bis[5-(p-tert-butylphenyl)-1,3,4- Diazol-2-yl]benzene (OXD-7), etc. Diazole derivatives, 3-(4-t-butylphenyl)-4-phenyl-5-(4-biphenyl)-1,2,4-triazole (TAZ) and 3-(4- a triazole derivative such as a third butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenyl)-1,2,4-triazole (p-EtTA吖Z), An imidazole derivative such as 2,2',2"-(1,3,5-benzenetriyl) gin[1-phenyl-1H-benzimidazole] (TPBI), or to Bonothhenanthroline (BPhen) And phenanthroline derivatives such as Bathocuproine (BCP).

As the material of the electron injecting layer, for example, Alq ₃ , Almq ₃ , BeBq ₂ , BAlq, Zn(BOX) ₂ , Zn(BTZ) ₂ , PBD, OXD-7, TAZ, p-EtTAZ, TPBI, BPhen, and BCP can be used. Electron transport materials. As the electron injecting layer, an ultra thin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF ₂ , or an ultrathin film composed of an alkali metal oxide such as Li ₂ O may be used. Further, an alkali metal complex such as lithium acetylacetate (Li(acac)) or lithium quinolate (Liq) may also be used. A substance exhibiting donor properties may be added to the electron injecting materials, and for example, an alkali metal, an alkaline earth metal or a rare earth metal may be used as the donor. For example, a person who adds a lithium donor to BCP or a donor lithium to Alq ₃ can be used.

As the material of the hole blocking layer, a material excellent in film formability and capable of preventing the holes passing through the light-emitting layer from reaching the electron injecting layer can be used. Such a material may, for example, be an aluminum complex compound such as bis(8-hydroxyquinoline)(4-phenylphenol)aluminum or bis(2-methyl-8-hydroxyquinoline) (4-phenylphenol). a gallium complex compound such as gallium, and a nitrogen-containing condensed aromatic compound such as 2,9-dimethyl-4,7-diphenyl-1,10-morpholine (BCP).

The light-emitting layer that emits white light is not particularly limited, and for example, the following may be used. In other words, a white light-emitting organic electroluminescence device in which the energy levels of the respective layers are optimized and the light is injected by the channel can be used, as described in the European Patent No. 0390551, and the like, and the element injected through the channel is also used. A white light-emitting organic electroluminescence device of the embodiment of the Japanese Patent Publication No. Hei. No. 3-230584, which is described in Japanese Laid-Open Patent Publication No. Hei No. 2-220390 A white light-emitting organic electroluminescence device, wherein the light-emitting layer is divided into a plurality of portions, and the white light-emitting organic electroluminescence device is made of a material having a different light-emitting wavelength, as described in Japanese Laid-Open Patent Publication No. Hei 4-51491; JP-A-6-207170 discloses a white light-emitting organic electroluminescence device in which a blue light-emitting layer (fluorescent peak portion 380 to 480 nm) and a green light-emitting layer (480 to 580 nm) are laminated, and a red phosphor is further contained; A laminate comprising a blue light-emitting layer and a green light-emitting layer, and a blue light-emitting layer made of a blue light-emitting material, is arbitrarily described in Japanese Patent Application Laid-Open No. Hei. Heteroaryl blue fluorescent dye, and a green light emitting layer is comprised of the green light emitting material doped with a red fluorescent dye portion, any additional portion of the green fluorescent dye doped white light emitting organic electroluminescent layer of the light emitting element.

As the luminescent material, a material which has been conventionally known as a luminescent material can be used. Preferred compounds for emitting blue, green, and orange or red light are exemplified below. In addition, the luminescent material is not limited to the following specific examples.

Blue light, can be used, for example , 2,5,8,11-tetra-t-butyl (TBP), and 9,10-diphenylfluorene derivatives are obtained as guest materials. Further, blue luminescence may be a styryl aryl derivative such as 4,4'-bis(2,2-diphenylvinyl)biphenyl (DPVBi) or 9,10-di-2-naphthyl fluorene ( DNA) and an anthracene derivative such as 9,10-bis(2-naphthyl)-2-tert-butylindole (t-BuDNA). Further, a polymer such as poly(9,9-dioctylfluorene) can also be used.

More specific examples are shown in Table 30.

For green luminescence, coumarin pigments such as coumarin 30 and coumarin 6 or bis(2-(2,4-difluorophenyl)pyridine]pyridinium ruthenate (FIrpic) and bis(2-) can be used. Phenylpyridine)Ethylpyridinium oxime (Ir(ppy)(acac)) or the like is obtained as a guest material. In addition, green luminescence can also be carried out by ginseng (8-hydroxyquinoline) aluminum (Alq3), BAlq, Zn (BTZ), and bis(2-methyl-8-hydroxyquinoline) chlorogallium (Ga(mq) ₂ Cl ) A metal complex is obtained. Further, a polymer such as poly(p-phenylene vinyl) can also be used.

More specific examples are shown in Table 31.

For orange or red luminescence, for example, rubrene, 4-(dicyanomethylidene)-2-[p-(dimethylamino)styryl]-6-methyl-4H-pyran (DCM1), 4-(dicyanomethylidene)-2-methyl-6-(9- Ethidyl)ethynyl-4H-pyran (DCM2), 4-(dicyanomethylidene)-2,6-bis[p-(dimethylamino)styryl]-4H-pyran (BisDCM , bis[2-(2-thienyl)pyridine]ethindolone oxime (Ir(thp) ₂ (acac)), and bis(2-phenylquinoline)acetamidacetone oxime (Ir(pq)) (acac)) is obtained as a guest material. The orange or red luminescence can also be obtained from a metal complex such as bis(8-hydroxyquinoline)zinc (Znq ₂ ) or bis[2-cinnadecyl-8-hydroxyquinoline]zinc (Znsq ₂ ). Further, a polymer such as poly(2,5-dialkylamino-1,4-phenylenevinyl) may also be used.

More specific examples are shown in Table 32.

As the material of the anode of the organic electroluminescence device, a metal having a large work function (4 eV or more), an alloy, a conductive compound or a mixture thereof is preferably used. Specific examples of such an electrode material include metals such as Au and conductive materials such as CuI, ITO, SNO ₂ and ZNO. The anode can be obtained by forming a thin film of the electrode material by a method such as a vapor deposition method or a sputtering method. When the light from the above-mentioned light-emitting layer is taken out from the anode, the anode preferably has a transmittance of light from the light-emitting layer of more than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω/cm ² or less. The thickness of the anodic film varies depending on the material, but is usually selected from the range of 10 nm to 1 μm, preferably from 10 to 200 nm.

As the material of the cathode of the organic electroluminescence device, a metal having a small work function (4 eV or less), an alloy, a conductive compound or a mixture thereof can be used. Specific examples of such an electrode material include sodium, a sodium-potassium alloy, magnesium, lithium, magnesium, a silver alloy, aluminum/aluminum oxide, aluminum/lithium alloy, indium, and a rare earth metal. The cathode can be obtained by forming a thin film made of the electrode materials by a method such as vapor deposition or sputtering. When the cathode is taken out of the light from the light-emitting layer by the cathode, the light transmittance for light is preferably greater than 10%. The sheet resistance of the cathode is preferably several hundred Ω/cm ² or less. The cathode film thickness is usually in the range of 10 nm to 1 μm, preferably in the range of 50 to 200 nm.

The organic electroluminescence device can be formed, for example, by using the above materials and methods to form an anode, a light-emitting layer, a hole injection layer as needed, and an electron injection layer as needed, and finally forming a cathode. Further, the organic electroluminescence device can also be fabricated by reversing the order of lamination.

The organic electroluminescence device is produced, for example, on a light-transmissive substrate. The light-transmitting substrate is a substrate supporting the organic electroluminescence element, and the transmittance in the entire region of the visible region of 400 to 700 nm is preferably 50% or more, more preferably 90% or more. Further, it is preferable to use a smooth substrate.

The light-transmitting substrate is not particularly limited as long as it has mechanical and thermal strength and is transparent. As the light-transmitting substrate, for example, a glass plate or a synthetic resin plate is preferably used. The glass plate may, for example, be a plate made of soda lime glass, glass containing ruthenium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz. Further, a synthetic resin sheet such as a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, or a plate made of a polyfluorene resin.

For each layer of the organic electroluminescence device, a wet film formation method such as vacuum deposition, electron beam irradiation, sputtering, plasma or ion plating, or a wet film formation method such as spin coating, dipping, flow coating, or ink jet method can be used. A method of vapor-depositing an illuminant on a donor film, and LITI (Laser Induced Thermal) described in JP-A-2002-534782 or ST Lee, et al., Proceedings of SID'02, p. 784 (2002) Imaging, laser thermal transfer) method, printing (lithographic, flexography, gravure, screen printing) method, or inkjet method.

The organic layer is particularly preferably a molecularly deposited film. Here, the molecular deposition film is a film formed by depositing a compound in a gas phase state, or a film formed by solidifying a compound in a solution state or a liquid phase state. In general, the molecular deposition film and the thin film (molecular accumulation film) formed by the LB method can be distinguished by a difference in an agglutination structure or a high-order structure, or a function difference due to a structure. In the case where a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and the film is formed by a spin coating method or the like, an organic layer can be formed as disclosed in JP-A-57-51781. The film thickness of each layer is not particularly limited. However, if the film thickness is too thick, in order to obtain a predetermined light output, it is necessary to apply a large voltage, and the efficiency is deteriorated. On the other hand, if the film thickness is too thin, pinholes are generated, and it is difficult to obtain an electric field even if an electric field is applied. Full radiance. Therefore, the film thickness of each layer is preferably in the range of 1 nm to 1 μm, and more preferably in the range of 10 nm to 0.2 μm.

Further, in order to improve the stability of the organic electroluminescence device with respect to temperature, humidity, and gas atmosphere, a protective layer may be provided on the surface of the device, or the entire device may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin which is cured by light can be suitably used.

The current applied to the organic electroluminescent element is usually direct current, but pulse current or alternating current can also be used. The current value and the voltage value are not particularly limited as long as they do not damage the element. However, in consideration of the power consumption and life of the element, it is preferable to efficiently emit light with as little electric energy as possible.

The driving method of the organic electroluminescence element is not only a passive matrix method but also an active matrix method. Further, the method of extracting light from the organic electroluminescence element may be a bottom emission in which light is taken out from the anode side, or a top emission in which light is taken out from the cathode side. These methods or techniques are described in the city of "The Whole of Organic EL" and the Japanese Industrial Publishing Company (issued in 2003).

In this aspect, a color filter can be used for color display, such as full color display. The color filter method is a method in which white light emitted from a white light-emitting organic electroluminescence device is incident on a color filter to extract light of three primary colors. In addition to the three primary colors, when a part of white light is taken out in the original state and used for light emission, the luminous efficiency of the entire element can be improved.

A microcavity structure can be employed in the organic electroluminescent element. The organic electroluminescent element has a structure in which the light-emitting layer is interposed between the anode and the cathode, and the light of the light can undergo multiple interference between the anode and the cathode. The optical characteristics of the anode and the cathode can be enhanced to interfere with light of a predetermined wavelength by appropriately selecting, for example, reflectance and transmittance, and the film thickness of the organic layer. Thereby, the chromaticity of the luminescence can also be improved. The mechanism of this multiple interference effect is described in J. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77 to 80 (2002).

An organic EL display including a color filter can be obtained by forming a color filter layer on, for example, a substrate, and disposing the above organic electroluminescence element thereon. In this display, if a predetermined circuit including a TFT is provided for each pixel, an extremely high contrast ratio can be realized.

[Example F]

The present invention will be described below based on the examples, but the present invention is not limited to these. In addition, in the examples, "parts" and "%" each mean "parts by mass" and "% by mass". Further, the weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The measurement of the weight average molecular weight (Mw) was carried out by using a TSKgel column (manufactured by Tosoh Corporation) using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector. The solvent was developed using THF.

First, an organic electroluminescence device, an acrylic resin solution, a fine pigment, a resin (a) having a cationic group in a side chain, a salt-forming product (A), and a salt-forming product (A), which are used in the examples and the comparative examples, will be described. a compound, a pigment dispersion, a resin solution containing a salt-forming product, and a The resin solution of the compound, the blue resist material, the red resist material, and the method for producing the green resist material, and the examples and comparative examples of the present invention are described in detail.

<Production Example of Organic Electroluminescence Element>

An example of the production of an organic electroluminescence device used as a white light source is shown below. In the production example of the organic electroluminescence device, the mixing ratio indicates the mass ratio unless otherwise specified. The vapor deposition (vacuum evaporation) was carried out in a vacuum of 10 ^-6 Torr without temperature control such as substrate heating and cooling. Further, the evaluation of the light-emitting characteristics of the device was carried out by measuring the characteristics of an organic electroluminescence device having an electrode area of 2 mm × 2 mm.

(Manufacture of Organic Electroluminescent Element (EL-1))

The washed ITO electrode-attached glass plate was treated with oxygen plasma for about 1 minute, and then 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl was vacuum-deposited thereon. α-NPD), a hole injection layer having a film thickness of 150 nm was obtained. On the hole injection layer, the compound (R-2) of Table 3 and the compound (R-3) were co-deposited at a composition ratio of 100:2 to form a first light-emitting layer having a film thickness of 10 nm. Next, the compound (B-1) of Table 1 and the compound (B-4) were co-deposited at a composition ratio of 100:3 on the first light-emitting layer to form a second light-emitting layer having a film thickness of 20 nm. Next, α-NPD was vacuum-deposited to a thickness of 5 nm on the second light-emitting layer, and the compound (G-3) of Table 2 was vacuum-deposited at a thickness of 20 nm to form a third light-emitting layer. In this manner, a light-emitting layer composed of the first to third light-emitting layers was obtained.

Next, ginseng (8-hydroxyquinoline) aluminum complex was vacuum-deposited on the light-emitting layer to prepare an electron injecting layer having a film thickness of 35 nm. Next, lithium fluoride was vacuum-deposited to a thickness of 1 nm on the electron injecting layer, and aluminum was vapor-deposited to a thickness of 200 nm to form an electrode. As described above, an organic electroluminescence device (EL-1) was obtained.

Further, in order to protect the organic electroluminescent element (EL-1) from the surrounding environment, it is hermetically sealed in a dry glove box filled with pure nitrogen. When a direct current voltage of 5 V was applied between the electrodes of 5 V, the organic electroluminescent element (EL-1) was caused to emit light, and white light emission having a luminance of 950 cd/m ² , a maximum luminance of 55,000 cd/m ^{2 ,} and a luminous efficiency of 3.91 m/W was obtained. Figure 2 shows the luminescence spectrum.

(Manufacture of organic electroluminescent element (EL-2))

Vacuum evaporation of 4,4'-bis[N-(1-naphthyl)-N-aniline through a glass plate with an ITO electrode treated in the same manner as in the manufacture of an organic electroluminescent element (EL-1) Biphenyl] (α-NPD) forms a hole injection layer having a film thickness of 50 nm. On the hole injection layer, the compound (R-2) of Table 3 and the compound (R-3) were co-deposited at a composition ratio of 100:0.5 to obtain a first light-emitting layer having a film thickness of 20 nm. Next, the compound (B-3) of Table 1 and the compound (B-4) were vapor-deposited at a composition ratio of 100:2 on the first light-emitting layer to form a second light-emitting layer having a film thickness of 40 nm. Next, a ruthenium (8-hydroxyquinoline) aluminum complex was vacuum-deposited on the second light-emitting layer to form a third light-emitting layer having a film thickness of 30 nm. In this manner, a light-emitting layer composed of the first to third light-emitting layers was obtained.

Next, on the light-emitting layer, α-NPD was vacuum-deposited to a thickness of 5 nm, and ginseng (8-hydroxyquinoline) aluminum complex was vacuum-deposited to prepare an electron injecting layer having a film thickness of 20 nm. Next, lithium fluoride was deposited on the electron injecting layer to a thickness of 1 nm, and aluminum was vapor-deposited to a thickness of 300 nm to form an electrode. As described above, an organic electroluminescence device (EL-2) was obtained.

Further, in order to protect the organic electroluminescent element (EL-2) from the surrounding environment, it is hermetically sealed in a dry glove box filled with pure nitrogen. For the application of 5V of a DC voltage of 5V between the electrodes, so that an organic electroluminescent element (EL-2) after the emission, resulting luminance of 1500cd / m ^2, the maximum emission luminance 68000cd / m ² and a luminous efficiency of 3.11m / W white light. Figure 3 shows the luminescence spectrum.

Further, the organic electroluminescent elements (EL-1) and (EL-2) have peak wavelengths λ2 in the wavelength range of λ1 and 580 nm to 620 nm in the wavelength range of 430 nm to 485 nm, respectively. Shown in Table 33. Further, the ratio I2/I1 between the luminous intensity I2 at the wavelength λ2 and the luminous intensity I1 at the wavelength λ1 is also shown in Table 33.

<Method for Producing Acrylic Resin Solution> (Preparation of acrylic resin solution 1F)

The acrylic resin solution 1F was prepared in the same manner as described for the acrylic resin solution 1A.

(Production of blue fine pigment)

200 parts of indigo blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1 gallon kneading of stainless steel. The machine (manufactured by Inoue Works Co., Ltd.) was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and then dried at 85 ° C for one day and night to obtain 190 parts of a blue fine pigment.

(Production of purple fine pigment)

Will be two 200 parts of purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) The mixture was kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, and the mixture was stirred for 2 hours while being heated to 80 ° C to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 85 ° C for one day and night to obtain 190 parts of a purple fine pigment.

(Production of red fine pigment 1F)

Red pigment CI Pigment Red 177 ("CROMOPHTAL RED A2B" manufactured by Ciba Japan Co., Ltd.) 152 parts, 8 parts of the pigment derivative A-2 shown in Table 5, 1600 parts of sodium chloride, and diethylene glycol (Tokyo Chemical Co., Ltd.) 190 parts were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the mixture was placed in about 5 liters of warm water, heated to about 70 ° C, and stirred in a high speed mixer for about 1 hour to form a slurry. Thereafter, the mixture was filtered and washed with water to remove sodium chloride and diethylene glycol, and dried at 80 ° C for 24 hours to obtain 156 parts of red fine pigment 1F.

(Production of red fine pigment 2F)

500 parts of red pigment CI Pigment Red 179 pigment ("Paliogen Maroon L-3920" manufactured by BASF JAPAN Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The product was kneaded at 120 ° C for 8 hours. Next, the kneaded product was placed in 5 liters of warm water, and heated to about 70 ° C, and stirred for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 80 ° C for one day and night to obtain 490 parts of red fine pigment 2F.

(Production of green fine pigment 1F)

500 parts of indigo green pigment CI Pigment Green 7 ("Leonol Green YS-07" manufactured by Toyo Ink Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneading machine made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), kneading at 120 ° C for 4 hours. Next, the kneaded product was placed in 5 liters of warm water, and heated to about 70 ° C while stirring for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 80 ° C for one day and night to obtain 490 parts of green fine pigment 1F.

(Production of green fine pigment 2F)

500 parts of indigo green pigment CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneading machine made of stainless steel (Inoue In the production), it was kneaded at 120 ° C for 4 hours. Next, the kneaded product was placed in 5 liters of warm water, and heated to about 70 ° C while stirring for 1 hour to form a slurry. After repeatedly filtering and washing with water, sodium chloride and diethylene glycol were removed, and dried at 80 ° C for one day and night to obtain 490 parts of green fine pigment 2F.

(Production of yellow fine pigment 1F)

The indigo green pigment CI Pigment Green 7 was changed to the isoporphyrin yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by Lanxess Co., Ltd.), and the kneading time was changed from 4 hours to 8 hours, and other than green. The preparation of the fine pigment 1F was carried out in the same manner to obtain 490 parts of a yellow fine pigment 1F.

(Production of yellow fine pigment 2F)

The indigo green pigment CI pigment green 7 was changed to isodecyl ketone yellow pigment CI Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), and the kneading time was changed from 4 hours to 8 hours. The preparation of the green fine pigment 1F was carried out in the same manner to obtain 490 parts of a yellow fine pigment 2F.

(Production of yellow fine pigment 3F)

The indigo green pigment CI pigment green 7 was changed to the isoporphyrin yellow pigment CI Pigment Yellow 185 ("Paliogen Yellow(R) D1155" manufactured by BASF Corporation), and the kneading time was changed from 4 hours to 8 hours, in addition to green The preparation of the fine pigment 1F was carried out in the same manner to obtain 490 parts of a yellow fine pigment 3F.

<Preparation method of resin (a1) having a cationic group in a side chain> (Preparation of Resin 1F having a cationic group in a side chain)

Resin 1F having a cationic group in a side chain was prepared by the same method as that described for the resin 1D.

(Preparation of Resin 2F having a cationic group in a side chain)

Resin 2F having a cationic group in a side chain was prepared by the same method as described for the resin 2D.

(Preparation of Resin 3F having a cationic group in a side chain)

Resin 3F having a cationic group in a side chain was prepared by the same method as described for the resin 3D.

(Preparation of Resin 4F having a cationic group in a side chain)

Resin 4F having a cationic group in a side chain was prepared by the same method as that described for the resin 4D.

(Preparation of Resin 5F having a cationic group in a side chain)

Resin 5F having a cationic group in a side chain was prepared by the same method as that described for resin 5D.

<Method for producing salt-forming product> (salt-forming product (A-1F))

The salt-forming product (A-1F) was prepared in the same manner as described for the salt-forming product (A-1D).

(salt-forming product (A-2F))

The salt-forming product (A-2F) was prepared in the same manner as described for the salt-forming product (A-2D).

(salt-forming product (A-3F))

The salt-forming product (A-3F) was prepared in the same manner as described for the salt-forming product (A-3D).

(salt-forming product (A-4F))

The salt-forming product (A-4F) was prepared in the same manner as described for the salt-forming product (A-4D).

(salt-forming product (A-5F))

The salt-forming product (A-5F) was prepared in the same manner as described for the salt-forming product (A-5D).

(salt-forming product (A-6F))

The salt-forming product (A-6F) was prepared in the same manner as described for the salt-forming product (A-6D).

(salt-forming product (A-7F))

The salt-forming product (A-7F) was prepared in the same manner as described for the salt-forming product (A-7D).

(salt-forming product (A-8F))

The salt-forming product (A-8F) was prepared in the same manner as described for the salt-forming product (A-8D).

(salt-forming product (A-9F))

The salt-forming product (A-9F) was prepared in the same manner as described for the salt-forming product (A-9D).

(salt-forming product (A-10F))

The salt-forming product (A-10F) was prepared in the same manner as described for the salt-forming product (A-10D).

(salt-forming product (A-11F))

The salt-forming product (A-11F) was prepared in the same manner as described for the salt-forming product (A-11D).

(salt-forming product (A-12F))

The salt-forming product (A-12F) was prepared in the same manner as described for the salt-forming product (A-19E).

< Method for producing a compound > ( Compounds (C-1F) and (C-2F))

Use and for The compounds (C-1A) and (C-2A) are described in the same manner and separately prepared. Compounds (C-1F) and (C-2F).

<Method for Producing Pigment Dispersion>

[Pigment Dispersion (BP-1F), (BP-2F), (VP-1F), (RP-1F), (RP-2F), (GP-1F), (GP-2F), (YP-1F) Preparation of (YP-2F) and (YP-3F)

The mixture of the pigment derivative, the pigment, the acrylic resin solution 1F, the resin-based dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.) and the organic solvent described in Table 34 was uniformly mixed with the blending described in Table 35, and then a diameter of 1 mm was used. The zirconia beads were subjected to a dispersion treatment for 5 hours using Eigermil ("Minimodel M250 MKII" manufactured by Eiger Japan Co., Ltd.). Thereafter, 30.0 parts of propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMAc) was added to the dispersion, and the mixture was filtered through a 5 μm filter to obtain a pigment dispersion.

<Method for Producing Resin Solution Containing Salt-Forming Product> (Preparation of resin solution (DA-1F) containing salt-forming product)

The mixture was stirred well, and then filtered through a 5.0 μm filter to obtain a resin solution (DA-1F) containing a salt-forming product.

Salt-forming product (A-1F): 11.0 parts

Acrylic resin solution 1F: 40.0 parts

Cyclohexanone: 49.0 parts

(Resin solution containing salt-forming products (DA-2F) to (DA-12F), containing Preparation of resin solution (DC-1F), (DC-2F)

The salt-forming product (A-1F) is changed to the salt-forming product (A) shown in Table 36 or In addition to the above-mentioned resin solution (DA-1F) containing a salt-forming product, a resin solution (DA-2F) to (DA-12F) containing a salt-forming product and containing the compound are prepared. A resin solution (DC-1F) and (DC-2F) of the compound. The content of the pigment component is shown in Table 36. In addition, the pigment content A represents a salt forming product (A) or The content (% by mass) of the effective pigment component in the compound. Further, the dye content B represents the content (% by mass) of the effective dye component in the resin solution containing the colorant.

*1 Pigment component content A: salt-forming product (A) or Effective pigment component content of the compound (% by weight)

*2 Pigment content B: Effective pigment component content (% by weight) in the resin solution containing the colorant

<Production of Blue Resist Material (Blue Coloring Composition) (BR-1F) to (BR-21F)> (Blue resist material (BR-1F))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable blue resist (BR-1F).

Resin solution containing salt-forming product (DA-1F): 21.0 parts

Pigment dispersion (BP-1F): 39.0 parts

Acrylic resin solution 1F: 11.0 parts

Trimethylolpropane triacrylate ("NK EST ER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Blue resist (BR-2F) to (BR-21F)) The alkali-developing blue was obtained in the same manner as the blue resist (BR-1F) except that the resin solution and the pigment dispersion containing the coloring agent and the blending amount thereof were changed as shown in Table 37. Color resist (BR-2F) to (BR-21F).

(Characteristics of resist material)

A coating film was formed from the resist materials (BR-1F) to (BR-21F), and the chromaticity and the amount of foreign matter of the coating films were examined by the following methods.

(production of blue filter section)

A black matrix of a light-shielding pattern was formed on the glass substrate, and then the blue resist shown in Table 38 was applied using a spin coater. The blue resist material is applied such that the film thickness is when the blue filter segment obtained from the blue resist material is combined with the organic electroluminescent element (EL-1) or (EL-2) The chromaticities x and y are the values shown in Table 38. For the coating film, an ultraviolet ray was irradiated with an ultrahigh pressure mercury lamp through a reticle at an exposure amount of 150 mJ/cm 2 . The coating film was then subjected to spray development to remove unexposed portions, and washed with ion-exchanged water. Here, the developer was an alkali developer containing 0.15 parts by mass of sodium carbonate, 0.05 parts by mass of sodium hydrogencarbonate, 0.1 parts by mass of an anionic surfactant ("PELEX NBL" manufactured by Kao Corporation), and 99.7 parts by mass of water. Thereafter, the substrate was heated at 230 ° C for 20 minutes to obtain a blue filter segment.

(chroma)

The chromaticity when the blue filter segment is combined with the organic electroluminescent element (EL-1) or (EL-2) is shown in Table 38.

(Test method for foreign matter in coating film)

The blue resist material was coated on a transparent substrate to have a dry film thickness of about 2.5 μm, and the coating film was entirely exposed to ultraviolet rays. Thereafter, the mixture was heated at 230 ° C for 20 minutes in the oven, and then allowed to cool to obtain an evaluation substrate. Next, the surface of each test substrate was observed using a metal microscope "BX60" manufactured by Olympus System. Here, the magnification is set to 500 times and observed in a penetration mode. Further, the number of particles that can be confirmed is calculated for any five fields of view, and the total number of particles is calculated. The results are shown in Table 38.

In addition, in Table 38, the meaning of the mark in the "coating foreign matter" column is as follows.

◎: The total number of particles is less than 5

○: The total number of particles is 5 or more and less than 20

△: The total number of particles is 20 or more and less than 100

×: The total number of particles is 100 or more

Blue filter segment formed from blue resist (BR-1F) to (BR-14F) compared to blue filter formed by blue resist (BR-15F) The slice segment has a higher brightness Y. The blue filter segments formed of the blue resist materials (BR-16F) and (BR-17F) have a large amount of foreign matter in the coating film although the brightness Y is high. Further, the organic electroluminescence device (EL-2) having a different emission spectrum from that of the organic electroluminescence device (EL-1) is formed of a resist material containing a blue pigment and a salt-forming product (A). The blue filter section also shows the brightness Y.

<Manufacturing Method of Red Resist Material (RR-1F) and Green Resist Material (GR-1F) to (GR-4F)> (Production of red resist material (RR-1F))

The mixture was stirred well, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist (RR-1F).

Pigment dispersion (RP-1F): 30.0 parts

Pigment dispersion (RP-2F): 30.0 parts

Acrylic resin solution 1F: 11.0 parts

Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.2 parts

Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Production of green resist (GR-1F) to (GR-4F))

The green resist material (GR-1F) was obtained in the same manner as in the red resist material (RR-1F) except that the colorant dispersion and the blending amount thereof were changed as shown in Table 39. GR-4F).

[Example 1F] (Production of color filter (CF-1F))

A black matrix of a light-shielding pattern was formed on the glass substrate, and then a red resist (RR-1F) was applied using a spin coater. The red resist material is applied such that the film thickness is such that when the filter segment obtained from the resist material and the organic electroluminescent element (EL-1) are combined, the chromaticities x and y are as shown in Table 41. The value. The coating film was irradiated with ultraviolet rays through an illuminant at an exposure amount of 300 mJ/cm ² using an ultrahigh pressure mercury lamp. Next, the coating film was supplied to a spray developing using an alkali developing solution composed of a 0.2% by mass aqueous sodium carbonate solution, the unexposed portion was removed, and washed with ion-exchanged water. The substrate was further heated at 230 ° C for 20 minutes to obtain a red filter segment.

Next, a green resist (GR-1F) was applied on the glass substrate using a spin coater. The green resist (GR-1F) is applied so that the film thickness is a combination of the filter segment obtained from the resist material and the organic electroluminescent device (EL-1), and the chromaticity x and y becomes the value shown in Table 41. Thereafter, the same exposure, development, cleaning, and heating as described for the red filter segments were performed to obtain green filter segments.

Next, a blue resist (BR-1F) was applied onto the glass substrate using a spin coater. The blue resist (BR-1F) is applied such that the film thickness is such that when the filter segment obtained from the resist material and the organic electroluminescent element (EL-1) are combined, the chromaticity x And y becomes the value shown in Table 41. Thereafter, the same exposure, development, cleaning, and heating as described for the red filter segments were performed to obtain blue filter segments.

A color filter (CF-1F) was obtained as described above.

[Examples 2F to 19F and Comparative Examples 1F to 4F] (Production of color filter (CF-2F) to (CF-23F))

The color filter (CF-) was produced in the same manner as the color filter (CF-1F) except that the red, green, and blue resist materials and the organic electroluminescence device were changed as shown in Table 40. 2F) to (CF-19F).

Further, the red, green, and blue resist materials and the organic electroluminescence element were changed as shown in Table 40, and each of the resist materials was applied so that the film thickness was such that the filter obtained by the combination was combined. In the case of the segment and the organic electroluminescent device (EL-2), the chromaticity x and y are the values shown in Table 41, and the color filter is produced in the same manner as the color filter (CF-1F). (CF-20F) to (CF-23F).

[Hue evaluation of color filters]

The color filters produced in the examples and the comparative examples were combined with the organic electroluminescent elements (EL-1) and (EL-2) as shown in Table 40. Then, the organic electroluminescence device was caused to emit light, and the color characteristics of the color filter were measured by a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). The chromaticity coordinates (x, y), the NTSC ratio, and the brightness (Y value) in the CIE color system of each filter segment are shown in Table 41.

Comparing Examples 1F to 16F with Comparative Example 1F, when a blue filter segment is formed from a colored composition containing a blue pigment and a salt-forming product (A), it is compared with a copper indigo pigment and a second When the coloring composition of the pigment forms a blue color filter segment, the whiteness is high, the NTSC ratio is large, and the color reproducibility is good. Further, in Comparative Examples 2F and 3F, although the brightness at the time of white display was high, many foreign matters were generated as described above.

Further, from the results of Examples 17F to 19F and Comparative Example 4F, it is understood that the organic electroluminescence device is changed from an element (EL-1) having a different emission spectrum to a device (EL-2), and is composed of a blue pigment and In the case where the colored composition of the salt-forming product (A) forms a blue filter segment, good performance can be achieved.

Figure 1 shows the luminescence spectrum of a backlight.

Fig. 2 is a view showing the luminescence spectrum of an organic electroluminescence device.

Fig. 3 is a view showing the luminescence spectrum of another organic electroluminescence device.

Claims (30)

A blue coloring composition for a color filter, which comprises a binder resin and a coloring agent, and the coloring agent contains a blue pigment and a salt forming product, and the salt forming product is composed of An acid dye and a compound having a cationic group; the compound having a cationic group containing at least one selected from the group consisting of a quaternary ammonium compound, an amine, and a resin having a cationic group in a side chain; The compound having a cationic group includes a resin having a cationic group in a side chain, and the resin having a cationic group in a side chain is an acrylic resin containing a structural unit represented by the following general formula (2): (In the formula (2), R ₅ represents a hydrogen atom, or a substituted or unsubstituted alkyl group; and R ₆ to R ₈ each independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or a substituted aryl group, or two of R ₆ to R ₈ may be bonded to each other to form a ring; Q represents an alkyl group, an extended aryl group, -CONH-R ₉ -, or -COO-R ₉ -, And R ₉ represents an alkylene group; Y ^- represents an inorganic or organic anion); the blue pigment is an indigo pigment and/or a triarylmethane lake pigment. A coloring composition for a color filter according to the first aspect of the invention, wherein the compound having a cationic group contains a quaternary ammonium compound represented by the following formula (1): (In the formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group; and Y ^- represents an inorganic or organic anion). A coloring composition for a color filter according to item 2 of the patent application, wherein the cation of the quaternary ammonium compound represented by the formula (1) has a molecular weight of from 190 to 900. The color filter of the second aspect of the invention is the blue coloring composition, wherein in the formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms. And two or more of R ₁ to R _{4 have} 5 to 20 carbon atoms. A coloring composition for a color filter according to claim 1, wherein the compound having a cationic group contains an amine selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine. At least one of the groups. The color filter of claim 5 is a blue coloring composition in which the molecular weight of the amine is in the range of 129 to 591. A blue coloring composition for a color filter according to claim 5, wherein the amine is represented by the following general formula (3): general formula (3): R ₁₀ R ₁₁ R ₁₂ N (general formula (3) In the above, two of R ₁₀ to R ₁₂ each independently represent an alkyl group or a benzyl group having 8 to 22 carbon atoms, and one of them represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms or Benzyl). A coloring composition for a color filter according to the first aspect of the invention, wherein the salt-forming product is a resin having a cationic group in a side chain and An acid dye mixed in an aqueous solution, and a relative anion of the resin having a cationic group in the side chain and the A compound obtained by removing a salt composed of a relative cation of an acid dye. A blue coloring composition for a color filter according to the first aspect of the invention, wherein the blue pigment comprises an indigo pigment, and the indigo pigment is C.I. Pigment Blue 15:6. A coloring composition for a color filter according to claim 1 of the patent application, wherein the coloring composition Acid dyes are classified as CI acid red. For example, the color filter of claim 10 is a blue coloring composition, wherein The acid dye is selected from the group consisting of CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI Acid Red 388. The color filter of claim 1 is a blue coloring composition, wherein the coloring agent further comprises C.I. Pigment Violet 23. The color filter of claim 1 is a blue coloring composition, wherein the coloring agent further comprises two It is a pigment. The color filter of claim 1 is a blue coloring composition, which further comprises a copper indigo amine compound. A coloring composition for a color filter according to claim 14 of the invention, wherein the copper indigo amine compound has a structure represented by the formula (4): general formula (4): P-Lm (general formula In (4), P is an m-valent copper indigo pigment residue, m is an integer of 1 to 4, and L is selected from the group represented by the general formula (5), (6), or (7). Any of the substituents) (In the general formulae (5) to (7), X is -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ -, or direct bonding; Y ⁰ is -NH-, -O-, or a direct bond; n is an integer from 1 to 10; Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ -, or a direct bond; R ⁹ and R ¹⁰ Each is independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group; Z represents an alkyl group having 1 to 20 carbon atoms or 1 to 20 carbon atoms. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ^{2 are} integrated to further contain nitrogen. a heterocyclic ring of an oxygen or a sulfur atom; R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or carbon a aryl group having 6 to 20 atoms; R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; and R ⁸ is a substituent represented by the formula (5); Or a substituent represented by the formula (6); Q represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a substituent represented by the formula (5), or a compound represented by the formula (6) Base). For example, the color filter of claim 14 is a blue coloring composition, wherein The mass ratio of the dye to the copper indigo amine compound is in the range of 0.3 to 1.5. A coloring composition for a color filter according to claim 14 of the patent application, wherein the blue pigment is a copper indigo pigment. For example, the color filter of claim 14 is a blue coloring composition, wherein The dye is a rose red dye. The blue coloring composition for a color filter according to the first aspect of the invention, wherein the content of the effective pigment component in the salt-forming product is 5 to 150 parts by mass when the content of the blue pigment is 100 parts by mass. In the range. A coloring composition for a color filter according to the first aspect of the invention is further characterized in that it further contains a photopolymerizable compound and/or a photopolymerization initiator. The blue coloring composition for a color filter according to the first aspect of the patent application, further comprising an organic solvent containing propylene glycol monomethyl ether acetate as a main component. A blue coloring composition for a color filter according to the first aspect of the invention, wherein the coating film formed by the coloring composition having a spectral transmittance of 3% at a wavelength of 570 nm has the following spectral characteristics: spectroscopic The wavelength at which the transmittance is 50% is in the range of 490 to 510 nm, the spectral transmittance at a wavelength of 450 nm is 85% or more, and the spectral transmittance at a wavelength of 540 nm is 11% or less. A color filter comprising: a green filter segment; a red filter segment; and a blue filter formed by the blue coloring composition according to any one of claims 1 to 22 Section. For example, the color filter of claim 23 is used for solid-state photographic elements. For example, the color filter of claim 23 is used for an organic electroluminescent display. The color filter of claim 25, wherein the white light-emitting organic electroluminescent element emits white light, and the white light has an emission spectrum having two or more maximum values in a wavelength range of 400 to 700 nm, and The peak wavelengths λ ₁ and λ ₂ each having a maximum intensity of the luminescence intensity in the range of 430 to 485 nm and the wavelength of 580 to 620 nm, the luminescence intensity I ₂ at the wavelength λ _{2 and} the luminescence intensity I at the wavelength λ _{1 1} ratio of I ₂ / I ₁ is within the range of 0.4 to 0.9; when the white light is incident on the blue color filter segment, the blue color filter segment transmitted light emitted in the CIE color system The chromaticity coordinates (xB, yB) in the middle satisfy the relationship shown by the inequality xB ≦ 0.160 and yB ≦ 0.100. The color filter of claim 25, wherein white light is emitted from the white light-emitting organic electroluminescent element, and the white light has an emission spectrum having a maximum value of two or more in a wavelength range of 400 to 700 nm, and The peak wavelengths λ ₁ and λ ₂ each having a maximum intensity of the luminescence intensity in the range of 430 to 485 nm and the wavelength of 580 to 620 nm, and the luminescence intensity I ₂ at the wavelength λ _{2 and} the luminescence intensity at the wavelength λ ₁ ratio I ₂ / I ₁ I ₁ is within a range of 0.4 to 0.9; so that when the white light is incident on the red, green and blue filter sections, the blue, green and red filter sections The emitted transmitted light is plotted on the xy chromaticity diagram of the chromaticity coordinates (xR, yR), (xG, yG), and (xB, yB) of the CIE color system, and the triangles that are used as vertices are drawn. When the area of the triangle is vertices, the coordinates of the triangles of (0.67, 0.33), (0.21, 0.71), and (0.14, 0.08) are more than 85% of the area. The color filter of claim 23, wherein the red filter segment comprises at least one of C.I. Pigment Red 177 and C.I. Pigment Red 179. The color filter of claim 23, wherein the green filter segment comprises: at least one green selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 a pigment; and at least one yellow pigment selected from the group consisting of CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185. A color display comprising: a color filter according to claim 23; and a light-emitting device comprising a white light-emitting organic electroluminescence element as a light source.