JP2010256509A - Coloring composition, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition which allows formation of a pixel having higher brightness and contrast ratio than a pixel formed using C.I. pigment yellow 150 and is superior in storage stability. <P>SOLUTION: The coloring composition contains (A) a colorant, (B) a dispersant, (C) a binder resin, and (D) a polyfunctional monomer. The colorant (A) contains a clathrate compound having a metal complex of an azo barbituric acid as the host and having a melamine or the like as the guest, and the dispersant (B) contains a block copolymer having an A block having a quaternary ammonium salt and an amino group at the side chain and a B block having neither quaternary ammonium salt nor amino group at the side chain. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a colored composition, a color filter, and a liquid crystal display element, and more particularly, to formation of a colored layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a colored composition used, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

  As a method for forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. A method of obtaining pixels of each color by irradiating radiation through a photomask having a pattern (hereinafter referred to as “exposure”), developing to dissolve and remove unexposed portions, and then post-baking (for example, patents) Document 1 and Patent Document 2) are known. In addition, a method of obtaining pixels of each color by an ink jet method using a colored resin composition (for example, see Patent Document 3) is also known.

  Since liquid crystal display elements equipped with such color filters are required to have higher brightness and an expanded color reproduction area, the color pixels that make up the color filters have recently been increasing in light transmittance and color. It is required to have purity. As a method for increasing the light transmittance (brightness) of a red or green pixel in response to such a request, for example, C.I. I. It is known to use Pigment Yellow 150 (see, for example, Patent Document 4 and Patent Document 5).

  However, C.I. I. Even with the pigment yellow 150, it is not possible to sufficiently meet the recent demand for higher luminance and expansion of the color reproduction region. In contrast, in Patent Document 6, C.I. I. As a color filter pigment having improved transparency and color purity with respect to CI Pigment Yellow 150, an inclusion compound having a metal complex of azobarbituric acid as a host and melamine or the like as a guest is disclosed. However, no example has been reported in which the pigment disclosed in Patent Document 6 is stably dispersed with high contrast so as to meet the recent demand for high contrast for liquid crystal display elements.

On the other hand, it is known that it is effective to use a dispersing agent in order to stably disperse the atomized pigment, which realizes high contrast and high brightness of the liquid crystal display element. In Patent Document 7 and Patent Document 8, it is proposed to use a dispersant composed of a block having a quaternary ammonium base and a block having no quaternary ammonium base in order to improve the dispersion stability of the pigment. However, even with such a dispersant, it has been difficult to stably disperse the pigment having excellent characteristics disclosed in Patent Document 6 with high contrast. That is, in order to stably disperse the pigment, a large amount of dispersant must be used, and as a result, development with an alkaline developer becomes difficult. Conversely, when the amount of the dispersant used is reduced, sufficient brightness and There was a problem that the contrast ratio could not be obtained or the storage stability of the colored composition was deteriorated.
From the above background, C.I. I. There is a strong demand for the development of a coloring composition that can form a pixel having a higher luminance and contrast ratio than the pigment yellow 150 and has excellent storage stability.

JP-A-2-144502 JP-A-3-53201 JP 2000-310706 A JP-A-9-269410 JP 2007-13313 A JP 2001-354869 A JP 2004-182787 A JP 2004-287366 A

The subject of the present invention is C.I. I. An object of the present invention is to provide a coloring composition that can form a pixel having a higher luminance and contrast ratio than that using CI Pigment Yellow 150 and has excellent storage stability.
Furthermore, the objective of this invention is providing the color liquid crystal display element which comprises the color filter provided with the pixel formed from the said coloring composition, and the said color filter.

  In view of this situation, the present inventors have conducted extensive research and found that the above-described problems can be solved by using a combination of the pigment disclosed in Patent Document 6 and a dispersant having a specific structure. The present invention has been completed.

  That is, the present invention is a coloring composition containing (A) a colorant, (B) a dispersant, (C) a binder resin, and (D) a polyfunctional monomer, wherein (A) the colorant is An inclusion compound (hereinafter sometimes referred to as “specific pigment”) comprising a host represented by the following formula (I) or a tautomer thereof and a guest represented by the following formula (II). (B) a block co-polymer in which the dispersant has an A block having a quaternary ammonium base and an amino group in the side chain and a B block having no quaternary ammonium base and an amino group in the side chain The present invention provides a coloring composition characterized by containing a coalescence.

(In Formula (II), R ^{a to} R ^c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.)

  The present invention also provides a color filter comprising a colored layer formed using the colored composition, and a color liquid crystal display device comprising the color filter. Here, the “colored layer” means a layer composed of pixels and / or a black matrix used for a color filter.

  The present invention also provides a colorant dispersion containing the colorant, the dispersant and a solvent.

The coloring composition of the present invention can form a pixel having a high luminance and contrast ratio and is excellent in storage stability.
Therefore, the colored composition of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. .

Hereinafter, the present invention will be described in detail.
Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The colorant (A) used in the coloring composition of the present invention contains a specific pigment represented by the above formulas (I) and (II).
In the above formula (II), as R ^{a to} R ^c , at least one of them is preferably ^a hydrogen atom, and all of R ^{a to} R ^c are hydrogen atoms, that is, the above formula (II) It is particularly preferred that the guest represented by is melamine.
A specific pigment can be used individually or in mixture of 2 or more types.

In the present invention, other colorants can be used in combination with the specific pigment. Other colorants are not particularly limited, and are appropriately selected according to the use of the color filter, and may be any of pigments, dyes, and natural pigments. Since color filters are required to have heat resistance, organic pigments or inorganic pigments are preferred as other colorants. Organic pigments other than specific pigments (hereinafter sometimes referred to as “other organic pigments”) are classified as pigments in, for example, the Color Index (CI; issued by The Society of Dyers and Colorists). Specific examples of the compounds include those having color index (CI) numbers as shown below.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  In the present invention, the specific pigment and other organic pigments can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include polymers described in JP-A-8-259876, various commercially available polymers or oligomers for dispersing pigments, and the like. The polymer coating method on the carbon black surface is disclosed in, for example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like.
The other colorants can be used alone or in admixture of two or more.

  When the colored composition of the present invention is used to form a red pixel, (A) the colorant includes C.I. I. Pigment red 177 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Red 254. In this case, the content ratio of the specific pigment is preferably 1 to 30% by mass, more preferably 2 to 25% by mass in the total colorant. I. Pigment red 177 and C.I. I. The content ratio of at least one selected from the group consisting of CI Pigment Red 254 is preferably 50 to 99% by mass and more preferably 60 to 98% by mass in the total colorant.

  Moreover, when using the coloring composition of this invention for formation of a green pixel, (A) As a coloring agent, C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Green 58. In this case, the content ratio of the specific pigment is preferably 1 to 80% by mass, more preferably 2 to 70% by mass in the total colorant. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. The content ratio of at least one selected from the group consisting of CI Pigment Green 58 is preferably 20 to 99% by mass, and more preferably 30 to 98% by mass in all the colorants.

  In addition, when the colored composition of the present invention is used for forming a black matrix, (A) the colorant includes C.I. I. Pigment red 177 and C.I. I. Pigment Red 254 and at least one selected from the group consisting of C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Blue 15: 6. In this case, the content ratio of the specific pigment is preferably 2 to 30% by mass, more preferably 5 to 25% by mass in the total colorant. I. Pigment red 177 and C.I. I. The content ratio of at least one selected from the group consisting of CI Pigment Red 254 is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total colorant. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4 and C.I. I. The content ratio of at least one selected from the group consisting of CI Pigment Blue 15: 6 is preferably 5 to 40% by mass and more preferably 10 to 30% by mass in the total colorant.

By using the colorant as described above, a pixel having high luminance, contrast ratio, and color purity, or a black matrix having high light shielding properties can be formed.
In the present invention, the content of (A) the colorant is preferably 5 to 70% by mass in the total solid content from the viewpoint of forming a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties. 5 to 60% by mass is more preferable. Here, solid content is components other than the solvent mentioned later.

-(B) Dispersant-
(B) The dispersant used in the coloring composition of the present invention has an A block having a quaternary ammonium base and an amino group in the side chain and a B block having no quaternary ammonium base and an amino group in the side chain. Contains a block copolymer (hereinafter sometimes referred to as “specific dispersant”). The specific dispersant is preferably an AB block copolymer or a BAB block copolymer from the viewpoint of enhancing a desired effect.

The A blocks constituting the specific dispersing agent, a quaternary ammonium base, preferably ^{-N + R 1 R 2 R 3} · Y - ( ^where, R 1 to R ³ are, independently of one another, a hydrogen atom or a substituent, A chain or cyclic hydrocarbon group which may have a ring structure, and two or more of R ^{1 to} R ³ may be bonded to each other to form a cyclic structure, and Y ⁻ represents a counter anion. ) And an amino group, preferably —NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a chain optionally having a substituent). A cyclic or cyclic hydrocarbon group, and R ⁵ and R ⁶ may be bonded to each other to form a cyclic structure). The quaternary ammonium base and amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Among the substituents on the hydrocarbon group represented by R ^{1 to} R ⁶ , examples of the substituent on the chain hydrocarbon group include a halogen atom, an alkoxy group, and a benzoyl group. Examples of the substituent on the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, and an alkoxy group. Further, the chain hydrocarbon groups represented by R ^{1 to} R ⁶ include both linear and branched chains.

In —N ⁺ R ¹ R ² R ³ , as the cyclic structure formed by combining two or more of R ^{1 to} R ³ with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or 2 Examples include condensed rings formed by individual condensation. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the formula (III), R is any one of R ^{1 to} R ^3. )
These cyclic structures may further have a substituent.
-N ⁺ R ¹ R ² The ^R 1 to R ³ in R ^3, which may have a substituent alkyl group having 1 to 4 carbon atoms, carbon atoms which may have a substituent 7-16 Are more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group are particularly preferable.

Moreover, in —NR ⁵ R ⁶ , R ⁵ and R ⁶ are bonded to each other, and examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

These cyclic structures may further have a substituent.
^{R 5} and ^{R 6} in the -NR ⁵ R ^6, more preferably be an alkyl group having 1 to 4 carbon atoms have a substituent, a methyl group, an ethyl group, a propyl group, a butyl group particularly preferred.

  The A block is a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “repeating unit (1)”) and a repeating unit represented by the following formula (2) (hereinafter referred to as “repeating unit”). Those containing (2) "may be preferred.

(In Formula (1), R < ¹ > -R < ³ > shows the hydrogen atom or the chain-like or cyclic hydrocarbon group which may have a substituent mutually independently, Of R < ¹ > -R < ³ > Two or more may be bonded to each other to form a cyclic structure, R ⁴ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.)

(In Formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or a chain-like or cyclic hydrocarbon group which may have a substituent, and R ⁵ and R ⁶ are And may be bonded to form a cyclic structure, wherein R ⁷ represents a hydrogen atom or a methyl group, and Z represents a divalent linking group.)

In the above formulas (1) and (2), examples of the divalent linking groups X and Z include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ¹³ — group, and —COO—. R ¹⁴ -group (provided that R ¹³ and R ¹⁴ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms). And preferably a —COO—R ¹⁴ — group. In the formula (1), examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ −, BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  In the A block, the repeating unit (1) and the repeating unit (2) may be contained in any form of random copolymerization and block copolymerization. In addition, the repeating unit (1) and the repeating unit (2) may be contained in two or more types in one A block, in which case each repeating unit is randomly copolymerized in the A block, It may be contained in any form of block copolymerization. The copolymerization ratio of repeating unit (1) / repeating unit (2) in the A block is preferably 99/1 to 50/50, more preferably 95/5 to 70/30 (mass ratio).

  Moreover, the repeating unit which does not have a quaternary ammonium base and an amino group may be contained in the A block. Examples of such a repeating unit are derived from a (meth) acrylic acid ester monomer described later. And the like. The content of the repeating unit having no quaternary ammonium base and amino group in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. However, such a repeating unit is contained in the A block. Most preferably it is not contained.

  On the other hand, the B block constituting the specific dispersant may be a repeating unit derived from a (meth) acrylic acid ester monomer represented by the following formula (3) (hereinafter, referred to as “repeating unit (3)”). .). In the present specification, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl or methacryl”, “acrylate or methacrylate” and the like, for example, “(meth) acrylic acid” It shall mean “acrylic acid or methacrylic acid”.

(In Formula (3), R ⁸ represents a chain or cyclic alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁹ represents a hydrogen atom. Or represents a methyl group.)
Examples of the substituent on the alkyl group represented by R ⁸ include a halogen atom and an alkoxy group. Examples of the substituent on the aryl group or aralkyl group include a chain alkyl group, a halogen atom, and an alkoxy group. Further, the linear hydrocarbon group represented by R ⁸ includes both linear and branched chains.
R ⁸ in the above formula (3) is preferably a chain alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms, methyl group, ethyl group, propyl group. Group, butyl group, 2-ethylhexyl group, phenyl group, benzyl group and phenylethyl group are particularly preferred.

  The B block constituting the specific dispersant may be further referred to as a repeating unit derived from a (meth) acrylic acid ester monomer represented by the following formula (4) (hereinafter referred to as “repeating unit (4)”). ). Such a repeating unit is considered to enhance the compatibility of the specific dispersant with a binder component such as a solvent and further improve the dispersion stability of the colorant.

(In Formula (4), R ¹⁰ represents an ethylene group or a propylene group, R ¹¹ represents an alkyl group having 1 to 5 carbon atoms, R ¹² represents a hydrogen atom or a methyl group, and n is an integer of 1 to 20) Is shown.)

R ¹¹ in the above formula (4) is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. N is preferably 1 to 10, and more preferably 1 to 5.

  In the B block, the repeating unit (3) and the repeating unit (4) may be contained in any form of random copolymerization and block copolymerization. When the specific dispersant is a B-A-B block copolymer, a B1 block having a repeating unit (3) and not having a repeating unit (4), and a repeating unit (3) having a repeating unit (4) (3 B1-A-B2 block copolymer consisting of B2 block not having. Further, the repeating unit (3) and the repeating unit (4) may be contained in two or more kinds in one B block, in which case each repeating unit is randomly copolymerized in the B block, It may be contained in any form of block copolymerization. The copolymerization ratio of repeating unit (3) / repeating unit (4) in the B block is preferably 99/1 to 50/50, more preferably 99/1 to 80/20 (mass ratio). The same applies to the B1 block / B2 block ratio.

  A repeating unit other than the repeating unit (3) and the repeating unit (4) may be contained in the B block. Examples of such a repeating unit include styrene monomers such as styrene and α-methylstyrene. (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, croton Examples include acid glycidyl ether; repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (3) and the repeating unit (4) in the B block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably it is not contained in the block.

  The specific dispersant can be produced, for example, by living polymerizing a monomer that introduces each of the above repeating units. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

  Examples of the monomer for introducing the repeating unit (1) used in producing the specific dispersant include (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, and (meth) acryloyloxy. Examples thereof include ethyl triethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride and the like. Examples of the monomer for introducing the repeating unit (2) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. In the repeating unit (1), after polymerizing the monomer for introducing the repeating unit (2), the polymer is reacted with a halogenated hydrocarbon compound such as benzyl chloride to partially quaternize the amino group. Can also be introduced.

  Examples of the monomer for introducing the repeating unit (3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenylethyl (meth) acrylate. Examples of the monomer for introducing the repeating unit (4) include polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n = 1-5) ethyl ether (meth) acrylate, polyethylene glycol. (N = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1-5) ethyl ether (meth) acrylate, polypropylene glycol (n = 1-5) Propyl ether (meth) acrylate and the like.

  Whether the specific dispersant is an A-B block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer is from the viewpoint of dispersibility. It is preferable that it is 10 / 90-70 / 30, especially 25 / 75-55 / 45 (mass ratio).

  The amount of quaternary ammonium base in 1 g of the specific dispersant is preferably 0.1 to 10 mmol, and the amount of amino group in 1 g of the specific dispersant is preferably 0.1 to 10 mmol. By using such a dispersant, a pixel having a high contrast ratio can be formed, and a radiation-sensitive composition having excellent storage stability can be obtained.

  Further, the acid value of the specific dispersant is preferably lower from the viewpoint of dispersibility, and particularly preferably 0 mgKOH / g. Here, the acid value represents the number of mg of KOH necessary for neutralizing 1 g of the solid content of the dispersant.

  The molecular weight of the specific dispersant is preferably in the range of 1000 to 30,000 in terms of polystyrene-converted weight average molecular weight (hereinafter sometimes referred to as “Mw”). If the Mw is less than 1,000, the dispersion stability may be lowered. On the other hand, if it exceeds 30,000, the developability may be lowered, or dry foreign matter may be easily generated during coating by the slit nozzle method. is there.

  In the present invention, other dispersants can be used in combination with the specific dispersant. Examples of the other dispersing agent include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2000, Disperbyk-2001 (above, manufactured by Kick B) Commercial products such as Solsperse 24000, Solsperse 76500 (manufactured by Lubrizol Corp.), Addisper PB821, Addispar PB822, Addisper PB823, Addisper PB824, Addisper PB827 (Ajinomoto Fine Techno Co., Ltd.), and the like.

  In the present invention, the content of the dispersant is not particularly limited, but is preferably 0.5 to 70 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the (A) colorant. is there. Further, the content ratio of the specific dispersant is preferably 25% by mass or more, more preferably 50% by mass or more in the total dispersant. By incorporating a dispersant in such a manner, a colored composition having a high luminance and contrast ratio and having excellent storage stability and developability can be obtained.

-(C) Binder resin-
The (C) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (c1)”) and other copolymers. A copolymer with a possible ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (c2)”) (hereinafter referred to as “carboxyl group-containing copolymer”) is preferred.

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, and the like. it can. These unsaturated monomers (c1) can be used alone or in admixture of two or more.
In the carboxyl group-containing copolymer, the copolymerization ratio of the unsaturated monomer (c1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Examples of the unsaturated monomer (c2) include:
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide of paracumylphenol Unsaturated carboxylic esters such as modified (meth) acrylates;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (c2) can be used alone or in admixture of two or more.

  Specific examples of the carboxyl group-containing copolymer include, for example, JP-A-7-140654, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11- Examples thereof include copolymers disclosed in Japanese Patent Nos. 258415, 2000-56118, and 2004-101728.

In the present invention, for example, as disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-2008-181095, etc., a (meth) acryloyl group or the like is present in the side chain. A carboxyl group-containing copolymer having a polymerizable unsaturated bond can also be used as a binder resin.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 45,000, preferably 3,000 to 30,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

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

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(D) polyfunctional monomer-
The (D) polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene, both end hydroxypolycaprolactone;
Examples include tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide-modified triacrylate, poly (meth) acrylate having a urethane structure, poly (meth) acrylate having a caprolactone structure, and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products, poly (meth) acrylates having a urethane structure, and poly (meth) acrylates having a caprolactone structure (Meth) acrylate is preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Monoesterified products of acrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified product of hexaacrylate, pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of colored layer, excellent surface smoothness of colored layer, and unexposed This is preferable in that ground stains, film residue, and the like hardly occur on the substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The content of the (D) polyfunctional monomer in the present invention is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (C) alkali-soluble resin. In this case, when the content of the polyfunctional monomer is less than 5 parts by mass, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, when the content exceeds 500 parts by mass, for example, alkali developability is reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as mono [(meth) acryloyloxyalkyl] ester of acid, ω-carboxypolycaprolactone mono (meth) acrylate, and N- (meth) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% by mass or less, more preferably 50% by mass or less, with respect to the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by mass, the strength and surface smoothness of the pixel tend to be lowered.

-(E) Photopolymerization initiator-
The coloring composition of the present invention can be provided with radiation sensitivity by incorporating a photopolymerization initiator. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The (E) photopolymerization initiator used in the present invention is obtained by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. It is a compound that generates an active species capable of initiating polymerization of a functional monomer.
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds , At least one selected from the group of O-acyloxime compounds is preferred.

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

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

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

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

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

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

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

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (D) polyfunctional monomers, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is less than 0.01 parts by mass, curing by exposure may be insufficient. On the other hand, if the content exceeds 120 parts by mass, the formed colored layer becomes a substrate during development. There is a tendency to drop off easily.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, anionic surfactants, and the like Surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-Chloropropylmethyldimethoxy Adhesion promoters such as lan, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulant such as sodium acrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3 -Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-a The residue improving agent such as Roh-1,2-butanediol, and the like.

-(F) Solvent-
The colored composition of the present invention contains the above components (A) to (D) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent.
As the solvent, as long as the components (A) to (D) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the solvent is appropriately used. You can choose to use.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 -Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually An amount of 5 to 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly desirable.

In the present invention, the coloring composition can be prepared by an appropriate method. For example, the coloring composition is prepared by mixing the components (A) to (D) together with a solvent and other components optionally added. Can do. As a preferred method for preparing the coloring composition, (A) a coloring agent is added to (F) a solvent in the presence of (B) a dispersing agent and, if necessary, a dispersing aid. Along with the part, for example, using a bead mill, a roll mill or the like, mixed and dispersed while being pulverized to obtain a colorant dispersion. To this colorant dispersion, components (C) to (D) and, if necessary, further added The method of preparing by adding a solvent and another component and mixing can be mentioned.
Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative, and specifically include a copper phthalocyanine derivative.

Color filter The color filter of the present invention comprises a colored layer formed from the colored composition of the present invention.
As a method for forming a color filter, first, a colored radiation-sensitive composition coating film is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a photo having a predetermined pattern is formed. There is known a method of obtaining pixels of each color by exposing radiation through a mask, developing to dissolve and remove unexposed portions, and then post-baking.
Specifically, first, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a pixel forming portion, and, for example, a radiation sensitive material in which a red pigment is dispersed. After applying the liquid composition, the composition is pre-baked to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
Further, the black matrix can be formed in the same manner as in the case of forming the pixel by using the colored composition of the present invention.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition of the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method is used. In particular, spin coating and slit die coating are preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

As a second method of forming a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 is also known.
Since the color filter of the present invention thus obtained has a high luminance and contrast ratio, it is extremely useful particularly for color liquid crystal surface elements represented by TV.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

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

Dispersant analysis Dispersant B1
Dispersant B1 is a commercial product of a pigment wetting and dispersing agent, and is a propylene glycol methyl ether acetate / butyl cellosolve = 1/1 (mass ratio) solution of a modified acrylic block copolymer (solid content concentration 40% by mass, Acid value = 0). A block having a repeating unit derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, dispersant B, and methyl methacrylate, butyl methacrylate, 2-ethylhexyl by pyrolysis GC-MS, FT-IR measurement, and proton NMR It was confirmed to be a block copolymer (A / B = 38/62) composed of B blocks having repeating units derived from methacrylate, benzyl methacrylate and triethylene glycol ethyl ether methacrylate. The copolymerization ratio of each repeating unit was methacryloyloxyethylbenzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate / triethylene glycol ethyl ether methacrylate = 34/4/16/17. / 12/10/7 (mass ratio).

Dispersant b1
Dispersant b1 is a commercial product of a pigment wetting and dispersing agent, and is a propylene glycol methyl ether acetate / butyl cellosolve = 1/1 (mass ratio) solution of a modified acrylic block copolymer (solid content concentration 40% by mass, Acid value = 0). According to pyrolysis GC-MS, FT-IR, and proton NMR measurement, the dispersant b1 has an A block having a repeating unit derived from methacryloyloxyethylbenzyldimethylammonium chloride, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and It was confirmed to be a block copolymer (A / B = 16/84) consisting of a B block having a repeating unit derived from triethylene glycol ethyl ether methacrylate. The copolymerization ratio of each repeating unit was methacryloyloxyethylbenzyldimethylammonium chloride / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate / triethylene glycol ethyl ether methacrylate = 16/16/15/18/29/6 ( Mass ratio).

Dispersant synthesis Dispersant B2
A flask equipped with a condenser and a stirrer was charged with 1.0 part by weight of AIBN (2,2′-azobisisobutyronitrile) and 186 parts by weight of propylene glycol monomethyl ether acetate, followed by 27 parts by weight of methyl methacrylate and butyl methacrylate. 27 parts by mass, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate and 3.6 parts by mass of cumyldithiobenzoate were charged, and the atmosphere was replaced with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 1.0 part by weight of AIBN and 35 parts by weight of dimethylaminoethyl methacrylate in 70 parts by weight of propylene glycol monomethyl ether acetate and replacing with nitrogen for 30 minutes was added to this reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. As a result, a solution of the block copolymer was obtained.
To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added and reacted at 80 ° C. for 2 hours to obtain a solution containing the dispersant B2. Dispersant B2 comprises an A block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. A block copolymer. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloyloxyethylbenzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34/4/18/18 / 14/12 (mass ratio).

Dispersant b2
A flask equipped with a condenser and a stirrer was charged with 1.0 part by weight of AIBN and 186 parts by weight of propylene glycol monomethyl ether acetate, followed by 27 parts by weight of methyl methacrylate, 27 parts by weight of butyl methacrylate, 19 parts by weight of 2-ethylhexyl methacrylate, and benzyl methacrylate. 16 parts by mass, 16 parts by mass of triethylene glycol ethyl ether methacrylate and 3.6 parts by mass of cumyldithiobenzoate were charged, and the atmosphere was replaced with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution in which 1.0 part by mass of AIBN and 54 parts by mass of dimethylaminoethyl methacrylate were dissolved in 108 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen for 30 minutes was added to this reaction solution, and living at 60 ° C. for 24 hours. A solution containing the dispersant b2 was obtained by radical polymerization.
Dispersant b2 is composed of an A block having repeating units derived from dimethylaminoethyl methacrylate and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and triethylene glycol ethyl ether methacrylate. It is a block copolymer. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate / triethylene glycol ethyl ether methacrylate = 34/17/17/12/10. / 10 (mass ratio).

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Red 254, 3.75 parts by mass, C.I. I. 8.25 parts by mass of Pigment Red 177, 3 parts by mass of a specific pigment in which the guest represented by the formula (II) is melamine, and 3 parts by mass of a dispersant B1 as a specific dispersant (B) as a dispersant ( Solid content conversion), using propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent as solvent so that the solid content concentration becomes 18% by mass, and mixed and dispersed for 12 hours by a bead mill. Thus, a pigment dispersion (A-1) was prepared.

Preparation Example 2
In Preparation Example 1, a pigment dispersion (A-2) was prepared in the same manner as Preparation Example 1, except that the dispersant B2 was used as the dispersant (B).

Preparation Example 3
(A) C.I. I. 6.75 parts by mass of Pigment Green 7; 8.25 parts by mass of a specific pigment in which the guest represented by the formula (II) is melamine; and 3 parts by mass of Dispersant B1 as a specific dispersant as a dispersant (B). Parts (in terms of solid content), as a solvent, ethyl 3-ethoxypropionate / propylene glycol monomethyl ether = 80/20 (mass ratio) mixed solvent is used for a solid content concentration of 18% by mass, and mixed for 12 hours by a bead mill. Dispersion was carried out to prepare a pigment dispersion (A-3).

Preparation Example 4
(A) C.I. I. 9.6 parts by mass of CI Pigment Green 36, 5.4 parts by mass of a specific pigment in which the guest represented by the above formula (II) is melamine, and 3 parts by mass of Dispersant B1 as a specific dispersant as a dispersant (B) Parts (solid content conversion), propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 90/10 (mass ratio) mixed solvent as solvent, solid content concentration of 18% by mass, mixed and dispersed by bead mill for 12 hours Thus, a pigment dispersion (A-4) was prepared.

Preparation Example 5
(A) C.I. I. 9.0 parts by weight of CI Pigment Green 58, 6.0 parts by weight of a specific pigment in which the guest represented by the above formula (II) is melamine, and 3 parts by weight of dispersant B1 as a specific dispersant as (B) dispersant A pigment dispersion (A-5) was prepared by mixing and dispersing for 12 hours with a bead mill using propylene glycol monomethyl ether acetate as a part (solid content conversion) and a solvent so as to have a solid content concentration of 18% by mass.

Comparative Preparation Example 1
In Preparation Example 1, a pigment dispersion (a-1) was prepared in the same manner as Preparation Example 1, except that the dispersant b1 was used as the dispersant (B).

Comparative Preparation Example 2
A pigment dispersion (a-2) was prepared in the same manner as in Preparation Example 1 except that the dispersant b2 was used as the dispersant (B) in Preparation Example 1.

Comparative Preparation Example 3
In Preparation Example 1, (A) C.I. I. Pigment red 254, C.I. I. Pigment red 177 and C.I. I. The same procedure as in Preparation Example 1 was performed except that pigment yellow 150 was used to adjust the chromaticity coordinate value y at the chromaticity coordinate value x = 0.650 to be equivalent to that of the pigment dispersion (A-1). Thus, a pigment dispersion (a-3) was prepared.

Comparative Preparation Example 4
In Preparation Example 3, a pigment dispersion (a-4) was prepared in the same manner as Preparation Example 3, except that the dispersant b1 was used as the dispersant (B).

Comparative Preparation Example 5
In Preparation Example 3, a pigment dispersion (a-5) was prepared in the same manner as Preparation Example 3, except that the dispersant b2 was used as the dispersant (B).

Comparative Preparation Example 6
In Preparation Example 3, (A) C.I. I. Pigment green 7 and C.I. I. The same procedure as in Preparation Example 3 except that pigment yellow 150 was used to adjust the chromaticity coordinate value x at the chromaticity coordinate value y = 0.600 to be equivalent to that of the pigment dispersion (A-3). Thus, a pigment dispersion (a-6) was prepared.

Comparative Preparation Example 7
In Preparation Example 4, a pigment dispersion (a-7) was prepared in the same manner as Preparation Example 4 except that the dispersant b1 was used as the dispersant (B).

Comparative Preparation Example 8
A pigment dispersion (a-8) was prepared in the same manner as in Preparation Example 4 except that the dispersant b2 was used as the dispersant (B) in Preparation Example 4.

Comparative Preparation Example 9
In Preparation Example 4, (A) C.I. I. Pigment green 36 and C.I. I. The same procedure as in Preparation Example 4 was performed except that pigment yellow 150 was used to adjust the chromaticity coordinate value x at the chromaticity coordinate value y = 0.600 to be equivalent to that of the pigment dispersion (A-4). Thus, a pigment dispersion (a-9) was prepared.

Comparative Preparation Example 10
In Preparation Example 5, a pigment dispersion (a-10) was prepared in the same manner as in Preparation Example 5 except that the dispersant b1 was used as the dispersant (B).

Comparative Preparation Example 11
In Preparation Example 5, a pigment dispersion (a-11) was prepared in the same manner as Preparation Example 5 except that the dispersant b2 was used as the dispersant (B).

Comparative Preparation Example 12
In Preparation Example 5, (A) C.I. I. Pigment green 58 and C.I. I. The same procedure as in Preparation Example 5 was performed except that pigment yellow 150 was used to adjust the chromaticity coordinate value x at the chromaticity coordinate value y = 0.600 to be equivalent to that of the pigment dispersion (A-5). Thus, a pigment dispersion (a-12) was prepared.

(C) Synthesis of binder resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts by weight of AIBN and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, 20 parts by weight of N-phenylmaleimide, 55 parts by weight of benzyl methacrylate, and 10 parts by weight of styrene. In addition, 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) was charged as a molecular weight regulator, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 16,000 and Mn = 7,000. This binder resin solution is referred to as “resin solution (C1)”.

Example 1
Preparation of radiation sensitive composition Pigment dispersion (A-1) 100 parts by mass, (C) 10 parts by mass (solid content conversion) of resin solution (C1) as binder resin, (D) Difunctional monomer as difunctional monomer 15 parts by mass of pentaerythritol hexaacrylate, (E) 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator and 4,4′-bis ( Diethylamino) benzophenone (1 part by mass) and (F) propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (CR1) having a solid content concentration of 22%.
The liquid composition (CR1) was evaluated according to the following procedure. The evaluation results are shown in Table 1.

Evaluation of chromaticity characteristics and contrast Three liquid compositions (CR1) were formed on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater with variable number of rotations. After coating, pre-baking was performed on a hot plate at 90 ° C. for 4 minutes to form three coating films having different film thicknesses.
Next, after cooling these substrates to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 J / m ² using a high-pressure mercury lamp. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged onto these substrates at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 1 minute. Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a cured film for evaluation.

Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) for the three cured films obtained, the chromaticity coordinate value (x, y) and the stimulation value in the CIE color system with a C light source and a 2-degree field of view. (Y) was measured.
Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta) The maximum value and the minimum value of the transmitted light intensity were measured. A value obtained by dividing the maximum value by the minimum value was defined as the contrast ratio.
From the measurement result, the stimulus value (Y) and contrast ratio at the chromaticity coordinate value x = 0.650 were obtained. The evaluation results are shown in Table 1.

Evaluation of Storage Stability The viscosity of the liquid composition (CR1) on the day of preparation was measured using an E-type viscometer manufactured by Tokyo Keiki. The liquid composition (CR1) was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer manufactured by Tokyo Keiki. At this time, the increase rate of the viscosity after standing with respect to the viscosity on the day of preparation is calculated. When the increase rate is less than 5%, “◯”, when 5% or more and less than 10%, “Δ”, 10% or more Cases were evaluated as “x”. The evaluation results are shown in Table 1.

Examples 2-5 and Comparative Examples 1-12
Liquid compositions (CR2) to (CR17) were prepared in the same manner as in Example 1, except that the type of pigment dispersion was changed as shown in Table 1 in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (CR2) to (CR17) were used instead of the liquid composition (CR1). In addition, regarding the red liquid compositions (CR2) and (CR6) to (CR8), the stimulation value (Y) and the contrast ratio at the chromaticity coordinate value x = 0.650 are set as the green liquid composition (CR3) to For (CR5) and (CR9) to (CR17), the stimulus value (Y) and contrast ratio at the chromaticity coordinate value y = 0.600 were determined, respectively. The evaluation results are shown in Table 1.

In Table 1, “R254” means C.I. I. Pigment Red 254, “R177” is C.I. I. Pigment Red 177, “G7” is C.I. I. Pigment Green 7, “G36” is C.I. I. Pigment Green 36, “G58” is C.I. I. Pigment Green 58, “Y150” is C.I. I. Pigment Yellow 150 and “specific pigment” mean specific pigments in which the guest represented by the formula (II) is melamine.

Claims (10)

(A) A coloring composition containing (B) a dispersing agent, (C) a binder resin, and (D) a polyfunctional monomer, wherein (A) the coloring agent is represented by the following formula (I) Or a tautomer thereof, and a clathrate compound consisting of a guest represented by the following formula (II), and (B) a dispersant is quaternary ammonium in the side chain A coloring composition comprising a block copolymer having an A block having a base and an amino group, and a B block not having a quaternary ammonium base and an amino group in a side chain.

(In Formula (II), R ^{a to} R ^c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.) The A block has a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and the B block has a repeating unit represented by the following formula (3). Item 2. The coloring composition according to Item 1.

(In Formula (1), R < ¹ > -R < ³ > shows the hydrogen atom or the chain-like or cyclic hydrocarbon group which may have a substituent mutually independently, Of R < ¹ > -R < ³ > Two or more may be bonded to each other to form a cyclic structure, R ⁴ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.)

(In Formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or a chain-like or cyclic hydrocarbon group which may have a substituent, and R ⁵ and R ⁶ are And may be bonded to form a cyclic structure, wherein R ⁷ represents a hydrogen atom or a methyl group, and Z represents a divalent linking group.)

(In Formula (3), R ⁸ represents a chain or cyclic alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁹ represents a hydrogen atom. Or represents a methyl group.) The coloring composition according to claim 2, wherein the B block further has a repeating unit represented by the following formula (4).

(In Formula (4), R ¹⁰ represents an ethylene group or a propylene group, R ¹¹ represents an alkyl group having 1 to 5 carbon atoms, R ¹² represents a hydrogen atom or a methyl group, and n is an integer of 1 to 20) Is shown.)   The colored composition according to any one of claims 1 to 3, wherein the guest represented by the formula (II) is melamine.   (A) The colorant is further C.I. I. Pigment red 177 and C.I. I. The coloring composition according to any one of claims 1 to 4, which contains at least one selected from the group consisting of CI Pigment Red 254.   (A) The colorant is further C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. The colored composition according to any one of claims 1 to 4, which contains at least one selected from the group consisting of CI Pigment Green 58.   Furthermore, (E) The coloring composition in any one of Claims 1-6 containing a photoinitiator.   The color filter provided with the pixel formed using the coloring composition in any one of Claims 1-7.   A color liquid crystal display device comprising the color filter according to claim 8.   A colorant dispersion containing (A) a colorant, (B) a dispersant, and (F) a solvent, wherein (A) the colorant is represented by the above formula (I) or a tautomer thereof And an A block having a quaternary ammonium base and an amino group in the side chain, and a clathrate compound comprising a guest represented by the above formula (II), A colorant dispersion liquid comprising a block copolymer having a quaternary ammonium base and a B block having no amino group in a side chain.