JP6031807B2 - Coloring composition, color filter and display element - Google Patents

Description

  The present invention relates to a colored composition, a color filter, and a display element. More specifically, the present invention is useful for a color filter used for a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, and the like. The present invention relates to a coloring composition for a color filter used for forming a colored layer, a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (see, for example, Patent Documents 1 and 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (see, for example, Patent Document 4).

  In recent years, in the technical field of color filters, the movement to shorten the tact time by lowering the exposure amount has become the mainstream, and highly sensitive colored compositions that enable pattern formation at a low exposure amount are strong. It has been demanded. In addition, since the color filter manufacturing process undergoes a heating (post-bake) step exceeding 200 ° C., the color filter formed from the colored composition is also required to have heat resistance.

  In response to such a demand, application of a fluorene polymer has been proposed. For example, Patent Document 5 forms a coating film with high sensitivity in a photosensitive resin composition containing a fluorene polymer having a specific structure. It has been reported that it is possible.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent No. 4733231

However, according to the study by the present inventors, simply applying the specific fluorene polymer reported in Patent Document 5 to the colored composition makes the colored composition inferior in storage stability and is extremely difficult to put into practical use. It became clear.
Therefore, the subject of this invention is providing the coloring composition which contains a specific fluorene polymer and is excellent in storage stability. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer 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 problems can be solved by incorporating a specific solvent, and the present invention has been completed.

That is, the present invention comprises the following components (A), (B1) and (C);
(A) a colorant,
(B1) a polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as “(B1) specific polymer”), and (C) at least selected from the group consisting of alcohols and ketones. Containing a solvent containing one species,
The content ratio of the said alcohols and ketones is 3-50 mass% in all the solvents, and provides the coloring composition characterized by the above-mentioned.

[In Formula (1),
Ring Z ¹ and ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups.
R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group.
R ^2a and R ^2b each independently represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group.
R ^3a and R ^3b each independently represent a hydrogen atom or a methyl group.
R ^a represents a group having a (meth) acryloyloxy group.
R ^b represents a group having a hydrogen atom or a (meth) acryloyloxy group.
k1 and k2 each independently represent an integer of 0 to 4.
m1 and m2 each independently represent an integer of 0 to 3.
n1 and n2 each independently represent an integer of 0 to 10.
t and u each independently represent an integer of 0 to 3. ]

The present invention also includes the following components (A), (B2) and (C);
(A) a colorant,
(B2) At least a step of adding a (meth) acrylate compound having an oxygen-containing saturated heterocyclic group to a polymer obtained by reacting a compound represented by the following formula (2) with tetrabasic dianhydride Containing a solvent (hereinafter also referred to as “(B2) specific polymer”) obtained through the process, and (C) a solvent containing at least one selected from the group consisting of alcohols and ketones;
The content ratio of the said alcohols and ketones is 3-50 mass% in all the solvents, and provides the coloring composition characterized by the above-mentioned.

[In Formula (2),
Ring Z ¹ and ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group.
R ^2a and R ^2b each independently represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group.
R ^3a and R ^3b each independently represent a hydrogen atom or a methyl group.
k1 and k2 each independently represent an integer of 0 to 4.
m1 and m2 each independently represent an integer of 0 to 3.
n1 and n2 each independently represent an integer of 0 to 10.
p1 and p2 each independently represent an integer of 1 to 4. ]

  Furthermore, this invention provides the color filter provided with the colored layer formed using this coloring composition, and the display element which comprises this color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

The coloring composition of the present invention has good storage stability. The colored composition is highly sensitive and can form a colored layer exhibiting high heat resistance.
Therefore, the colored composition of the present invention is used for various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for production.

Hereinafter, the present invention will be described in detail.
Coloring composition Hereinafter, the structural component of the coloring composition of this invention is demonstrated.
-(A) Colorant-
The (A) colorant in the present invention can be used without any particular limitation, and the color and material can be appropriately selected according to the use such as a color filter. Specific examples of the colorant include pigments, dyes, and natural pigments, and these can be used alone or in combination of two or more. Among them, an organic pigment is preferable as the pigment and an organic dye is preferable as the dye from the viewpoint of obtaining a pixel having high brightness, contrast, and color purity.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. Can be mentioned.

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 61, C.I. I. Pigment yellow 61: 1, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 133, 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 169, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 183, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 191: 1, C.I. I. Pigment yellow 206, C.I. I. Pigment yellow 209, C.I. I. Pigment yellow 209: 1, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 212;

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 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 54, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 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 200, 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 237, C.I. I. Pigment red 239, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 247, 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 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 27, 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. I. Pigment violet 39;
C. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 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 17: 1, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 56, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Pigment blue 80;
C. I. Pigment green 1, C.I. I. Pigment green 4, C.I. 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.

  Moreover, as an organic dye, what has the following color index (CI) name can be mentioned, for example.

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

C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;
C. I. Basic violet 1, C.I. I. Basic violet 3, C.I. I. Basic violet 14, C.I. I. Acid Blue 7, C.I. I. Basic Blue 1, C.I. I. Basic Blue 5, C.I. I. Basic Blue 7, C.I. I. Basic Blue 11, C.I. I. Basic Blue 26, C.I. I. Basic Green 1, C.I. I. Basic green 4 and other triarylmethane dyes;

C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42;
Methine dyes such as Disperse Yellow 201.

  In the present invention, the pigment 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. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  Moreover, in this invention, a well-known dispersing agent and a dispersing aid can also be included with a pigment. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrizol) As a polyethylenimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. As a polyester-based dispersant, Azisper PB8 1, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the (C) solvent mentioned later.

-(B) polymer-
The colored composition of the present invention contains the aforementioned (B1) specific polymer or (B2) specific polymer, and these polymers function as a binder resin and also as a curing component. In this specification, (B1) specific polymer and (B2) specific polymer are collectively referred to as (B) polymer.

(B2) The specific polymer is a polymer obtained by reacting a compound represented by the following formula (2) with tetrabasic dianhydride (hereinafter also referred to as “(B2 ′) polymer”). And a polymer obtained through at least a step of adding a (meth) acrylate compound having an oxygen-containing saturated heterocyclic group.

[In Formula (2),
Ring Z ¹ and ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group.
R ^2a and R ^2b each independently represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group.
R ^3a and R ^3b each independently represent a hydrogen atom or a methyl group.
k1 and k2 each independently represent an integer of 0 to 4.
m1 and m2 each independently represent an integer of 0 to 3.
n1 and n2 each independently represent an integer of 0 to 10.
p1 and p2 each independently represent an integer of 1 to 4. ]

First, the compound represented by Formula (2) is demonstrated.
Ring Z ¹ and ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring, and examples of the monocyclic hydrocarbon include monocyclic hydrocarbons such as benzene. It is done. Examples of the condensed polycyclic hydrocarbon include condensed bicyclic hydrocarbons having 8 to 20 carbon atoms such as indene and naphthalene; condensed polycyclic hydrocarbons having three or more rings such as anthracene and phenanthrene. be able to. As the condensed polycyclic hydrocarbon, a condensed bicyclic hydrocarbon having 10 to 16 carbon atoms is preferable. Of these, benzene, naphthalene and anthracene are preferred. Ring Z ¹ and ring Z ² may be the same or different.

R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, or a propyl group. Isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group and the like. Especially, a C1-C4 alkyl group is preferable and a methyl group is more preferable. R ^1a and R ^1b may be the same or different.
k1 and k2 each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When k1 and k2 are 2 or more, a plurality of R ^1a and R ^1b may be the same or different.
The substitution positions of R ^1a and R ^1b are not particularly limited, and can be substituted with any carbon atom on the benzene ring constituting the fluorene skeleton.

R ^2a and R ^2b each independently represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group. Examples of the hydrocarbon group include an alkyl group and a cycloalkyl group. , Aryl group, aralkyl group and the like.
As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and specific examples include a heptyl group, an octyl group, a decyl group, a dodecyl group, etc. in addition to the alkyl groups exemplified in R ^1a and R ^1b . Can do. Among these, a C1-C8 alkyl group is more preferable, and a C1-C6 alkyl group is still more preferable.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and specific examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, a C5-C8 cycloalkyl group is more preferable, and a C5-C6 cycloalkyl group is still more preferable.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable, and specific examples thereof include a phenyl group and an alkylphenyl group. For example, a methylphenyl group, a dimethylphenyl group, etc. can be mentioned. Among these, an aryl group having 6 to 8 carbon atoms is more preferable, and a phenyl group is still more preferable. Examples of the methylphenyl group include an o-tolyl group, m-tolyl group, and p-tolyl group. Examples of the dimethylphenyl group include a xylyl group.
As the aralkyl group, an aralkyl group having 7 to 14 carbon atoms is preferable, and specific examples include a group in which an alkyl group having 1 to 4 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples include a benzyl group and a phenethyl group. Among these, a group in which an alkyl group having 1 to 2 carbon atoms is bonded to an aryl group having 6 to 8 carbon atoms is more preferable.

As said alkoxy group, a C1-C4 alkoxy group is preferable, and a methoxy group, an ethoxy group, a butoxy group etc. can be mentioned specifically ,.
As said acyl group, a C1-C6 acyl group is preferable, and an acetyl group etc. can be mentioned specifically ,.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 4 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, as R ^2a and R ^2b , an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkoxy group are preferable, and an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and carbon An aryl group having 6 to 10 carbon atoms, a group in which an alkyl group having 1 to 2 carbon atoms is bonded to an aryl group having 6 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms An aryl group having 6 to 8 carbon atoms and an alkoxy group having 1 to 4 carbon atoms are particularly preferable. R ^2a and R ^2b may be the same or different.
m1 and m2 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. When m1 and m2 are 2 or more, a plurality of R ^2a and R ^2b may be the same or different.
The substitution position of R ^2a and R ^2b is not particularly limited, and can be substituted on any carbon atom on ring Z ¹ and ring Z ² .

R ^3a and R ^3b are each independently a hydrogen atom or a methyl group. When a plurality of R ^3a and R ^3b are present, they may be the same or different.

p1 and p2 are independently in the range of 1 to 4, but an integer of 1 to 3 is preferable, and 1 or 2 is more preferable. The substitution position of the hydroxyl group-containing group is not particularly limited, and can be substituted with any carbon atom on ring Z ¹ or ring Z ² .

  n1 and n2 each independently represent an integer of 0 to 10, but an integer of 0 to 4 is preferable, and an integer of 0 to 2 is more preferable. When n1 and n2 are 2 or more, the (poly) alkyleneoxy group may be composed of the same alkoxy group or may be composed of different types of alkoxy groups. Examples of combinations of different alkoxy groups include ethoxy group and propyleneoxy group.

  Among the compounds represented by the formula (2), compounds represented by the following formulas (4) and (5) can be exemplified as more preferred examples.

[In Formula (4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1, k2, m1, m2, n1, n2, p1 and p2 are as defined above. ]

[In Formula (5), R ^<1a> , R ^<1b> , R ^<2a> , R ^<2b> , R ^<3a> , R ^<3b> , k1, k2, m1, m2, n1, n2, p1, and p2 are synonymous with the above. ]

  As the compound represented by the formula (4), 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes are preferable.

  Examples of 9,9-bis (hydroxyalkoxynaphthyl) fluorenes include 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxy). Propoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [5- (2-hydroxypropoxy) -1-naphthyl] fluorene Etc.

The 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes are preferably 9,9-bis (hydroxydialkoxynaphthyl) fluorenes, specifically, 9,9-bis {6- [2- (2 -Hydroxyethoxy) ethoxy] -2-naphthyl} fluorene, 9,9-bis {6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl} fluorene, 9,9-bis {5- [2- 9,9-bis (hydroxydi) such as (2-hydroxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxypropoxy) propoxy] -1-naphthyl} fluorene C _2-4 alkoxynaphthyl) fluorene and the like.

  Examples of the compound represented by the formula (5) include 9,9-bis (hydroxyalkoxyphenyl) fluorenes, 9,9-bis (hydroxypolyalkoxydialkylphenyl) fluorenes, and 9,9-bis (hydroxyalkoxyarylphenyl). ) Fluorenes and 9,9-bis (hydroxypolyalkoxyarylphenyl) fluorenes are preferred.

  Examples of 9,9-bis (hydroxyalkoxyphenyl) fluorenes include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxypropoxy) phenyl. Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9 -Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenoxyethanol] fluorene, 9,9-bis [4- (2- Hydroxypropoxy) phenoxyethanol] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenol Nyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,6-dimethylphenyl] fluorene, 9-bis [4- (2-hydroxypropoxy) -2,6-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -2,4-dimethylphenyl] fluorene, 9,9- Bis [3- (2-hydroxypropoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,4-di Butylphenyl] fluorene, mention may be made of 9,9-bis [2- (2-hydroxypropoxy) -3,4-dimethylphenyl] 9,9-bis (hydroxyalkoxy alkylphenyl) fluorene such as fluorene.

  As 9,9-bis (hydroxypolyalkoxyphenyl) fluorenes, 9,9-bis (hydroxydialkoxyphenyl) fluorenes are preferable. Specific examples thereof include 9,9-bis [4- (2-hydroxydiethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) phenyl] fluorene, and 9,9-bis [ 4- (2-hydroxydiethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxydiethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxydipropoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,6-dimethylphenyl] fluorene, , 9-bis [4- (2-hydroxydipropoxy) -2,6-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -2,4-dimethylphenyl] fluorene, 9 , 9-bis [3- (2-hydroxydipropoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,4-dimethylphenyl] fluorene, 9 , 9-bis [2- (2-hydroxydipropoxy) -3,4-dimethylphenyl] fluorene and the like.

  As 9,9-bis (hydroxyalkoxyarylphenyl) fluorenes, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxy) 9,9-bis (hydroxyalkoxyarylphenyl) fluorene such as propoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-tolylphenyl] fluorene, preferably 9, And 9-bis (2-hydroxyethoxyarylphenyl) fluorene.

  As 9,9-bis (hydroxypolyalkoxyarylphenyl) fluorenes, 9,9-bis (hydroxydialkoxyarylphenyl) fluorenes are preferable, and specifically, 9,9-bis {4- [2- 9,9-bis (hydroxydialkoxyarylphenyl) fluorene, such as (2-hydroxyethoxy) ethoxy] -3-phenylphenyl} fluorene, preferably 9,9-bis [2- (2-hydroxyethoxy) ethoxyarylphenyl ] Fluorene etc. are mentioned.

  In the present invention, as the compound represented by the above formula (2), those produced by a conventional method may be used, but commercially available products such as BPEF, BOPPEF, and BNFEO (above, manufactured by Osaka Gas Chemical Co., Ltd.). Can also be used.

Next, tetrabasic acid dianhydride will be described.
Examples of tetrabasic acid dianhydrides include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride , Cyclohexanetetracarboxylic dianhydride, cycloheptanetetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride Biphenyl ether tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5- Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydride Naphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and the like can be mentioned, and these can be used alone or in admixture of two or more. Can do. Among these, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, benzophenone tetracarboxylic acid dianhydride And biphenyltetracarboxylic dianhydride are preferred.

  In the reaction of the compound represented by the formula (2) and the tetrabasic acid dianhydride, the tetrabasic acid dianhydride is added in an amount of 0.5 mol to 1.5 mol with respect to 1 mol of the compound represented by the formula (2). It is preferable to make it react by the ratio of 0.65 mol-1.25 mol. When the ratio of tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, a (B2 ′) polymer having a sufficient molecular weight may not be obtained.

  A catalyst may be used in the reaction of the compound represented by the formula (2) and tetrabasic dianhydride. The catalyst to be used is not particularly limited as long as it promotes the reaction. Examples thereof include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N , N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] nonene-5, etc .; quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide; Fin, triphenylphosphine and the like and mixtures thereof. Further, the amount of the catalyst to be used is not particularly limited, but a range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass in total of the compound represented by the formula (2) and tetrabasic dianhydride. Is preferred. If the amount of the catalyst is more than 2.0 parts by mass, the storage stability of the (B2) specific polymer may be adversely affected.

In the reaction of the compound represented by the formula (2) and tetrabasic dianhydride, a solvent may be used for the purpose of dissolving the reaction raw material and reducing the viscosity. The type of solvent is not particularly limited as long as it does not inhibit the reaction, but examples include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether. Glycol ether acetates such as acetate;
Propylene glycol ethers such as dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether;
Propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Acetates such as ethyl acetate and butyl acetate;
Dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  Although there is no restriction | limiting in particular also in the quantity of the solvent to be used, The range of 25-150 mass parts is preferable with respect to a total of 100 mass parts of the compound represented by Formula (2) and tetrabasic acid dianhydride. If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

  The compound represented by the formula (2) and tetrabasic acid dianhydride are reacted by adding a solvent or a catalyst, if necessary, but the reaction is preferably heated, the raw material is dissolved by heating, and the reaction rate Is also accelerated. The heating temperature can be appropriately set according to the type of the compound represented by the formula (2) and the tetrabasic acid dianhydride and the apparatus to be used, but is preferably in the range of 60 to 220 ° C, preferably 90 to 160 ° C. The range of is more preferable. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, when the reaction temperature is higher than 220 ° C., side reactions such as coloring may occur, or the reaction rate may decrease due to the equilibrium of acid anhydride ring closure.

Next, the reaction between the (B2 ′) polymer and the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group will be described.
The (meth) acrylate compound having an oxygen-containing saturated heterocyclic group is not particularly limited as long as it is a compound having at least one oxygen-containing saturated heterocyclic group and (meth) acryloyl group in the molecule. Here, the “oxygen-containing saturated heterocyclic group” means a saturated heterocyclic group having an oxygen atom as a hetero atom constituting the heterocyclic ring. In addition, the bonding position of the oxygen-containing saturated heterocyclic group and the (meth) acryloyl group in the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group is not limited.

  As the oxygen-containing saturated heterocyclic group in the present invention, a cyclic ether group having 3 to 7 atoms constituting the ring is preferable, and specifically, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a tetrahydrofuran group. Nyl group etc. can be mentioned. Among these, from the viewpoint of reactivity, an oxiranyl group, an oxetanyl group, and a 3,4-epoxycyclohexyl group are preferable.

  Examples of the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group include compounds represented by the following formula (3-1), formula (3-2), and formula (3-3).

[In the formulas (3-1), (3-2) and (3-3),
R ⁴ represents a hydrogen atom or a methyl group.
R ⁵ represents a single bond or a group represented by the following formula (6).
R ⁶ represents an alkyl group having 1 to 6 carbon atoms. ]

[In Formula (6),
q, r, and s each independently represent an integer of 0 to 9.
However, q, r and s are not simultaneously 0, and the —C ₂ H ₄ O— group, —C ₃ H ₆ O— group and —C ₄ H ₈ O— group are bonded in any order. It may be. ]

In Formula (6), the —C ₂ H ₄ O— group means a linking group including an ethylene group and an ethane-1,1-diyl group, and the —C ₃ H ₆ O— group means propane-1, A linking group including a 1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a propane-2,2-diyl group is meant. Further, -C ₄ H ₈ O-butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, butane-2,2-diyl group, butane -2, A linking group including a 3-diyl group and the like is meant.

R ⁶ is preferably an alkyl group having 1 to 4 carbon atoms, and specific examples thereof are the same as those described above.

Examples of the compound represented by the formula (3-1) include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl ( Examples thereof include (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, and polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether.
Examples of the compound represented by the formula (3-2) include 3,4-epoxycyclohexylmethyl (meth) acrylate.
Furthermore, as the compound represented by the formula (3-3), 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl)- Examples include 3-methyloxetane and 3- (acryloyloxymethyl) -3-ethyloxetane.

  In the reaction between the (B2 ′) polymer and the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group, a catalyst may be used for the purpose of promoting the reaction. The catalyst can be appropriately selected depending on the type of the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group. As an example, pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4 , 0] -7-undecene, amines such as 1,5-diazabicyclo [4,3,0] nonene-5; tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc. Quaternary ammonium compounds; tributylphosphine, may be mentioned triphenylphosphine, and the like, and mixtures thereof.

  The amount of the catalyst used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the (B2 ′) polymer. If the amount of the catalyst is too large, the storage stability of the colored composition of the present invention may be adversely affected.

  Moreover, when making the (meth) acrylate compound which has an oxygen-containing saturated heterocyclic group react, it is preferable to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited as long as it suppresses the reaction of unsaturated bond. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitroso. Aniline or N-nitrosophenylhydroxylamine / ammonium salt (Wako Pure Chemical Industries, Ltd .: Q-1300), N-nitrosophenylhydroxylamine / aluminum salt (Wako Pure Chemical Industries, Ltd .: Q-1301), 2, Examples include 2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. In particular, N-nitrosophenylhydroxylamine aluminum salt and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable. The amount of the polymerization inhibitor can be appropriately determined depending on the type and reaction conditions, but is usually in the range of 5 to 2000 ppm with respect to the whole (B2 ′) polymer. If the amount is less than this range, unsaturated bonds may react during production and gelation may occur. If the amount is more than this range, the sensitivity of the colored composition of the present invention may decrease, which is not preferable.

(B2 ′) When the polymer and the (meth) acrylate compound having an oxygen-containing saturated heterocyclic group are reacted, it is preferable to heat for the purpose of improving the reaction rate. Although heating temperature can be suitably set with the kind and apparatus of (meth) acrylate compound which has an oxygen-containing saturated heterocyclic group, it is the range of 60-150 degreeC normally. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, when the reaction temperature is higher than 150 ° C., side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.
The polymer thus obtained may be used as it is as the (B2) specific polymer, but after the remaining carboxyl group is sealed with glycidyl ethers or the like (B2) the specific polymer It can also be used as By sealing a part of the carboxyl group, the acid value of the (B2) specific polymer can be controlled.

  Thus, the specific polymer (B2) can be obtained, and among them, a polymer having a structural unit represented by the following formula (1) is preferable.

[In the formula (1), ring Z ¹ , ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1, k2, m1, m2, n1 and n2 are as defined above. .
Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups.
R ^a represents a group having a (meth) acryloyloxy group.
R ^b represents a group having a hydrogen atom or a (meth) acryloyloxy group.
t and u each independently represent an integer of 0 to 3. ]

  Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups, specifically, four carboxylates from a tetrabasic acid corresponding to the aforementioned tetrabasic acid dianhydride. Residues excluding groups can be mentioned.

In the formula (1), Ra represents ^a group having a (meth) acryloyloxy group, and examples thereof include a group derived from the above-mentioned (meth) acrylate compound having an oxygen-containing saturated heterocyclic group.
R ^b represents a hydrogen atom or a (meth) acryloyloxy group.
t and u each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and more preferably 0.

  In the present invention, the molecular weight of the polymer (B) is not particularly limited, but is preferably 1,000 to 200,000 from the viewpoints of coating film strength, coatability or developability, and more preferably 2,500. ~ 50,000 is preferred. In the present specification, the molecular weight of the polymer (B) is a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran).

  In the present invention, the acid value of the polymer (B) is preferably 30 to 150 mgKOH / g, but from the viewpoint of developability, more preferably 30 to 130 mgKOH / g, and still more preferably 50 to 100 mgKOH / g. . If the acid value is too low, the development speed may be reduced and a required pattern may not be obtained. On the other hand, if the acid value is too high, the pattern may be peeled off due to excessive development. In this specification, the “acid value” represents the number of mg of KOH required to neutralize 1 g of the nonvolatile content excluding the solvent of the polymer solution.

  In the present invention, a resin other than the polymer (B) (hereinafter, also referred to as “(b) another polymer”) can be contained as the binder resin. Thereby, the binding property to a board | substrate, alkali developability, and storage stability can be improved. Such a polymer 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, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as “unsaturated monomer (b-1)”) and other. A copolymer with a copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b-2)”) can be given.

  Specific examples of the copolymer of the unsaturated monomer (b-1) and the unsaturated monomer (b-2) include, for example, JP-A-7-140654 and JP-A-8-259876. It is disclosed in Kaihei 10-31308, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, (b) the other polymer can be used alone or in admixture of two or more.

In the present invention, the content of the component (B) is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the colorant (A). In this case, when there is too little content of (B) component, there exists a possibility that alkali developability may fall, for example, or the storage stability of the coloring composition obtained may fall. On the other hand, when the content of the component (B) is too large, the colorant concentration is relatively lowered, and it may be difficult to achieve the target color density as a thin film.
Further, when (b) another polymer is used in combination, the content of the polymer (B) is 10% by mass or more, further 15% by mass or more, and further 20% by mass or more with respect to the total amount of the binder resin. It is preferable.

-(C) Solvent-
The colored composition of the present invention contains 3 to 50% by mass of at least one solvent selected from the group consisting of alcohols and ketones (hereinafter also referred to as “solvent (c1)”) in the total solvent. Thereby, the coloring composition excellent in storage stability can be obtained.

Examples of the alcohols include:
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;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, 3-methoxybutanol, octanol, 2-ethylhexanol, cyclohexanol;
Examples thereof include keto alcohols such as diacetone alcohol.

  Of these alcohols, (poly) alkylene glycol monoalkyl ethers and (cyclo) alkyl alcohols are preferred, and ethylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether are particularly preferred. , Propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethanol and 3-methoxybutanol are preferred. Alcohol can be used individually or in mixture of 2 or more types.

  Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Among them, cyclohexanone is preferable. The ketones can be used alone or in admixture of two or more.

Examples of the solvent other than the solvent (c1) (hereinafter also referred to as “solvent (c2)”) include, for example:
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, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

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

  Of these solvents (c2), (poly) alkylene glycol monoalkyl ether acetates, ethers, diacetates, and alkoxycarboxylic acid esters are preferred, especially ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol. Monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate are preferred. A solvent (c2) can be used individually or in mixture of 2 or more types.

  In this invention, 5-50 mass% is preferable in all the solvents, as for the content rate of a solvent (c1), 10-40 mass% is more preferable, 15-35 mass% is still more preferable. When the content ratio of the solvent (c1) is less than 3% by mass, foreign matters are likely to be generated in the colored composition or the cured film. On the other hand, when the content ratio of the solvent (c1) exceeds 50% by mass, the viscosity of the colored composition tends to increase with time.

  (C) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, Especially 10-40 mass% Is preferred. By setting it as such an aspect, the coloring composition with favorable dispersibility, applicability | paintability, and stability can be obtained.

-Crosslinking agent-
In the present invention, the curability of the colored layer can be further enhanced by incorporating a crosslinking agent. A cross-linking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the crosslinking agent is preferably a compound having two or more (meth) acryloyloxy groups (excluding the above component (B)) or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyloxy groups (excluding the component (B)) include a polyfunctional compound obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid ( (Meth) acrylate, polyfunctional (meth) acrylate modified with caprolactone, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) obtained by reacting hydroxyl-containing (meth) acrylate and polyfunctional isocyanate Examples thereof include polyfunctional (meth) acrylates having a carboxyl group obtained by reacting acrylate and hydroxyl group-containing (meth) acrylate with an acid anhydride.

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

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

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

Among these crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethanes ( (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N′— Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, a crosslinking agent can be used individually or in mixture of 2 or more types.

  As for content of the crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agent, and 20-500 mass parts is especially preferable. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is an active species capable of initiating polymerization of the component (B) and an optional crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a generated compound.

  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 compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, an onium salt compound, etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator preferably contains at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime compounds, and particularly O-acyl oximes. The inclusion of a compound is preferable in that it has good compatibility with the polymer (B) and hardly generates foreign matter.

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

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

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

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

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

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

  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. Moreover, in this invention, the sensitivity of a coloring composition can be improved by including the polyfunctional thiol which acts as a chain transfer agent. Examples of such chain transfer agents include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 2,4,6-trimercapto-s-triazine, 2 -(N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned.

  In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and more preferably 1 to 100 parts by mass with respect to 100 parts by mass in total of the component (B) and the optional crosslinking agent. Preferably, 7-50 mass parts is further preferable, and 10-30 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-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 acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: 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-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

  The coloring composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (B) components together with (C) a solvent and other components optionally added. , Can be prepared by mixing. (A) When using a pigment as a colorant, the pigment is pulverized in a solvent (C) in the presence of a dispersant, optionally with a part of the component (B), for example, using a bead mill, a roll mill or the like. It is preferable to prepare a pigment dispersion by mixing and dispersing, and then adding the component (B) and, if necessary, additional solvent and other components to the pigment dispersion and mixing them. (A) When both a dye and a pigment are used as the colorant, the dye solution was passed through the first filter and then passed through the first filter as disclosed in JP 2010-132874 A A method of preparing a dye solution by mixing it with a separately prepared pigment dispersion or the like and passing the resulting colored composition through a second filter can be employed. In addition, the dye, the component (B), and other components to be used as necessary are dissolved in a solvent, and the solution obtained after passing through the first filter is passed through the first filter. Alternatively, a method may be adopted in which the mixture is mixed with a separately prepared pigment dispersion and the resulting colored composition is passed through a second filter. Moreover, after passing a dye solution through a 1st filter, the dye solution which passed the 1st filter, the said (B) component, and the other component used as needed were obtained by mixing and dissolving. A method is also adopted in which the solution is passed through the second filter, the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through the third filter. can do.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of the radiation-sensitive colored composition of the present invention in which a red pigment is dispersed on this substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and blue color. Are sequentially formed on the same substrate. Thereby, a color filter in which 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 pixels of each color is not limited to the above. In the first method for producing a color filter, any one or more of the red, green, and blue pixel arrays may be a colored layer formed using the colored composition of the present invention.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the color filter 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 radiation-sensitive 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, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples thereof include a light source, a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The radiation is preferably in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / 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, 1, 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.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, after the liquid composition of the thermosetting coloring composition of the present invention in which a red pigment is dispersed in the formed partition wall is ejected by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Subsequently, using each thermosetting coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns 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 pixels of each color is not limited to the above. In the second method for producing a color filter, any one or more of the red, green, and blue pixel arrays may be a colored layer formed using the colored composition of the present invention.

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and 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. Further, 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.

  The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Plane Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  Moreover, the organic EL display element provided with the color filter of the present invention can have an appropriate structure, for example, the structure disclosed in JP-A-11-307242.

  In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

  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.

<Measurement of acid value>
Hereinafter, the acid value of the polymer (B) obtained in each synthesis example was measured as follows. 0.5 g of the polymer solution was precisely weighed to a unit of 1 mg and placed in a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titrated with 0.1 N ethanolic potassium hydroxide aqueous solution, and the point colored in pink was the end point. Similarly, a blank test was performed. (B) The acid value (unit: mgKOH / g) was calculated from the amount of the polymer and 0.1N ethanolic potassium hydroxide aqueous solution dropped in the blank test.

<Synthesis of polymer>
Synthesis Example 1 (Synthesis of (B) polymer)
In a 1000 mL flask equipped with a stirrer and a condenser tube, 90 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product name: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka) Gas Chemical Co., Ltd. (trade name: BPEF) 110 g, 4-dimethylaminopyridine 1 g, and propylene glycol monomethyl ether acetate 134 g were added and heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: trade name ADK STAB LA-7RD), 4-hydroxybutyl acrylate 80 g of glycidyl ether (Nippon Kasei Co., Ltd. product name: 4HBAGE) was added and stirred at 120 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous polymer solution. The obtained polymer had a polystyrene-reduced weight average molecular weight of 4920 by GPC and an acid value of 61 mgKOH / g. This polymer is referred to as “polymer (B-1)”.

Synthesis Example 2 ((b) Synthesis of other polymer)
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 12 parts by mass of styrene, 41 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, n-butyl methacrylate A mixed solution of 2 parts by mass, 15 parts by mass of N-phenylmaleimide, 0.5 parts by mass of 2,2′-azobisbutyronitrile, and 2 parts by mass of dipentaerythritol tetrakis-2-mercaptopropionate was brought to 80 ° C. And polymerized for 4 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a polymer solution (solid content concentration = 40% by mass). The obtained polymer had Mw = 24,000, Mn = 1480, Mw / Mn = 1.60, and an acid value of 98 mgKOH / g. This polymer is referred to as “polymer (B-2)”.

Synthesis Example 3 ((b) Synthesis of other polymer)
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer solution (solid content concentration = 40% by mass). The obtained polymer had Mw = 11,000, Mn = 6000, Mw / Mn = 1.83, and the acid value was 130 mgKOH / g. This polymer is referred to as “polymer (B-3)”.

<Preparation of pigment dispersion>
Preparation Example 1
(A) C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 138 = 15.0 parts by mass of 60/40 (mass ratio) mixture, BYK-LPN21116 (produced by BYK) as a dispersant, solvent ratio (mass%): propylene glycol monomethyl ether acetate / ethylene glycol mono-n -Butyl ether / ethanol = 48.7 / 50 / 1.3) 11.1 parts by weight (solid content concentration 40% by mass), (b) 13.8 masses of polymer (B-3) solution as other polymer Part (solid content concentration: 40% by mass), propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 25%, mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-1) did.

Preparation Example 2
(A) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 60/40 (mass ratio) 15.0 parts by mass of the mixture, 11.1 parts by weight of BYK-LPN21116 (solid content concentration 40% by mass) as a dispersant, (b) a polymer ( B-3) 13.8 parts by mass of the solution (solid content concentration 40% by mass), propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 25%, and mixed and dispersed by a bead mill for 12 hours, A pigment dispersion (A-2) was prepared.

Preparation Example 3
As a coloring agent, C.I. I. Pigment Blue 15: 6 / C.I. I. Basic Blue 7 = 60/40 (mass ratio) 15.0 parts by weight of mixture, 11.1 parts by weight of BYK-LPN21116 (solid content concentration 40% by weight) as a dispersant, propylene glycol monomethyl ether acetate and propylene glycol mono as solvents Using ethyl ether, the content ratio of propylene glycol monoethyl ether in the entire solvent is 20% and the solid content concentration is 25%, and then mixed and dispersed by a bead mill for 12 hours to obtain a pigment dye mixture (A-3) Was prepared.

<Preparation and evaluation of coloring composition>
Example 1
Preparation of colored radiation-sensitive coloring composition (A) 210 parts by mass of pigment dispersion (A-1) as colorant, 11.1 parts by mass of polymer (B-1) solution as polymer (B) (solid content concentration) = 50% by mass), 36 parts by mass of KAYARAD MAX-3510 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., Ltd. as a crosslinking agent, and 2-benzyl-2-dimethyl as a photopolymerization initiator 5.3 parts by mass of amino-1- (4-morpholinophenyl) butan-1-one and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime) 2.0 parts by mass, 0.2 parts by mass of DIC Corporation Megafac F-554 as a fluorosurfactant, and a solvent ( Select propylene glycol monomethyl ether acetate as C-1) and propylene glycol monoethyl ether as solvent (C-4), and mix so that the content ratio of solvent (C-4) in all the solvents is 30% by mass. Then, a green radiation-sensitive colored composition (S-1) having a solid content concentration of 15% by mass was prepared.

Sensitivity evaluation The colored composition (S-1) is applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface using a slit die coater, and then on a hot plate at 90 ° C. Pre-baking was performed for 4 minutes to form six coating films having a film thickness after pre-baking of 2.5 μm.
Next, after these substrates are cooled to room temperature, radiation containing 365 nm, 405 nm, and 436 nm is applied to the coating film through a photomask using a high-pressure mercury lamp, 100, 200, 300, 500, 800, or 1 The exposure was performed at an exposure amount of 1,000 J / m ² . Then, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) on these substrates, shower development was further performed, followed by 220. Post-baking was carried out at 30 ° C. for 30 minutes to form a 200 μm × 200 μm dot pattern on the substrate.

  The dot pattern on each substrate on which the pattern was formed with each exposure amount was observed with a scanning electron microscope, the pattern was formed well, and the remaining film ratio calculated as the film thickness ratio before and after development (film thickness after development) × 100 / thickness before development) was 90% or more, “◯”, the pattern was formed satisfactorily, but the residual film ratio was less than 90%, or a part of the pattern was missing The case where the pattern was formed was evaluated as “Δ”, and the case where the pattern was not formed was evaluated as “x”. The evaluation results are shown in Table 3.

Evaluation of heat resistance The colored composition (S-1) was applied on a soda glass substrate having a SiO ₂ film on its surface to prevent elution of sodium ions, using a slit die coater, and then heated at 90 ° C. The plate was pre-baked for 4 minutes to form two coating films having a film thickness of 2.5 μm after pre-baking.
Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 1,000 J / m @ 2 through a photomask using a high-pressure mercury lamp. Then, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm), the substrate is further showered, and further 220 ° C. Was post-baked for 30 minutes to form a 200 μm × 200 μm dot pattern on the substrate.

  The two substrates obtained were additionally baked for 60 minutes at 230 ° C. and 250 ° C., respectively, and the pattern after the additional baking was observed with an optical microscope. Generation of foreign matter was observed in both 230 ° C. and 250 ° C. additional baking. If there is no foreign matter generated in the additional baking at 230 ° C. and no foreign matter is observed in the additional baking at 250 ° C., “△” is indicated. did. The evaluation results are shown in Table 3.

  Moreover, the following foreign material evaluation and viscosity stability evaluation were implemented as storage stability evaluation of coloring composition (S-1).

Evaluation of foreign matter Colored composition (S-1) which was allowed to stand at 5 ° C. for 3 days on a 10 cm × 10 cm soda glass substrate on which a SiO 2 film for preventing elution of sodium ions was formed using a slit die coater After coating, pre-baking was performed for 4 minutes on a 90 ° C. hot plate to form a coating film having a film thickness of 2.5 μm after pre-baking. The obtained substrate is observed with an optical microscope. If no foreign matter is observed on the coating film, “◯” is indicated. If the number of foreign matters generated on the coating film is 1 or more and 10 or less, “△” is indicated. If the number of occurrences of foreign matter on the film was observed 11 or more, it was judged as “x”. The evaluation results are shown in Table 3.

Viscosity stability evaluation The viscosity immediately after the preparation of the colored composition (S-1) was measured using an E-type viscometer (manufactured by Tokyo Keiki). Next, the colored composition (S-1) 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). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “◯”, when 5% or more and less than 10%, “△”, when 10% or more Was evaluated as “×”. The evaluation results are shown in Table 3.

Examples 2-30 and Comparative Examples 1-14
In Example 1, the types and blending amounts of the pigment dispersion, the polymer solution, the crosslinking agent, and the photopolymerization initiator were changed as shown in Table 1, and the alcohols and ketones with respect to all the solvents in the coloring composition were changed. Colored compositions (S-2) to (S-44) were prepared by changing the type and blending amount of the solvent so that the content ratio (unit: mass%) was as shown in Table 2. Subsequently, the colored compositions (S-2) to (S-44) were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.
In Table 2, the solvents (C-12) and (C-13) were used when preparing the pigment dispersions (A-1) to (A-2) and the pigment dye mixture (A-3). It is a component in BYK-LPN21116.

In Table 1, each component is as follows.
D-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)
E-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
E-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OXE02, Ciba Specialty・ Made by Chemicals
E-3: NCI-930 (trade name: NCI-930, manufactured by ADEKA)

In Table 2, each component is as follows. The solvents (C-1) to (C-3) correspond to the solvent (c2), and the solvents (C-4) to (C-13) correspond to the solvent (c1).
C-1: Propylene glycol monomethyl ether acetate C-2: Ethyl 3-ethoxypropionate C-3: 3-methoxybutyl acetate C-4: Propylene glycol monoethyl ether C-5: Propylene glycol monomethyl ether C-6: 3 -Methoxybutanol C-7: Dipropylene glycol monomethyl ether C-8: Dipropylene glycol mono-n-propyl ether C-9: Propylene glycol mono-n-butyl ether C-10: Diethylene glycol monoethyl ether C-11: Cyclohexanone C -12: Ethylene glycol mono-n-butyl ether C-13: Ethanol

Claims (6)

The following components (A), (B1) and (C);
(A) a colorant,
(B1) contains a polymer having a structural unit represented by the following formula (1), and (C) a solvent,
(C) As a solvent, (c1) including at least one alcohol selected from (poly) alkylene glycol monoalkyl ethers and (cyclo) alkyl alcohols,
The content ratio of the alcohols is 3 to 50% by mass in the total solvent.
Coloring composition for forming color filter pixels or black spacers.

[In Formula (1),
Ring Z ¹ and ring Z ² each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
Y represents a residue obtained by removing four carboxyl groups from an organic compound having four carboxyl groups.
R ^1a and R ^1b each independently represent a hydrogen atom or an alkyl group.
R ^2a and R ^2b each independently represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group.
R ^3a and R ^3b each independently represent a hydrogen atom or a methyl group.
R ^a represents a group having a (meth) acryloyloxy group.
R ^b represents a group having a hydrogen atom or a (meth) acryloyloxy group.
k1 and k2 each independently represent an integer of 0 to 4.
m1 and m2 each independently represent an integer of 0 to 3.
n1 and n2 each independently represent an integer of 0 to 10.
t and u each independently represent an integer of 0 to 3. ]   The coloring according to claim 1, further comprising (C) at least one selected from (c2) (poly) alkylene glycol monoalkyl ether acetates, ethers, diacetates and alkoxycarboxylic acid esters as a solvent. Composition.   The coloring composition according to claim 1 or 2, wherein the pixels are red, green, or blue pixels.   (A) The coloring composition of any one of Claims 1-3 whose content rate of a coloring agent is 5-70 mass% in solid content of a coloring composition.   Furthermore, the coloring composition of any one of Claims 1-4 which contains an O-acyl oxime type compound as a photoinitiator. The process of forming the pixel pattern by forming the coating film of the coloring composition of any one of Claims 1-5 on a board | substrate, exposing and developing this coating film, and post-baking is included. The manufacturing method of a color filter.