JP2002273191A - Pigment dispersant and photosensitive coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant capable of enhancing the dispersibility and dispersion stability of pigment and a photosensitive coloring composition excellent in photosensitivity. SOLUTION: The pigment dispersion contains at least one kind of a compound with a weight average mol.wt. of 2,000-30,000 represented by formula (1): [A]-X-(Y)m-(Z)n (wherein, A is a polymer part, X is Cp H2p or SCp H2p wherein p is an integer of 0-4, Y is -NHCO-Q-, -CONH-Q-, -COO-Q- or -OCO-Q wherein Q is a hydrocarbon type aromatic compound or a heterocyclic compound, m is 0 or 1, Z is -SO3 H or -O.SO3 H and n is an integer of 1-4). The photosensitive coloring composition contains an alkali-soluble binder, a photopolymerizable monomer, a photopolymerization initiator, pigment and the pigment dispersant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant for improving the dispersibility and dispersion stability of a pigment, and a photosensitive coloring composition containing the pigment dispersant. The present invention relates to a pigment dispersant suitably contained in a photosensitive coloring composition to be used, and to the photosensitive coloring composition.

[0002]

2. Description of the Related Art A color filter manufactured by photolithography using a colored resist material in which an organic pigment or an inorganic pigment is dispersed (hereinafter referred to as a "pigment-dispersion color filter") is used in the case where the pigment used is light or light. Since it is stable to heat and is patterned by photolithography, it has excellent positional accuracy and can achieve a large screen and high definition.

However, pigment dispersion color filters are
The quality is greatly affected by the dispersibility and dispersion stability of the pigment contained in the used colored resist material.
Specifically, when the dispersibility of the pigment in the colored resist material is insufficient, fringes (referred to as jagged edges) and surface irregularities occur in the formed colored resist film,
There are problems in that the color purity and dimensional accuracy of the manufactured pigment dispersion color filter are reduced, and the display contrast ratio due to the depolarizing effect is significantly deteriorated. Further, when the dispersion stability of the pigment in the colored resist material is poor, the uniformity of the film thickness in the coating process of the colored resist material is reduced in the manufacturing process of the pigment dispersion color filter, In this case, problems such as a decrease in photosensitivity and a decrease in alkali solubility in the developing step are likely to occur. Furthermore, when the dispersion stability of the pigment is poor, there is a problem that the components of the colored resist material aggregate with time, the viscosity increases, and the pot life becomes extremely short.

[0004] Further, organic pigments have a fundamental problem that they have low polarity and poor dispersibility and miscibility in an organic medium such as an organic solvent or a polymer compound.

In order to solve such a problem, conventionally, a dispersant such as a low molecular surfactant, a high molecular surfactant, and a pigment derivative has been used to improve the dispersibility of the pigment in the colored resist material. Was. In particular, the pigment derivative is one in which solubility in an organic medium is improved by adding a side chain to the pigment, and when used in combination with a polymer type surfactant, dispersibility of the pigment in the colored resist material is improved. Improved dispersion stability.

For example, in JP-A-11-189732, the dispersibility in an acrylic resin having a carboxylic acid group is improved by adding a basic pigment derivative having a dialkylamino group introduced therein.

[0007]

However, when the above-mentioned pigment derivative is used as a dispersant for a resin composition such as a colored resist material, the pigment derivative itself is colored. There is a problem that it is difficult to adjust to a desired color. In particular, in a field where spectral characteristics are regarded as important, such as a pigment dispersion color filter, adjustment of the color of a colored resist material is important, and the use of a pigment derivative is limited.

Further, since the various types of conventional dispersants described above do not have a photosensitive reactive group in the molecule, a large amount of non-photocurable materials such as binder resins and dispersants are contained in the colored resist material. In the case where the colored resist material is present, there arises a problem that the photosensitivity at the time of patterning the colored resist material by photolithography is reduced.

[0009] The present invention has been made to solve the above problems, and a pigment dispersant capable of improving the dispersibility and dispersion stability of a pigment without using a pigment derivative. And a photosensitive colored composition having excellent photosensitive sensitivity.

[0010]

The pigment dispersant according to claim 1 has a weight average molecular weight of 2 represented by the following chemical formula 1.
000 to 30,000 compounds. (In Chemical Formula 1, A is .X representing the polymer portion represents C _p H _2p or SC _p H _{2p, p} is 0
4 is an integer. Y is -NHCO-Q-, -CONH-
Q-, -COO-Q- or -OCO-Q-,
Q represents a hydrocarbon-based aromatic compound or a heterocyclic compound, and m is 0 or 1. Z is -SO ₃ H or -O
Represents SO ₃ H, and n is an integer of 1 to 4. )

[0011]

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According to the present invention, the sulfonic acid group or the monosulfate group in the chemical formula 1 has a property of easily adsorbing to the basic pigment, and furthermore, the sulfonic acid group or the monosulfate group has a weight average molecular weight. 2000-3000
Since it has only 0 terminal of the linear polymer, the dispersibility and dispersion stability of the pigment, especially the basic pigment, can be remarkably improved.

These effects can be explained as follows. Pigment adsorption is probably caused by acid-base interactions between the acidic groups of the dispersant and the pigment. As a polymer dispersant, a polymer containing carboxylic acid, which is an acidic group, is often used, but the carboxylic acid group is weakly acidic as compared with sulfonic acid or monosulfuric acid ester. Does not work effectively. Therefore, it is necessary to add a pigment derivative having a strong basic group such as a dialkylamino group in order to improve dispersibility. On the other hand, the pigment dispersant of the present invention has a highly acidic sulfonic acid group or monosulfate group, effectively acts as an adsorptive group even for weak basicity, and is more difficult to desorb. Can be improved. In addition, a random copolymer having a large number of acidic groups in one molecule is often used as a polymer dispersant, but the dispersibility may not be improved due to multi-point adsorption and crosslinking between a plurality of pigments. On the other hand, since the pigment dispersant of the present invention has a sulfonic acid group or a monosulfate group only at the terminal, it does not crosslink between pigments and has good dispersibility.

According to a second aspect of the present invention, in the pigment dispersant of the first aspect, the polymer portion represented by A contains a polymerizable reactive group.

According to the present invention, when the compound of the above formula 1 has a polymerizable reactive group such as a radical polymerization type reactive group, a pigment dispersant containing the compound is contained in the photosensitive coloring composition. Thereby, the photosensitivity can be improved.

According to a third aspect of the present invention, there is provided the pigment dispersant according to the second aspect, wherein the polymerizable reactive group is an ethylenically unsaturated double bond, and 0.1 to 1 g of the compound.
It is characterized by containing 5 mmol.

According to the present invention, the pigment has an ethylenically unsaturated double bond group which is a polymerizable reactive group, and further has 0.1 to 5 mmol per 1 g of the ethylenically unsaturated double bond group. The radical polymerization reactivity of the dispersant itself can be improved. As a result, the photosensitive sensitivity can be further improved by including the pigment dispersant in the photosensitive coloring composition.

According to a fourth aspect of the present invention, in the pigment dispersant according to any one of the first to third aspects, the polymer unit represented by A contains at least a structural unit represented by a chemical formula 2. It has a special feature. (In the chemical formula 2, a ₁ and a ₂ may be the same or different and each represents a hydrogen atom or a hydrocarbon group. R represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Represents.)

[0019]

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According to the present invention, since a part of the polymer part of the compound is acrylic, the pigment dispersant is contained in the photosensitive coloring composition so that it is contained in the ordinary photosensitive coloring composition. Compatibility with an acrylic alkali-soluble binder. Further, since a (meth) acryloyl group, which is a photopolymerizable radical reactive group, is present in the polymer portion, the photosensitivity can be further improved.

The invention according to claim 5 is characterized in that an alkali-soluble binder, a photopolymerizable monomer, a photopolymerization initiator,
A photosensitive coloring composition comprising a pigment and a pigment dispersant, wherein the pigment dispersant contains at least one compound having a weight average molecular weight of 2000 to 30,000 represented by Chemical Formula 1. (In the chemical formula 1, A
Represents a polymer part. X represents C _p H _2p or SC _p H _{2p, p} is an integer of 0-4. Y is -NHCO-Q-,
-CONH-Q-, -COO-Q-, or -OCO-
Represents Q-, Q represents a hydrocarbon-based aromatic compound or a heterocyclic compound, and m is 0 or 1. Z is -SO ₃
H or —O · SO ₃ H, and n is an integer of 1 to 4. )

[0022]

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According to the present invention, a pigment dispersant containing at least one compound having a weight average molecular weight of 2000 to 30000 represented by the chemical formula 1 improves the dispersibility and dispersion stability of the pigment. It can be preferably used as a photosensitive coloring composition in a field where spectral characteristics are important such as a color filter. Since the photosensitive coloring composition of the present invention contains such a pigment dispersant,
There is an advantage that a conventional pigment derivative is not required and the color can be easily adjusted to a desired color. Further, since the compound of the above formula 1 has an ethylenically unsaturated double bond group acting as a photopolymerizable radical reactive group, the photosensitive coloring composition can improve the photosensitivity.

According to a sixth aspect of the present invention, in the photosensitive coloring composition according to the fifth aspect, the pigment is a basic pigment.

According to the present invention, the sulfonic acid group or the monosulfate group in the compound of the above formulas 1 and 2 contained in the pigment dispersant has a property of being extremely easily adsorbed on the basic pigment. Since the compound has a weight average molecular weight of 2,000 to 30,000, the pigment dispersibility and dispersion stability of the photosensitive coloring composition can be significantly improved.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) The pigment dispersant will be described. The pigment dispersant of the present invention is represented by the following chemical formula 1,
The polymer part has a polymerizable reactive group and contains at least one compound having a weight average molecular weight (hereinafter, referred to as “Mw”) of 2,000 to 30,000. The compound of Formula 1 is
It is composed of a polymer part (A) having a polymerizable reactive group, a sulfonic acid group or a monosulfate group (Z), and a linking group thereof (X, Y). In the following chemical formula 1,
A represents a polymer part. X represents C _p H _2p or SC _p H _{2p, p} is an integer of 0-4. Y is -NHCO-Q
-, -CONH-Q-, -COO-Q-, or -OC
Represents OQ-, Q represents a hydrocarbon-based aromatic compound or a heterocyclic compound, and m is 0 or 1. Z is -S
Represents O ₃ H or —O · SO ₃ H, and n is an integer of 1 to 4.

[0027]

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In the chemical formula 1, examples of the hydrocarbon aromatic compound represented by Q in the formula include benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, anthraquinone and the like. Also,
Examples of the heterocyclic compound include thiophene, pyrrole, pyridine, indole, thiazole, quinoline, acridone, phenothiazine, quinazoline, carbazole, benzanthrone and the like. Further, the sulfonic acid group and the monosulfate group are important functional groups that play a role of adsorbing to the base portion of the pigment described below and greatly contribute to the improvement of the dispersibility and dispersion stability of the pigment.

The polymer portion has a predetermined molecular weight, forms a steric hindrance around the adsorbed pigment, and plays a role of improving the dispersibility and dispersion stability of the pigment. It has a group and plays a role as a photopolymerizable radical reactive group.

Examples of the polymerizable reactive group in the polymer constituting the polymer portion include radically polymerizable reactive groups, cationically polymerizable reactive groups, and photopolymerizable reactive groups such as thiol / ene addition type reactive groups. May be a polymerizable reactive group other than the photopolymerization reaction. In the present invention, as the photopolymerizable reactive group, an ethylenically unsaturated double bond group which is a radical polymerization type reactive group, for example, an acryloyl group or a methacryloyl group (hereinafter, when these are collectively referred to as “(meth)
Acryloyl group ". Are preferred.

The pigment dispersant of the present invention is obtained by including a pigment dispersant containing the above-mentioned compound 1 having a polymerizable reactive group, preferably a radical polymerization type reactive group in a polymer part, in a photosensitive coloring composition. Further, the photosensitive sensitivity of the photosensitive coloring composition can be further improved, and excellent resist characteristics can be exhibited.

It is preferable to select a polymer to be bonded to the polymer part in consideration of compatibility. As used herein, the compatibility refers to the compatibility between the compound of Formula 1 and the alkali-soluble binder. Specifically, a compound to which an acrylic polymer such as polymethyl methacrylate is bonded exhibits favorable compatibility with an acrylic alkali-soluble binder contained in a general photosensitive coloring composition.

At this time, it is more preferable that the polymer portion contains at least the structural unit represented by the chemical formula 2. In Chemical Formula 2, a ₁ and a ₂ may be the same or different and each represents a hydrogen atom or a hydrocarbon group, and R represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Is represented.

[0034]

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A pigment dispersant is formed by adding a structural unit in which a part of the polymer part is made of an acrylic compound to the compound of the formula (1), and the pigment dispersant is contained in the photosensitive coloring composition. The compatibility between the dispersant and the acrylic alkali-soluble binder contained in the usual photosensitive coloring composition can be improved. Further, since a (meth) acryloyl group, which is a photopolymerizable radical reactive group, is present in the polymer portion, the photosensitivity can be further improved.

When the polymerizable reactive group is an ethylenically unsaturated double bond group, the amount of the ethylenically unsaturated double bond group may be 0.1 to 5 mmol per 1 g of the compound of the above formula (1). preferable. As a result, the pigment dispersant itself has photopolymerization initiating ability, and by including this pigment dispersant in the photosensitive coloring composition, the photosensitivity relating to the photopolymerization reaction can be further improved. In the above case, if the amount is less than 0.1 mmol per 1 g, the photosensitivity is not sufficient. For example, when the photosensitive coloring composition is used as a colored resist material, the photosensitivity at the time of patterning by photolithography decreases. Sometimes.

It is preferable to bind to the polymer part a polymer having an Mw capable of adjusting the Mw of the compound 1 to 2,000 to 30,000 out of the above-mentioned polymers. If the Mw of the compound is less than 2,000, steric hindrance that can improve the dispersibility around the adsorbed pigment is difficult to form,
Agglomeration easily occurs, and sufficient dispersibility cannot be exhibited. On the other hand, when the Mw of the above compound exceeds 30,000, the alkali solubility of the photocurable layer (specifically, the colored resist film) formed from the photosensitive coloring composition containing the pigment dispersant of the present invention may decrease. is there.

(2) An example of a method for synthesizing a pigment dispersant will be described. The compound of Formula 1 contained in the pigment dispersant of the present invention preferably has at least a sulfonic acid group or a monosulfate group, and further preferably has an ethylenically unsaturated double bond. The synthesis route of a compound having both an acid group (sulfonic acid group or monosulfate group) and an ethylenically unsaturated double bond can be largely classified into an introduction reaction of an acid group and an introduction reaction of an ethylenically unsaturated double bond. Separated
Either reaction may be performed first.

First, a method for introducing a sulfonic acid group or a monosulfate group into a polymer terminal will be described.

The introduction of a functional group into the polymer terminal is carried out by radical polymerization using a polymerization initiator containing a functional group and / or a chain transfer agent. Here, the functional group introduced into the terminal is a sulfonic acid group, a sulfonic acid, a carboxyl group that can be derived into a monosulfate, a hydroxyl group,
It is a functional group such as an amino group, a hydrocarbon-based aromatic ring, and a heterocyclic ring.

Examples of the chain transfer agent capable of directly introducing a sulfonic acid group into the polymer terminal include mercapto compounds such as 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acid, 2-iodoethanesulfonic acid, Examples thereof include iodized alkyl sulfonic acid compounds such as 3-iodopropanesulfonic acid.

A carboxyl group, a hydroxyl group, which is a reactive group derivable to a sulfonic acid or a monosulfate,
Examples of the polymerization initiator containing an amino group include, for example, 2,2.
2′-azobis (2-cyanopropanol), 2,2 ′
-Azobis (2-cyanopentanol), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4
-Cyanovaleric chloride), 2,2'-azobis [2
-(5-methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazoline-
2-yl) propane], 2,2′-azobis [2-
(3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2′-azobis {2- [1- (2
-Hydroxyethyl) -2-imidazolin-2-yl]
Propane｝, 2,2′-azobis [2-methyl-N-
(2-hydroxyethyl) -propionamide] and the like, and derivatives thereof.

Similarly, as a chain transfer agent containing a carboxyl group, a hydroxyl group, an amino group, a hydrocarbon-based aromatic ring or a heterocyclic ring, which is a reactive group that can be induced to a sulfonic acid or a monosulfate, for example, a mercapto compound (For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid,
3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, −
Mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mecapluimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or a disulfide compound which is an oxidized form of these mercapto compounds.

Next, a specific reactive group (carboxyl group, hydroxyl group, amino group, hydrocarbon aromatic ring, heterocycle, etc.) introduced into the polymer terminal using the above-mentioned polymerization initiator and chain transfer agent is converted to sulfone Means for converting to an acid group or a monosulfate group will be described.

The polymer having a sulfonic acid group at the terminal is
The hydrocarbon-based aromatic ring or heterocyclic ring introduced into the terminal of the polymer can be synthesized by sulfonation by a known method using chlorosulfonic acid, concentrated sulfuric acid or the like.

Further, it can also be synthesized by reacting a carboxyl group at the terminal of the polymer with an amino organic sulfonic acid or a hydroxy organic sulfonic acid. Examples of the amino organic sulfonic acid include aminoethanesulfonic acid, sulfanilic acid and the like. Also, as the hydroxy organic sulfonic acid,
Hydroxyethanesulfonic acid, sulfenyl acid and the like can be mentioned. This reaction can be carried out by dehydration condensation using N, N'-dicyclohexylcarbodiimide,
During the reaction, it is necessary to block the sulfonic acid group with a basic group.

The polymer having a monosulfate group at the terminal is synthesized by a reaction between a polymer having a terminal hydroxyl group and a known sulfate esterification reagent (chlorosulfonic acid, aminosulfonic acid, sulfuric acid, oxygen trisulfide, etc.).

Next, means for introducing an ethylenically unsaturated double bond group into a polymer will be described.

The means for introducing an ethylenically unsaturated double bond group can be achieved by a conventionally known method (JP-A-3-18845, Japanese Patent Publication No.
-99538). Specifically, by using a monomer containing a reactive group such as a carboxyl group, a hydroxyl group, an amino group, or an epoxy group as a copolymerized monomer, a reactive group is introduced into the polymer molecule, and the reactivity is increased. The group is reacted with a compound having an ethylenically unsaturated double bond to introduce an ethylenically unsaturated double bond.

In the case of a polymer containing a carboxyl group in the molecule, for example, a method of reacting an ethylenically unsaturated group-containing compound having an epoxy group, an ethylenically unsaturated group-containing compound having a hydroxyl group, or the like can be mentioned.
Examples of such a compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, acrylic glycidyl ether, allyl-2-methylglycidyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate and the like.

The introduction of an ethylenically unsaturated double bond into a polymer containing a hydroxyl group can be carried out by using, for example, a compound such as isocyanatoethyl methacrylate, (meth) acrylic acid, or acrylic acid chloride.

The pigment dispersant contains conventional dispersants such as general low-molecular surfactants, high-molecular surfactants and pigment derivatives as long as the object of the present invention is not impaired. It is also possible to make it. As such a conventional dispersant, commercially available (meth) acrylic acid-based (co) polymer Polyflow No. 75, no. 90, no. 95
(Manufactured by Kyoeisha Yushi Kagaku Kogyo), Megafac F171, F
172, F173 (manufactured by Dainippon Ink and Chemicals), Florad Fc430, Fc431 (manufactured by Sumitomo 3M), Solspass 12000, 13240, 20000, 240
Solsperse dispersants (manufactured by Avicia) such as 00, 26000 and 28000, Disperse Big 111 and 16
1, 164, 165, 182, 2000, 2001 (manufactured by Big Chemie), Addispar PB711, PB411,
PB111, PB821, PB822 (manufactured by Ajinomoto Fine-Techno) and the like.

As the pigment of the present invention, various conventionally known inorganic or organic pigments can be used.

The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt or the like. Specifically, iron pigment, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or the like is used. Metal oxides,
And a composite oxide of the metal oxide.

Examples of the organic pigment include a color index (CI: The Society of Dysers).
and Colorist, Inc.), specifically, those having the following color index numbers. For example, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I.
I. Pigment Yellow 16, 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 60, C.I. I. Pigment Yellow 6
1, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 71, C.I. I. Pigment Yellow 73,
C. I. Pigment yellow 74, C.I. I. Pigment Yellow 81, C.I. I. Pigment yellow 83, C.I.
I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I.
Pigment Yellow 98, C.I. I. Pigment Yellow 100, C.I. I. Pigment Yellow 101, C.I. I.
Pigment Yellow 104, C.I. I. Pigment Yellow 106, C.I. I. Pigment Yellow 108, C.I.
I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment Yellow 113,
C. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment Yellow 11
7, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment Yellow 1
26, C.I. I. Pigment yellow 127, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I.
Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.
I. Pigment Yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment Yellow 154,
C. I. Pigment yellow 155, C.I. I. Pigment Yellow 156, C.I. I. Pigment Yellow 16
6, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment Yellow 1
80, C.I. I. Pigment Yellow 185; I. Pigment Orange 1, C.I. I. Pigment Orange 5,
C. I. Pigment Orange 13, C.I. I. Pigment Orange 14, C.I. I. Pigment Orange 16, C.I.
I. Pigment Orange 17, 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 4
6, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 61,
C. I. Pigment Orange 63, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, C.I.
I. Pigment Orange 73; I. Pigment Violet 1, C.I. I. Pigment Violet 19,
C. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I.
I. Pigment Violet 38; C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I.
I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11,
C. I. Pigment Red 12, C.I. I. Pigment Red 14, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17,
C. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23,
C. I. Pigment Red 30, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 37, C.I. I. Pigment Red 38,
C. I. Pigment Red 40, C.I. I. Pigment Red 41, C.I. I. Pigment Red 42, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 4
8: 2, C.I. I. Pigment Red 48: 3, C.I. I.
Pigment Red 48: 4, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Red 49: 2, C.I.
I. Pigment Red 50: 1, C.I. I. Pigment Red 52: 1, C.I. I. Pigment Red 53: 1,
C. I. Pigment Red 57, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 57: 2,
C. I. Pigment Red 58: 2, C.I. I. Pigment Red 58: 4, C.I. I. Pigment Red 60:
1, C.I. I. Pigment Red 63: 1, C.I. I. Pigment Red 63: 2, C.I. I. Pigment Red 6
4: 1, C.I. I. Pigment Red 81: 1, C.I. I.
Pigment Red 83, C.I. I. Pigment Red 8
8, C.I. I. Pigment Red 90: 1, C.I. I. Pigment Red 97, C.I. I. Pigment Red 101,
C. I. Pigment Red 102, C.I. I. Pigment Red 104, C.I. I. Pigment Red 105, C.I.
I. Pigment Red 106, C.I. I. Pigment Red 108, C.I. I. Pigment Red 112, C.I. I.
Pigment Red 113, C.I. I. Pigment Red 1
14, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 14
4, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150,
C. I. Pigment Red 151, 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 172, C.I. I.
Pigment Red 174, C.I. I. Pigment Red 1
75, C.I. I. Pigment red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 17
8, C.I. I. Pigment Red 179, C.I. I. Pigment Red 180, C.I. I. Pigment Red 185,
C. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I.
I. Pigment Red 193, C.I. I. Pigment Red 194, C.I. I. Pigment Red 202, C.I. I.
Pigment Red 206, C.I. I. Pigment Red 2
07, C.I. I. Pigment red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 21
5, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 224,
C. I. Pigment Red 226, C.I. I. Pigment Red 242, C.I. I. Pigment Red 243, C.I.
I. Pigment Red 245, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I.
Pigment Red 264, C.I. I. Pigment Red 2
65; I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15:
4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 60; C.I. I. Pigment Green 7,
C. I. Pigment Green 36; I. Pigment Brown 23, C.I. I. Pigment Brown 25;
I. Pigment Black 1, Pigment Black 7, and the like.

The dispersant of the present invention can exhibit particularly excellent dispersibility, particularly for pigments having a basic surface. This is due to the strength of the interaction between the acidic groups in the dispersant and the basic part of the pigment. Examples of the pigment having a basic surface include an inorganic metal oxide having a basic OH group, a pigment having a basic N atom in the structural formula of the pigment, and a pigment surface-treated with a basic substance.

Examples of the pigment having a basic N atom in the structural formula of the pigment include C.I. I. Pigment Yellow 11, 24,
108, 109, 110, 138, 139, 150, 1
51, 154, 167; I. Pigment Orange 3
6; I. Pigment Red 122, 150, 17
1, 175, 177, 209; I. Pigment Violet 19, 32; I. Pigment Blue 16,
22, 66 and the like, but are not limited thereto.

The presence or absence of basicity of the inorganic metal oxide and the surface-treated pigment is determined by using the coloring materials 61 and 692 (198).
It can be evaluated by the non-aqueous potentiometric titration method described in 8).

(3) The photosensitive coloring composition will be described. The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing an alkali-soluble binder, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a pigment dispersant. In addition, a solvent is naturally included. Here, the pigment dispersant is the above-described pigment dispersant of the present invention, represented by Chemical Formula 1,
It contains at least one compound having a weight average molecular weight of 2,000 to 30,000.

As a method for preparing the photosensitive coloring composition, a coloring liquid comprising a pigment, a pigment dispersant and a solvent is first prepared in order to make it easy to disperse the aggregated pigment. Binder, photopolymerizable monomer,
It is prepared by mixing at least a photopolymerization initiator and a solvent. In the above-mentioned preparation of the coloring liquid, the pigment dispersant and the pigment are previously homogeneously mixed and then added to the solvent, or the pigment is added after the pigment dispersant is mixed in the solvent, or the pigment and the non-aqueous solvent are added. Can be adjusted by adding a pigment dispersant to the dispersion system consisting of For the adjustment, any dispersing machine may be used, and examples thereof include a ball mill, a sand mill, a visco mill, a roll mill, a kneader, an attritor, a high-speed mixer, and a homomixer.

As the pigment dispersant, the above-described pigment dispersant of the present invention is used, and is added in an amount of 5 to 80% by weight, preferably 10 to 40% by weight based on the pigment. If the amount is less than 5% by weight, the dispersion stability is insufficient, and the viscosity increases with time and the pigment sedimentation occurs. However, the optimum amount of the pigment dispersant to be added is appropriately adjusted depending on the type of pigment used, the type of solvent, the combination of resist components, and the like. As the pigment dispersant, the compounds represented by Chemical Formulas 1 and 2 may be used alone or in combination with the other pigment dispersants described above, as long as the purpose is not impaired.

Since the pigment dispersant has a sulfonic acid group or a monosulfate group, the photosensitive coloring composition containing the pigment dispersant is exposed to light to form a cured film such as a colored resist film. Later, there is also a remarkable effect that the alkali solubility of the cured film can be improved by the sulfonic acid group or monosulfate group bonded thereto.

The conventional dispersant does not have a photosensitive group in its molecule and does not act on the curing of the resist, but a dispersant having a polymerizable reactive group, for example, an ethylenically unsaturated double bond group is not used. It has photocurability, and when used for a pigment-dispersed resist, it can improve the sensitivity of the resist and improve the deterioration of the pattern shape.

As the pigment, the above-mentioned organic pigments, particularly those having a basic surface, are preferably used. In addition to the organic pigment, an inorganic pigment such as carbon black can be added as needed. In such a case, it is preferable to appropriately select and blend a pigment dispersant that suitably disperses the added other pigment.

Since the alkali-soluble binder greatly affects the dispersibility of the pigment and the compatibility with the photopolymerizable monomer or the photopolymerization initiator, an appropriate binder is appropriately selected and used. In the selection of an alkali-soluble binder, considerations that have conventionally been taken into account include excellent solubility in an alkali developing solution and solubility in an organic solvent, and in the pattern forming process including exposure and development, a long time is required for an alkali developing solution or a cleaning solution. Even if it is exposed for a long time, the adhesiveness to the substrate is excellent.

As the alkali-soluble binder satisfying such conditions, benzyl methacrylate, (meth)
There are acrylic acid esters, (meth) acrylic acid, and multi-component copolymers with other monomers.

Further, when the photosensitive colored composition is used as a colored resist material for a color filter, a reaction double bond is introduced for increasing the sensitivity, and an acid value is adjusted for a suitable alkali developing solution resistance. It is necessary to adjust the weight average molecular weight in order to prevent a decrease in pigment cohesion, composition life, substrate adhesion, pattern formability, coating film smoothness, etc., as described in JP-A-2000-298339. A multi-component copolymer containing a (meth) acryloyloxy group is effective. The alkali-soluble binder described in JP-A-2000-298339 is a product obtained by partially reacting a structural unit represented by the following chemical formulas 3 and 4 with a (meth) acryloyloxyalkyl isocyanate compound via its carboxyl group or hydroxyl group. It is a specific copolymer resin as a constituent unit. Here, R in the following formula represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ₁ represents 2 carbon atoms.
Represents an alkylene group of 4 to 4. A and b represent integers corresponding to the respective mol%.

[0068]

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[0069]

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The content of such an alkali-soluble binder is preferably from 10 to 60% by weight of the total solids in the photosensitive coloring composition.

The photopolymerizable monomer is a polyfunctional acrylate or a polyfunctional methacrylate having three or more double bond functional groups in one molecule (hereinafter, when an acrylate compound and a methacrylate compound are simultaneously shown, "( (Meth) acrylate) can be preferably used. When the number of functional groups of the polyfunctional (meth) acrylate exceeds 6, the photopolymerization reaction easily occurs, so that the cured film itself becomes brittle,
It may not be possible to obtain sufficient strength. On the other hand, if the number of functional groups is less than 4, the photopolymerization reaction is insufficient, and the strength of the cured film may be insufficient. Therefore, in practice, it is only necessary to have a functional group consisting of three or more double bond groups. In particular, dipentaerythritol penta (meth) acrylate having five double bond groups and derivatives thereof can be preferably used.

Other photopolymerizable monomers include, for example, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexaacrylate, hexanediol di (meth) acrylate,
Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, polyester acrylates,
Alternatively, those obtained by subjecting a polyfunctional alcohol such as glycerin to an addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated the same may be mentioned. Further, the above-mentioned acrylate and methacrylate can be used alone or in combination. In addition to the monomer, a dimer or trimer prepolymer can also be used. The content of such a photopolymerizable monomer,
It is 10 to 50% by weight of the total solids in the photosensitive coloring composition.

The photopolymerization initiator has a function of causing a radical polymerization reaction by causing a cleavage or a hydrogen abstraction reaction when irradiated with light. As the photopolymerization initiator, benzophenone derivatives such as benzoin and benzophenone, or derivatives thereof such as esters, xanthone and thioxanthone derivatives, chloromethyl heterocyclic compounds as halogen-containing compounds, chloromethylbenzophenones, triazines, and fluorenones , Haloalkanes, redox couples of a photoreducing dye and a reducing agent, organic sulfur compounds, peroxides, and the like, and these can be used alone or in combination of two or more. In the case of merging, it is preferable not to hinder the absorption spectral characteristics.

An amine-based or quinone-based photopolymerization accelerator can be added to the photopolymerization initiator, if necessary, for the purpose of improving the photosensitivity. The content of the photopolymerization initiator and the photopolymerization accelerator is preferably from 0.1 to 20% by weight based on the total solids of the photosensitive coloring composition.

The solvent is shown below in consideration of the applicability of the photosensitive coloring composition, the solubility in polymers and monomers such as alkali-soluble binders, pigment dispersants or photopolymerization initiators, and the dispersibility of pigments. One or more solvents can be appropriately selected and used. In particular, it is desirable to include one or more polyhydric alcohols or derivatives thereof. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol isoamyl ether, methoxymethoxy ether,
Ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether, 1-butoxyethoxypropanol, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, methoxy Butyl acetate, methyl amyl ketone, methyl lactate, ethyl lactate, methyl -α- hydroxyisobutyrate, methyl -β- methoxy isobutyrate and the like.

In addition to the above components, a sensitizer, a coating property improving agent, and the like can be appropriately added to the photosensitive coloring composition. The coating film property improver is a conventionally known one having an action of suppressing the tackiness of the colored layer after curing caused by the type of the alkali-soluble binder. In addition, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or the like can be added to the composition in order to impart adhesion to a substrate on which the photosensitive coloring composition is applied.

The photosensitive coloring composition of the present invention can be applied on a substrate by a known method, dried, and then cured by exposure to light. Specific examples of the coating method include a spinner, a wheeler roller coater, a curtain coater, a knife coater, a bar coater, and an extruder. At the time of exposure, a light source is selected according to the photosensitivity of the photosensitive coloring composition, and a known light source such as an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an argon laser can be used. As a developing solution for developing the pattern-exposed colored layer, an alkaline aqueous developer such as sodium hydroxide is used. The photosensitive coloring composition of the present invention is used for forming red, green and blue colored pixels on a transparent substrate. Then, a transparent electrode layer is further provided on the surface, and a pigment dispersion color filter is manufactured.

The photosensitive coloring composition of the present invention described above contains the above-described pigment dispersant of the present invention.
Excellent pigment dispersibility and dispersion stability. As a result, it can be preferably used as a photosensitive coloring composition in a field where spectral characteristics based on the color of the pigment are important.

Particularly when used as a colored resist material, it is not necessary to use a conventional pigment derivative, so that the color can be easily adjusted and the pigment dispersant also contains a photosensitive group. Therefore, the photosensitive sensitivity during patterning does not decrease. The pigment dispersion color filter manufactured using such a colored resist material is excellent in color purity and dimensional accuracy, and can suppress deterioration of the display contrast ratio due to depolarization. Also, in the pigment dispersion method color filter manufacturing process, it is necessary to improve the film thickness uniformity in the application step of the colored resist material, the photosensitivity in the exposure step, and the alkali solubility in the development step. In addition to this, there is an effect that the change in viscosity with time is small and the pot life is prolonged.

[0080]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. “Parts” in the examples means parts by weight.

(Example 1) <Synthesis of polymethyl methacrylate (D-1) containing sulfonic acid group at one end> Polymerization temperature into a mixed solution composed of 100 g of methyl methacrylate and 200 g of tetrahydrofuran (hereinafter abbreviated as THF). At 65 ° C. in a nitrogen atmosphere, 1.0 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 4.0 g of 1-naphthalene thiol.
And 20 g of THF was added dropwise over 30 minutes, and the mixture was reacted for 8 hours to perform radical chain transfer polymerization. After cooling the reaction solution, isopropanol 1000m
The solution was added dropwise with stirring. The supernatant was removed by decantation, the polymer precipitated with isopropanol was washed, and the polymer collected by filtration was dried under reduced pressure. The weight average molecular weight (converted to styrene by GPC measurement) of the polymer was 8,000.

40 g of the obtained polymethyl methacrylate having a naphthalene ring at one end was mixed with 100 g of chloroform.
Was cooled in an ice bath, and a solution of 2.3 g of chlorosulfonic acid and 10 g of chloroform was gradually added dropwise to the solution under a nitrogen atmosphere. After the addition, the mixture was stirred at room temperature for 3 hours.
The reaction solution was added dropwise to 1000 ml of n-hexane while stirring. The supernatant was removed by decantation, and the precipitated polymer was washed with isopropanol. The polymer collected by filtration and dried was dissolved in 100 ml of THF, and
-Purified by reprecipitation in hexane. The polymer collected by filtration was dried under reduced pressure. The acid value of the obtained polymer is 14 m
gKOH / solid content was 1 g.

(Example 2) <Synthesis of methacryloyl group-containing polymethyl methacrylate (D-2) having a sulfate group at one end> Polymerization temperature 65 ° C./nitrogen stream into a mixture of 100 g of methyl methacrylate and 200 g of THF Below, 1.0 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN),
A mixed solution consisting of 1.2 g of 2-mercaptoethanol and 20 g of THF was added dropwise over 30 minutes, and the mixture was further reacted for 8 hours. After cooling the reaction solution, isopropanol 1000
The solution was added dropwise to the solution while stirring. The supernatant was removed by decantation, and the precipitated polymer solid was washed with isopropanol. The polymer collected by filtration was dried under reduced pressure. The hydroxyl value of the polymer is 13 mgKOH / g
And the weight average molecular weight (converted to styrene by GPC measurement) was 8,800.

The obtained polymethyl methacrylate containing one terminal hydroxyl group (40 g) was mixed with dichloromethane (200 m).
and cooled the solution to 2-5 ° C. Next, a solution of 2.9 g of chlorosulfonic acid dissolved in 20 g of dichloromethane was gradually added at such a rate that the temperature did not exceed 20 ° C. The generated gaseous hydrogen chloride was absorbed by the aqueous sodium hydroxide solution. After the addition of chlorosulfonic acid was completed, the mixture was further stirred for 3 hours.

The reaction solution was added dropwise to 1000 ml of n-hexane while stirring. The supernatant was removed by decantation, and the solid polymer was washed with isopropanol. Then, the filtered and dried polymer was washed with THF10.
It was dissolved in 0 ml and purified by reprecipitation in n-hexane. The polymer collected by filtration was dried under reduced pressure. The acid value of the polymer was 15 mg KOH / g solid.

(Example 3) <Synthesis of methacryloyl group-containing polymethyl methacrylate (D-3) having sulfonic acid group at one terminal> A mixed solution comprising 80 g of methyl methacrylate, 20 g of 2-hydroxyethyl methacrylate and 200 g of THF was added. A mixture of 1.0 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN), 4.0 g of 2-naphthalenitol and 20 g of THF was added at a polymerization temperature of 65 ° C. under a nitrogen stream.
It was added dropwise over a period of 0 minutes, and then reacted for 8 hours. The resulting methyl methacrylate-hydroxyethyl methacrylate copolymer solution having a carboxylic acid group at one end is added with 3,5-
0.5 g of g-tert-butyl-4-hydroxytoluene (hereinafter abbreviated as BHT) is added, and 17.9 g of triethylamine and 26.5 g of methacrylic acid chloride are added so that the temperature of the polymer solution is kept at 25 ° C. or lower. Was added dropwise under stirring. After the addition, the mixture was heated to 60 ° C. and stirred for 2 hours. After cooling the reaction solution, isopropyl alcohol 1000
The solution was added dropwise to the solution while stirring. The supernatant was removed by decantation, and the precipitated polymer was washed with isopropyl alcohol. The precipitated polymer was collected by filtration, dried, dissolved in 100 ml of tetrahydrofuran, and reprecipitated in isopropyl alcohol for purification. The polymer collected by filtration was dried under reduced pressure. The weight average molecular weight of the polymer is 8500
Met.

A solution prepared by dissolving 40 g of the polymethyl methacrylate having a methacryloyl group having a naphthalene ring at one end in 100 g of chloroform was cooled in an ice bath, and 2.0 g of chlorosulfonic acid and 10 g of chloroform were added to the solution under a nitrogen atmosphere. Was slowly added dropwise. After the addition, the mixture was stirred at room temperature for 3 hours. The reaction solution was n-hexane 100
It was added dropwise to 0 ml with stirring. The supernatant was removed by decantation, and the solid polymer was washed with isopropanol. Then, the polymer was added to THF100m
and purified by reprecipitation in n-hexane. The polymer collected by filtration was dried under reduced pressure. The acid value of the obtained polymer was 12 mgKOH / g of solid content. Also,
When the amount of the introduced methacryloyl group was quantified by 1H-NMR analysis, it was 1.5 mmol per 1 g of the polymer.

(Comparative Example 4) <Synthesis of methacryloyl group-containing polymethyl methacrylate (D-4) having a carboxylic acid group at one end> From 80 g of methyl methacrylate, 20 g of 2-hydroxyethyl methacrylate and 200 g of 3-methoxybutyl acetate 1.0 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) under a nitrogen stream at a polymerization temperature of 70 ° C.
A mixed solution of 2.7 g of 3-mercaptopropionic acid and 20 g of 3-methoxybutyl acetate was added dropwise over 30 minutes, and the mixture was reacted for 8 hours. 0.5 g of BHT was added to the obtained methyl methacrylate-hydroxyethyl methacrylate copolymer solution having a carboxylic acid group at one end, and 2-methacryloyloxyethyl isocyanate 2 was added.
3.9 g, dibutyltin laurate 0.1 g and acetic acid 3-
A mixture consisting of methoxybutyl g was added dropwise over 30 minutes. The progress of the reaction was monitored by IR (infrared absorption spectrum), and the reaction was continued until the peak at 2200 cm ^{-1 due to} the isocyanate group disappeared. The reaction solution was added dropwise to 1000 ml of isopropanol with stirring. The supernatant was removed by decantation. Further, the precipitated polymer was washed with isopropanol. The polymer was collected by filtration, dried, dissolved in 100 ml of THF, and reprecipitated in isopropanol for purification. The polymer collected by filtration was dried under reduced pressure. The acid value of the obtained polymer was 11 mg KO.
H / solid content: 1 g; weight average molecular weight: 9200; methacryloyl group introduction amount: 1.2 mmol / g solid content.

(Preparation of Pigment Dispersion) Pigment Dispersion G-1
Is a green pigment (CI Pigment Green 36): 9
0 parts by weight and a yellow pigment (CI Pigment Yellow 1)
38): 40 parts by weight, a dispersant (one-terminal sulfonic acid group-containing polymethyl methacrylate (D-1) obtained in Example 1): 50 parts by weight, and hydroquinone monomethyl ether: 0.02 parts by weight. And propylene glycol monomethyl ether acetate: 820 parts by weight, and the mixture was sufficiently dispersed and prepared by a sand mill.

Pigment dispersions G-2 to G-4 were prepared in the same manner as in G-1 except that the polymers obtained in Examples 2 to 4 were used as dispersants.

(Measurement of Particle Size Distribution) The pigment dispersion obtained above was diluted, and the particle size of the pigment in the dispersion was measured with a particle size analyzer (Microtrack 9340UPA, manufactured by Nikkiso Co., Ltd.) to determine the dispersing ability. evaluated.

(Preparation of photosensitive coloring composition) The green photosensitive coloring composition (1) was prepared by mixing the above-mentioned green pigment dispersion G-1: 67.
Parts by weight and a benzyl methacrylate-styrene-methyl methacrylate-methacrylic acid copolymer (unit ratio (molar ratio) of each component is benzyl methacrylate: styrene: methyl methacrylate: methacrylic acid = 5/1 /
3/1 (molar ratio), weight average molecular weight 20,000, solid content 30 parts, propylene glycol monomethyl ether acetate solution 70 parts): 17 parts by weight, and dipentaerythritol pentaacrylate (DPPA, manufactured by Nippon Kayaku Co., Ltd.): 4 parts by weight, 3 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals), and 9 parts by weight of propylene glycol monomethyl ether acetate were stirred and mixed at room temperature to prepare.

The green photosensitive compositions (2) to (4) were prepared in the same manner as the green pigment dispersion G-
2 to G-5, and the others were prepared in the same manner as in the green photosensitive composition (1) described above.

(Preparation of Colored Layer) The prepared photosensitive colored composition was applied on a glass substrate by a spin coater (film thickness: 1.5 μm), and then dried on a hot plate at 80 ° C. for 3 minutes. Next, a photomask was arranged at a distance of 100 μm from the coating film, and only a region corresponding to the region where the colored layer was formed was irradiated with ultraviolet light by a proximity meter using an ultra-high pressure mercury lamp to ²⁰ to 500 mJ / m ² . Next, development was performed in a 0.05% aqueous solution of potassium hydroxide to remove only the uncured portion of the coating film of the photosensitive coloring composition. Thereafter, heat treatment was performed by placing the post-bake in an atmosphere at 200 ° C. for 30 minutes.

(Results) The evaluation results of the dispersibility of the obtained pigment dispersion, the dispersibility in the resist state, and the development characteristics (edge shape) of the photosensitive coloring composition are shown in the following table.

In Examples and Comparative Examples, each pigment dispersion was prepared using a pigment dispersant under the conditions shown in the following table, and the results of comparison of the 50% particle diameter of the pigment dispersion and the development characteristics of the resist were shown. It is shown in the table below.

[0097]

[Table 1]

The stability of the photosensitive coloring composition was judged by the change in viscosity of the resist on the day of preparation and two weeks after the preparation. In Table 1, 変 化: change in viscosity within 5 cps after the day and two weeks, ×: on the day And two weeks later, the change in viscosity was 5 cps or more.

From the results in the table, it is clear that the pigment dispersant of the present invention can disperse the pigment in a finely divided state. Furthermore, the photosensitive coloring composition prepared using the pigment dispersant of the present invention has excellent stability, high sensitivity,
Excellent in fine pattern formation.

[0100]

According to the pigment dispersant of the present invention, the dispersibility and dispersion stability of the pigment can be remarkably improved. This can contribute to improvement in sensitivity.

According to the photosensitive coloring composition of the present invention, since the pigment dispersant of the present invention described above is contained, the pigment has excellent dispersibility and dispersion stability. As a result, it can be preferably used as a photosensitive coloring composition in a field where spectral characteristics based on the color of the pigment are important. Especially when used as a colored resist material, it is not necessary to use a conventional pigment derivative, so that color adjustment is easy, and since the pigment dispersant also contains a photosensitive group, patterning is performed. Does not cause a decrease in photosensitivity during the process. The pigment dispersion color filter manufactured using such a colored resist material is excellent in color purity and dimensional accuracy, and can suppress deterioration of the display contrast ratio due to depolarization. In the process of manufacturing a pigment filter by a pigment dispersion method, it is necessary to improve the film thickness uniformity in the application step of the colored resist material, the photosensitivity in the exposure step, and the alkali solubility in the development step. In addition to this, there is an effect that the change in viscosity with time is small and the pot life is prolonged.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁷ identifications FI theme coat Bu (reference) C09B 67/20 C09B 67/20 L G02B 5/20 101 G02B 5/20 101 5/22 5/22 (72 ) Inventor Masayuki Ando 1-1-1 Kagamachi, Ichigaya-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. (reference) 2H048 BA02 BA45 BA47 BA48 BB02 BB42 CA04 CA14 CA19 4D077 AA01 AB03 AC05 BA02 DD03Y DD18Y DE02Y DE04Y DE09Y DE24Y DE29Y 4J011 AC04 PA02 PA22 PA69 PB25 PB39 QA12 QA22 QB03 RA03 SA21 SA31 SA64 SA73 SA76 SA78 SA83 UA01 VA01 WA01 4J027 AA01 BA07 BA19 BA23 BA24 CA03 CA11 CA21 CB10 CC05 CD10

Claims (6)

[Claims] The weight average molecular weight represented by the chemical formula 1 is 2
A pigment dispersant comprising at least one compound of 000 to 30,000. (In Chemical Formula 1, A is .X representing the polymer portion represents C _p H _2p or SC _p H _2p,
p is an integer of 0-4. Y is -NHCO-Q-, -C
ONH-Q-, -COO-Q-, or -OCO-Q-
And Q represents a hydrocarbon-based aromatic compound or a heterocyclic compound, and m is 0 or 1. Z represents -SO ₃ H or -O · SO ₃ H, n is an integer of 1 to 4. ) 2. The pigment dispersant according to claim 1, wherein the polymer portion represented by A contains a polymerizable reactive group. 3. The pigment dispersant according to claim 2, wherein the polymerizable reactive group is an ethylenically unsaturated double bond and is contained in an amount of 0.1 to 5 mmol per 1 g of the compound. 4. The polymer represented by A has a chemical formula 2
The pigment dispersant according to any one of claims 1 to 3, comprising at least a structural unit represented by the following formula:
(In the chemical formula 2, a ₁ and a ₂ may be the same or different, and each represent a hydrogen atom or a hydrocarbon group.
Represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. ) 5. A photosensitive coloring composition comprising an alkali-soluble binder, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a pigment dispersant, wherein the pigment dispersant is represented by the following chemical formula 1. A photosensitive colored composition comprising at least one compound having a weight average molecular weight of 2,000 to 30,000. (In the chemical formula 1, A represents a polymer part. X represents C _p H _2p or S
Represents C _p H _{2p, p} is an integer of 0-4. Y is -NH
Represents CO-Q-, -CONH-Q-, -COO-Q-, or -OCO-Q-, wherein Q represents a hydrocarbon-based aromatic compound or a heterocyclic compound, and m is 0 or 1.
Z represents -SO ₃ H or -O · SO ₃ H, n is 1 to
4 is an integer. ) 6. The photosensitive coloring composition according to claim 5, wherein the pigment is a basic pigment.