KR20100037002A - Pigment dispersion for color filter and pigment dispersed resist composition for color filter containing the same - Google Patents

Abstract

PURPOSE: A pigment dispersion for a color filter is provided to ensure excellent pigment dispersibility, mobility and dispersion stability, and to improve coating competence and development property of a pigment dispersion resist composition. CONSTITUTION: A pigment dispersion for a color filter comprises pigment, pigment dispersant, and organic solvent. The pigment dispersant is obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring within molecule, with an active hydrogen group having a carbazole ring and/or an azobenzene skeleton.

Description

Pigment dispersion for color filters and pigment dispersion resist composition for color filters containing the same {PIGMENT DISPERSION FOR COLOR FILTER AND PIGMENT DISPERSED RESIST COMPOSITION FOR COLOR FILTER CONTAINING THE SAME}

This invention relates to the pigment dispersion for color filters which enables manufacture of a color filter and a black matrix used for a color liquid crystal display device, etc., and the pigment dispersion resist composition for color filters containing the same.

The color liquid crystal display device has excellent features such as light weight in structure and low power consumption. In addition, the recent high technology development power has been applied, and the improvement in image quality, such as high brightness, high precision, and high contrast, is continuously pursued. As a result, it is recognized that the total balance of performance is high in that it can always exhibit stable performance in various fields from the small screen to the large screen, which leads to the expansion of the use.

However, in order to further expand the spread of color liquid crystal display devices, there are a number of technical problems that must be overcome while competition with existing PDPs and the practical use of image display devices using organic EL have entered the field of view.

For example, one of these challenges is the further improvement of color reproducibility. In order to improve color reproducibility, basically, high color purity and contrast are required in each color pixel of RGB displayed on a display.

In a color liquid crystal display device, first, light generated from a light source such as a backlight is white light, and the color of the RGB colored film is installed after controlling the amount of light by the shutter action of the liquid crystal for each portion corresponding to the pixel of each color of RGB. By passing through the filter, it is colored to display pixels of each color on the display. Therefore, by the method of coloring such white light with a color filter (colored film), in order to raise the color purity of colored light, it is indispensable that the color purity of the colored film provided with the color filter itself is high. Moreover, when coarse particle exists in said colored film, the polarization property of the light which permeate | transmits is disturbed (fragmentation), and as a result, contrast falls. Therefore, it is necessary not to contain crude particle in a colored film.

In recent years, pigments have been used as color materials in colored coatings. Therefore, in order to improve the factors such as color development (saturation), transparency (brightness), etc. according to the color purity, and also suppress the fragmentation, the pigment must be dispersed more finely.

In addition, when the above-mentioned colored film is superimposed on the color filter, the color purity decreases due to osmosis, and when there is a gap, the contrast decreases due to leakage of light. Therefore, in order to prevent these, a black matrix is provided for shielding between the colored films. Therefore, performance such as the formability of the black matrix is also greatly affected by the improvement of color reproducibility.

The black matrix is formed by forming a light shielding film in a lattice shape or a band shape. The light shielding film is as thin as possible, its width is thin (also called thin line), and the edge of the film is required to be sharp and straight. In recent years, the coating agent which used black pigments, such as carbon black, as a light shielding material, is used for formation of a black matrix. In the coating agent for forming a black matrix, in order to maintain high light-shielding property with a thin film, it is necessary to raise the content concentration of a light-shielding material. Moreover, such a coating agent is a type hardened | cured by an ultraviolet-ray etc., and the fine black matrix is formed through the image development process which removes an uncured part. Therefore, in order to raise the formability of the film with a thin line and an edge, and high linearity, hardened part remains reliably and the development ability which can remove a non-hardened part reliably must also be favorable.

However, when a pigment is disperse | distributed in a coating agent, re-agglomeration tends to occur with the increase of the surface area of a pigment, and there exists a tendency for dispersion stability to fall. The same applies to the RGB colored pigment or the black pigment. And since the refinement | miniaturization and high density | concentration of the pigment particle which are requested | required above are connected with the increase of surface area, the problem that the dispersion stability of a pigment falls is solved.

Moreover, the coating agent which contains a pigment in high density | concentration, especially the coating agent for black matrix formation which uses carbon black with a large specific surface area as a light-shielding material tends to reduce coating ability and image development characteristics, and the countermeasure is also needed.

In order to solve these problems, there is a method of improving the leakage (affinity) between the dispersion medium and the pigment surface in the coating agent, and various pigment dispersants have been studied as the means.

For example, the use of a polymeric dispersant comprising a polyester or polyether having a basic functional group (see, for example, Patent Document 1), 30 to 70% by weight of a copolymer derived from ethylene oxide and / or propylene oxide and basic The use of the polymeric dispersing agent of the weight average molecular weights 5,000-40,000 containing a functional group (for example, refer patent document 2) is proposed.

[Patent Document 1] Japanese Unexamined Patent Publication No. 10-082908

[Patent Document 2] Japanese Unexamined Patent Publication No. 10-246812

The technique of patent document 1, 2 improves pigment dispersibility, dispersion stability, and fluidity to some extent. But it was never completely improved and there was a limit. Moreover, coating aptitude and image development characteristics still had room for improvement.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pigment dispersion resist composition for color filters having excellent coating suitability and development characteristics by using a novel pigment dispersion for color filters excellent in pigment dispersibility, fluidity and dispersion stability, and the pigment dispersion for color filters. To provide.

The present invention is characterized by using a polyurethane dispersant having an isocyanurate ring, a carbazole ring and / or an azobenzene skeleton as a pigment dispersant for dispersing the pigment. In particular, when an isocyanate compound having an isocyanurate ring in the molecule and a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton are reacted in a specific amount, the effect is more excellent.

That is, this invention is a pigment dispersion for color filters containing (1) a pigment, a pigment dispersant, and the organic solvent, The said pigment dispersant is a compound which satisfy | fills following condition 1, The pigment dispersion for color filters characterized by the above-mentioned. It is about.

Condition 1: A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton in the molecule of the obtained compound. The number of carbazole rings and azobenzene skeletons is based on the sum of three numbers of isocyanate groups derived from isocyanate compounds having isocyanurate rings and urethane bonds and urea bonds formed by reaction of the isocyanate groups with active hydrogen groups. 15 to 85%.

Moreover, this invention relates to the pigment dispersion for color filters as described in said (1) which further contains (2) pigment dispersion adjuvant.

Moreover, this invention relates to the pigment dispersion resist composition for color filters characterized by containing (3) the pigment dispersion for color filters as described in said (1) or (2).

The pigment dispersion for color filters of this invention has the outstanding pigment dispersibility, fluidity, and dispersion stability. Moreover, the pigment dispersion resist composition for color filters containing this pigment dispersion is excellent in coating ability and image development characteristics.

Hereinafter, the pigment dispersion for color filters (henceforth a "pigment dispersion") of this invention is demonstrated in detail.

The pigment dispersion of the present invention contains a polyurethane-based dispersant having an isocyanurate ring, a carbazole ring and / or an azobenzene skeleton as an pigment and a pigment dispersant, and an organic solvent. First, the constituent materials will be described below.

<Material of Pigment Dispersion>

(Pigment)

As the pigment (pigment suitable for colored images such as red, green, blue, black, etc.) in the present invention, C.I. Pigment Red 19, 38, 43, 88, 122, 123, 144, 149, 166, 168, 177, 178, 179, 188, 190, 207, 208, 209, 216, 224, 226, 242, 254, 264 Red pigment such as: CI Pigment blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64 and the like; C.I. Green pigments such as pigment green 7, 10, and 36; C.I. Pigment Yellow 24, 81, 83, 93, 95, 97, 108, 109, 110, 117, 123, 128, 137, 138, 139, 150, 153, 154, 166, 168, 180, 185 Pigments; Purple pigments such as C.I. pigment violet 19, 23, 29, 30, 31, 37, 88, etc .; C.I. Orange pigments such as pigment orange 31, 38, 40, 43, 61, 71; Black pigments, such as carbon black, etc. can be used.

In the present invention, in order to obtain a red color pigment, a green color pigment, and a blue color liquid liquid, a single pigment may be used, or other pigments may be mixed and used. For example, in order to obtain a reddish colored image, a single red pigment may be used, or a color obtained by mixing a yellow pigment, an orange pigment, or the like with a red pigment may be used. In addition, a single green pigment may be used to obtain a green-colored image, or a color mixture obtained by mixing a yellow pigment or the like with a green pigment may be used, or a single blue pigment may be used to obtain a blue-based colored image. A mixture obtained by mixing a purple pigment or the like with a blue pigment may be used.

In addition, in order to obtain a more vivid color as the pigment dispersion composition, and in order to increase the permeability and contrast ratio of the pigment dispersion resist composition described later, the pigment is treated by a conventionally known method by premixing, salt milling, or the like. It is preferable to use. In particular, it is more preferable to perform salt milling so that the primary particle diameter of the pigment becomes finer by grinding the pigment with an inorganic salt, using a kneading machine or a kneading apparatus for revolving motion while automatically interlocking three stirring blades, respectively. In this invention, the usage-amount of the said pigment becomes like this. Preferably it is 1-40 mass% in the pigment dispersion resist composition for color filters of this invention.

(Pigment dispersant)

The pigment dispersant is a compound obtained by reacting an isocyanate compound having an isocyanurate ring in a molecule with a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton, and isocyanur in the molecule of the obtained compound. The number of the carbazole ring and the azobenzene skeleton is 15 to a total of three numbers of the isocyanate group derived from an isocyanate compound having a rate ring and the urethane bond and the urea bond produced by the reaction of the isocyanate group and the active hydrogen group. The pigment dispersant which is 85% is used.

Moreover, as an isocyanate compound which has an isocyanurate ring in the said molecule of this invention, the thing of the following structural formula can be illustrated. However, the isocyanate compound having an isocyanurate ring in the molecule of the present invention is not limited to the following structural formula. For example, the number and position of the isocyanate groups exemplify those having 3 to 6 isocyanate groups in the following structural formula. It is also possible to use different numbers and positions as appropriate.

Moreover, as a compound obtained by reacting the isocyanate group of the isocyanate compound which has an isocyanurate ring in the said molecule | numerator, and the active hydrogen group of the compound which has an active hydrogen group in a molecule | numerator and has a carbazole ring and / or an azobenzene skeleton, it is a following structural formula. Can be illustrated, but other ones can be used as appropriate.

Here, "isocyanate group derived from the isocyanate compound which has an isocyanurate ring" is an isocyanate group of the polyisocyanate compound used in order to synthesize | combine the isocyanate compound which has an isocyanurate ring. In addition, the "urethane bond and urea bond formed by reaction of its isocyanate group and active hydrogen group" includes the urethane bond and urea bond produced by reaction of the isocyanate group and active hydrogen group in every step.

In this regard, when the isocyanate group is reacted with a compound having an active hydrogen group capable of reacting with an isocyanate group and having a polyurethane molecular chain, and a compound having an active hydrogen group capable of reacting with an isocyanate group and having a polyurea molecular chain, and Even in the case of having a molecular chain finally having the same structure as that, the number of urethane bonds or urea bonds produced by the reaction of the isocyanate group and the active hydrogen group is naturally one. By using such a pigment dispersant, since the affinity of a dispersion medium and a pigment surface becomes high, the pigment dispersion excellent in pigment dispersibility, fluidity, and dispersion stability can be obtained. And when this pigment dispersion is used for a black matrix and a color filter, the outstanding coating ability and developability are obtained.

As said diisocyanate compound, For example, Aliphatic diisocyanate, such as ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, 4-4'-dicyclohexyl methane diisocyanate, norbornane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5 Aromatic diisocyanate, such as naphthalene diisocyanate, etc. are mentioned.

Based on these diisocyanate compounds, in order to synthesize the isocyanate compound which has an isocyanurate ring in a molecule | numerator, a well-known method can be used. As one example thereof, a diisocyanate compound is introduced into a single or mixed solvent such as an ester solvent, a ketone solvent, an alcohol solvent, and, if necessary, in the presence of an isocyanurated catalyst and a cocatalyst, preferably from 30 to It is isocyanurated by making it react at 100 degreeC reaction temperature, and the isocyanate compound which has an isocyanurate ring in a molecule | numerator can be synthesize | combined. In addition, about formation of an isocyanurate ring and the number of isocyanate groups, it can carry out by titration, a refractive index, a viscosity, IR measurement, etc.

As a compound which has an active hydrogen group and a carbazole ring in the said molecule | numerator, if it has an active hydrogen group (amino group, a hydroxyl group, a carboxyl group, etc.) which can react with an isocyanate group, and also has a carbazole ring, the kind is not specifically limited, For example, 3-aminocarbazole, 2-aminocarbazole, 3-amino-N-9-ethylcarbazole, etc. are mentioned.

The compound having an active hydrogen group and an azobenzene skeleton in the molecule is not particularly limited as long as the compound has an active hydrogen group (amino group, hydroxyl group, carboxyl group, etc.) capable of reacting with an isocyanate group, and also has an azobenzene skeleton. 3-amino azobenzene, 4-amino azobenzene, etc. are mentioned.

By using a pigment dispersant in which a polyisocyanate compound having an isocyanurate ring in a molecule and a compound having an active hydrogen group in the molecule and further having a carbazole ring and / or an azobenzene skeleton are reacted to meet the above conditions. The effect of the present invention can be obtained satisfactorily.

The pigment dispersant may also react a polyester or polyether having an active hydrogen group (amino group, hydroxyl group, carboxyl group, etc.) reacting with an isocyanate group at one end, in addition to the compound having the carbazole ring and / or azobenzene skeleton. have.

The said pigment dispersant may be used independently and may use 2 or more types together. In addition, it can be said that the compound which has an azobenzene skeleton is more advantageous than the compound containing a carbazole ring from the viewpoint of the ease of manufacture of the compound itself.

In the pigment dispersion of this invention, the usage-amount of the said polyurethane type dispersing agent is 1-200 mass parts normally with respect to 100 mass parts of all the pigments used, Preferably it is 1-60 mass parts. When the usage-amount of a polyurethane-type dispersing agent is less than 1 mass part, pigment dispersibility may fall. On the other hand, when it exceeds 200 mass parts, there exists a possibility that developability may fall.

(Organic solvent)

Specifically as an organic solvent used for the pigment dispersion of this invention, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, di Ether-based organic solvents such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; Ether ester organic solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 6-butyrolactone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxypropionate, 3- Ester organic solvents such as ethyl methoxy propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate and n-amyl formate; Alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol; Nitrogen containing organic solvents, such as N-methylpyrrolidone, N, N- dimethylformamide, and N, N- dimethylacetamide, etc. can be illustrated. These can be used individually or in mixture of 2 or more types.

(Pigment Dispersion Aid)

Moreover, in this invention, in order to improve pigment dispersibility, dispersion stability during storage, and fluidity | liquidity, it is preferable to use together a pigment dispersion adjuvant.

Phthalocyanine derivatives, anthraquinone derivatives, diketopyrrolopyrrole derivatives, dianthraquinonyl derivatives, dioxazine derivatives, benzimidazolone derivatives, quinacridone derivatives may be used as the pigment dispersion aid. A pigment dispersion adjuvant may be suitably selected and used independently according to the kind of pigment, and may use 2 or more types together.

In the pigment dispersion of this invention, the usage-amount of the said pigment dispersion adjuvant is 30 mass% or less normally with respect to all pigment, Preferably it is 0.1-20 mass%. Even when the usage-amount of a pigment dispersion adjuvant exceeds the said range, there exists a tendency for a pigment dispersion effect not to improve further.

<Method of Manufacturing Pigment Dispersion>

The example of the method of manufacturing a pigment dispersion using the above material is demonstrated.

In order to manufacture the pigment dispersion of this invention, a conventionally well-known manufacturing method can be used, For example, it can manufacture by the following manufacturing methods.

First, a mixture containing a pigment, a pigment dispersant, an organic solvent and, if necessary, a pigment dispersion aid is obtained. The obtained mixture is kneaded using various dispersers such as a roll mill, a kneader, a high speed stirring device bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high pressure disperser, and dispersed to obtain a pigment dispersion.

In addition, the pigment dispersion of this invention may be made to contain binder resin (alkali-soluble resin, a photopolymerizable compound, etc.) beforehand.

<Pigment Dispersion Resist Composition for Color Filter>

Next, the pigment dispersion resist composition for color filters containing the said pigment dispersion for color filters is demonstrated in more detail.

The pigment dispersion resist composition for color filters is an active energy ray curable and alkali developable resist composition. In addition to the pigment dispersion, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a silane coupling agent, a titanate coupling agent, and an ultraviolet ray for improving adhesion with an organic solvent, a thermal polymerization inhibitor, a substrate, as necessary. Various additives, such as an absorbent and antioxidant, are contained suitably.

When using the pigment dispersion resist composition for color filters used for the black matrix of this invention for a black matrix use, the usage-amount of the pigment in a composition is the total amount of the pigment to be used as a mass fraction with respect to the total solid of the pigment dispersion resist composition for color filters. Preferably it is 5-60 mass%, More preferably, it is the range of 10-30 mass%.

In addition, when using for the use of each color pixel formation of a color filter, the usage-amount of the organic pigment in a composition is a mass fraction with respect to the total solid of the pigment-dispersion resist composition for color filters, Preferably it is a total amount of the organic pigment to use 5 To 80 mass%, More preferably, it is the range of 20-50 mass%.

In the said pigment dispersion resist composition for color filters, the usage-amount of a pigment dispersant is 1-200 mass parts normally with respect to 100 mass parts of organic pigments, Preferably it is 1-60 mass parts. If it is less than 1 mass part, pigment dispersibility may fall. On the other hand, when it exceeds 200 mass parts, there exists a possibility that developability may fall.

In the said pigment dispersion resist composition for color filters, the usage-amount of a pigment dispersion adjuvant is 30 mass% or less normally with respect to a coloring pigment, Preferably it is 0.1-20 mass%. Even if it exceeds 30 mass%, there exists a tendency for a pigment dispersion effect not to improve further.

(Alkali-soluble resin)

Next, as alkali-soluble resin which comprises the pigment-dispersion resist composition for color filters of this invention for the purpose of provision of image development characteristics, etc., the developing solution used at the developing process process at the time of manufacturing a color filter, Especially preferably, alkali It will not specifically limit, if it has solubility with respect to a developing solution. Especially, alkali-soluble resin which has a carboxyl group is preferable, and the copolymer of the ethylenically unsaturated monomer which has one or more carboxyl groups with another copolymerizable ethylenically unsaturated monomer is especially preferable.

Specifically, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl copolymerizable with an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid, and an ethylenically unsaturated monomer having the carboxyl group. Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl And copolymers with at least one ethylenically unsaturated monomer selected from the group consisting of methacrylate macromonomers.

As an acid value of the said copolymer, 50-300 mgKOH / g is preferable. In this case, when an acid value is less than 50 mgKOH / g, there exists a tendency for the solubility with respect to the alkaline developing solution of a resist composition to fall. On the other hand, when it exceeds 300 mgKOH / g, the solubility with respect to an alkaline developing solution will become large too much, and when developing with an alkaline developing solution, there exists a tendency which comes out from the board | substrate of a colored layer and the film | membrane roughness of the colored layer surface easily.

In addition, the acid value in this invention is a theoretical acid value, and says the value arithmetically calculated based on the ethylenically unsaturated monomer which has a carboxyl group, and its usage-amount.

As for the weight average molecular weight of alkali-soluble resin in this invention, 1,000-100,000 are preferable normally. When the weight average molecular weight of alkali-soluble resin is less than 1,000, the solubility with respect to an alkali developer will become high too much, and the hardened resist film may elute.

On the other hand, when it exceeds 100,000, solubility to an organic solvent will fall, a background contamination and a film residue may arise on the board | substrate or the light-shielding layer of the uncured part of a resist film, and the viscosity of a resist composition may increase. .

In the pigment dispersion resist composition for color filters, the amount of the alkali-soluble resin used is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of all the pigments used. When the usage-amount of alkali-soluble resin is less than 10 mass parts, alkali developability may fall, for example, or a background contamination and a film residue may generate | occur | produce on the board | substrate or the light shielding layer of an unexposed part. On the other hand, when it exceeds 1,000 mass parts, since the density | concentration of a pigment falls relatively, there exists a possibility that it may become difficult to achieve the target color density when it sets as a thin film.

(Photopolymerizable compound)

Next, in order to form a cured film in an exposure part, the photopolymerizable compound which comprises the pigment dispersion resist composition for color filters of this invention is demonstrated.

As said photopolymerizable compound, the monomer, oligomer, etc. which have one or more photopolymerizable unsaturated bonds in a molecule | numerator are mentioned.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Acrylates or acrylates; Aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; Alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; Aminoalkyl methacrylates or acrylates such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethyl acrylate; Methacrylic acid esters or acrylic acid esters of polyalkylene glycol alkyl ethers such as diethylene glycol ethyl ether, triethylene glycol butyl ether, and dipropylene glycol methyl ether; Methacrylic acid ester or acrylic acid ester of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Isobornyl methacrylate or acrylate; Glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate, an acrylate, etc. can be illustrated.

In addition, as a monomer which has two or more photopolymerizable unsaturated bonds in a molecule | numerator, bisphenol A dimethacrylate, 1, 4- butanediol dimethacrylate, 1, 3- butylene glycol dimethacrylate, diethylene glycol di Methacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, penta Erythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1, 4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glyc Cerrol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. are mentioned. These monomers can be used individually or in combination of 2 or more types.

In this invention, the usage-amount of the said photopolymerizable compound is a mass fraction with respect to the total solid in the pigment dispersion resist composition for color filters, Preferably it is the range of 3-50 mass%.

(Photoinitiator)

Next, in order to superpose | polymerize photopolymerization, it does not specifically limit as a photoinitiator which comprises the pigment dispersion resist composition for color filters of this invention, For example, benzophenone, N, N'- tetraethyl-4,4 '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenylketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro 2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholino propane-1-one, a triazine type photoinitiator, etc. are mentioned. These photoinitiators are used individually or in combination of 2 or more types.

In this invention, the usage-amount of the said photoinitiator is a mass fraction with respect to the total solid in the pigment dispersion resist composition for color filters, Preferably it is the range of 1-20 mass%.

(Organic solvent)

Subsequently, in order to improve the dilution and fluidity to an appropriate density | concentration, as an organic solvent which comprises the pigment dispersion resist composition for color filters of this invention, it is the same as the pigment dispersion for color filters mentioned above, Preferably Ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon solvents and nitrogen-containing organic solvents having a boiling point of 100 to 220 ° C. at atmospheric pressure (1.013 × 10 ² kPa). .

As these organic solvents, the same thing as the above-mentioned organic solvent is mentioned specifically ,. Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexa, Paddy, 2-heptanone, 2-hydroxypropionate ethyl, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, and the like, More preferably, it is propylene glycol monomethyl ether acetate.

Moreover, these organic solvents contain 50 mass% or more, and 70 mass% or more in all the organic solvents used for the pigment dispersion resist composition for color filters of this invention from the solubility, pigment dispersibility, applicability | paintability, etc. of the said alkali-soluble resin. It is preferable to make it.

If the boiling point contains a large amount of an organic solvent of more than 220 ° C, the organic solvent may remain in the dry coating film without evaporating sufficiently when precoated the coated film to be formed, and the heat resistance of the dry coating film may be lowered. Moreover, when it contains a large amount of the organic solvent below boiling point 100 degreeC, it will become difficult to apply uniformly, without being nonuniform, and there exists a possibility that the coating film excellent in surface smoothness may not be obtained.

(Other additives)

Various additives, such as another photopolymerizable compound, a thermal polymerization inhibitor, a ultraviolet absorber, antioxidant, can be suitably used for the pigment dispersion resist composition for color filters of this invention as needed.

<The manufacturing method of the pigment dispersion resist composition for color filters>

The method of manufacturing the pigment dispersion resist composition for color filters of this invention using the above structural material is demonstrated. This is an example of a preferred embodiment, and the present invention is not limited thereto.

In order to manufacture the pigment dispersion resist composition for color filters of this invention from said structural material, the said photopolymerizable compound, the photoinitiator, alkali-soluble resin, the organic solvent as needed in the pigment dispersion obtained by the said method. , Other additives can be added, and a method of stirring and mixing using a stirring device or the like can be used.

<Examples>

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples. In addition, "%" means "mass%" and "part" means "mass part" unless there is particular notice.

[Black pigment dispersion for color filters, Black pigment dispersion resist composition for color filters]

Pigment Dispersant

<Dispersant 1>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod and a thermometer, 220 parts of polycaprolactone having a molecular weight of 2000 having a hydroxyl group at one end and a polyethylene glycol having a molecular weight of 1000 having a hydroxyl group at one end (brand name: UNI) 54.6 parts of Oak M-1000 Nichiyu Co., Ltd., 179.1 parts of butyl acetate 50% solution of a toluene diisocyanate type polyisocyanate (brand name: Colonate 2030 Nippon Polyurethane Co., Ltd. product) were prepared, and it is made into about 80 degreeC. It is kept for 3 hours to react the isocyanate group and the hydroxyl group, and then 35.9 parts of 3-amino-9-ethylcarbazole are added, and it is maintained at about 90 DEG C for 1 hour to react the isocyanate group and the amino group, followed by propylene glycol monomethyl ether acetate. 510g was thrown in and the pigment dispersant 1 (solid content 40%) was obtained (carbazole ring ratio: about 50%).

<Dispersant 2>

A butyl acetate 50% solution of toluene diisocyanate polyisocyanate 245 parts of molecular weight 3000 polycaprolactone having a hydroxyl group at one end in a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer. : 171.5 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react an isocyanate group with a hydroxyl group, followed by 51.5 parts of 3-amino-9-ethylcarbazole, and The mixture was kept at 90 ° C for 1 hour to react an isocyanate group with an amino group, and then 487 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 2 (solid content 40%) (carbazole ring ratio: about 75%).

<Dispersant 3>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod and a thermometer, 220 parts of polycaprolactone having a molecular weight of 2000 having a hydroxyl group at one end and a polyethylene glycol having a molecular weight of 1000 having a hydroxyl group at one end (brand name: UNI) 54.6 parts of Oak M-1000 Nichiyu Co., Ltd., 172.3 parts of butyl acetate 50% solution of a toluene diisocyanate type polyisocyanate (brand name: Colonate 2030 Nippon Polyurethane Co., Ltd. product) were thrown in, and about 80 degreeC Maintained for 3 hours to react the isocyanate group and the hydroxyl group, and then 32.4 parts of 4-aminoazobenzene were added thereto, and maintained at about 90 ° C. for 1 hour to react the isocyanate group and the amino group, followed by adding 500 g of propylene glycol monomethyl ether acetate. A pigment dispersant 3 (solid content 40%) was obtained (azobenzene skeleton ratio: about 50%).

<Dispersant 4>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 245 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name: 222.8 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react an isocyanate group and a hydroxyl group, followed by addition of 34.9 parts of 4-aminoazobenzene and at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 475 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 4 (solid content 40%) (azobenzene skeleton ratio: about 42%).

<Dispersant 5>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 245 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name: 173.3 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, and then 17.3 parts of 3-amino-9-ethylcarbazole were added, and about 90 parts The mixture was kept at 1 ° C. for 1 hour to react the isocyanate group with the amino group, and then 436 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 5 (solid content 40%) (carbazole ring ratio: about 25%).

<Dispersant 6>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas inlet tube, a stirring rod, and a thermometer, 245 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name) : 173.3 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react an isocyanate group and a hydroxyl group, and then 16.3 parts of 4-aminoazobenzene were added and then heated at about 90 ° C. for 1 hour. It was kept for a while to react the isocyanate group with the amino group, and then 435 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 6 (solid content 40%) (azobenzene skeleton ratio: about 25%).

<Dispersant 7>

245 parts of molecular weight 3000 polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate polyisocyanate in a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer (brand name: 171.5 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react an isocyanate group and a hydroxyl group, and then 48.3 parts of 4-aminoazobenzene were added and then heated at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 482 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 7 (solid content 40%) (azobenzene skeleton ratio: about 75%).

<Dispersant 8>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 245 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name: 222.8 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, followed by 14.9 parts of 3-amino-9-ethylcarbazole and 4-amino. 20.9 parts of azobenzene was added and maintained at about 90 ° C. for 1 hour to react the isocyanate group with the amino group, and then 475 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 8 (solid content 40%) (carbazole ring + azobenzene). Skeletal ratio: about 42%).

<Dispersant 9>

48.5 parts of molecular weight 2000 polycaprolactone having a hydroxyl group at one end, and a 50% solution of butyl acetate of toluene diisocyanate polyisocyanate in a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer (brand name: 157.5 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, followed by addition of 54.2 parts of 4-aminoazobenzene and at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 193 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 9 (solid content 40%) (azobenzene skeleton ratio: about 92%).

<Dispersant 10>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 160 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name: 47.3 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, and then 1.5 parts of 4-aminoazobenzene were added and then heated at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 254 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 10 (solid content 40%) (azobenzene skeleton ratio: about 8%).

<Dispersant 11>

48.5 parts of molecular weight 2000 polycaprolactone having a hydroxyl group at one end, and a 50% solution of butyl acetate of toluene diisocyanate polyisocyanate in a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer (brand name: 157.5 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, followed by adding 57.8 parts of 4-aminoazobenzene, and then at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 198 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 11 (solid content 40%) (carbazole ring ratio: about 92%).

<Dispersant 12>

In a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring rod, and a thermometer, 160 parts of polycaprolactone having a hydroxyl group at one end and a 50% solution of butyl acetate of toluene diisocyanate-based polyisocyanate (brand name: 47.3 parts of Collonate 2030 Nippon Polyurethane Co., Ltd.) was added and held at about 80 ° C. for 3 hours to react the isocyanate group and the hydroxyl group, and then 1.5 parts of 4-aminoazobenzene were added and then heated at about 90 ° C. for 1 hour. Then, the isocyanate group and the amino group were reacted, and then 254 g of propylene glycol monomethyl ether acetate was added to obtain a pigment dispersant 12 (solid content 40%) (carbazole ring ratio: about 8%).

In addition, said carbazole ring and azobenzene skeleton ratio are carbazole ring and azobenzene skeleton with respect to the sum total of three numbers of the urethane bond and the urea bond formed by making active isocyanate group and isocyanate group react in the molecule | numerator of a pigment dispersant. The ratio of the number is shown.

<Pigment>

Printex 25

(Carbon black, manufactured by Degussa Co., Ltd., oil absorption: 45 ml / 100 g, pH: 9.3)

Pigment Dispersant

BYK-167 (BYK-Kemi company make, 52% solids)

Pigment Dispersion Aids

Sol Spaz 5000 (manufactured by Lubrizol, phthalocyanine pigment dispersant)

<Alkali Soluble Resin>

ZAH-110 (brand name, acrylic resin varnish manufactured by Soken Chemical Industries, Ltd.)

<Photopolymerizable Compound>

DPEHA (Dipentaerythritol hexaacrylate)

<Photoinitiator>

Irgacure 907 (Ciba specialty chemicals company make, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholino propane-1-one)

<Organic solvent>

PGMEA (propylene glycol monomethyl ether acetate)

[Production of black pigment dispersion for color filters of Examples 1 to 8 and Comparative Examples 1 to 5, black pigment dispersion resist composition for color filters]

First, various materials were mixed so as to have the composition shown in Table 1 below, they were ground overnight with a bead mill to obtain black pigment dispersions (A) to (H) and (M) for color filters.

Further, using a high speed stirrer, the black pigment dispersions for color filters (A) to (H) and (M) were mixed uniformly with the other materials so as to have the composition of Table 2 below, followed by filtration with a filter having a pore diameter of 3 μm. Then, the resist compositions for black matrices of Examples 1 to 8 and Comparative Example 5 were obtained (for Comparative Examples 1 to 4, since black pigment dispersions (I) to (L) for color filters could not be obtained, No evaluation)

<Evaluation test>

(Dispersion stability)

The black pigment dispersion resist composition (A)-(H) and (M) for each color filter, and the black pigment dispersion resist composition for each color filter of Examples 1-8 and Comparative Example 5 were employ | adopted in a glass bottle, respectively, and it was made intact and room temperature. The state after 7 days storage at was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.

A: No thickening or sediment is recognized

B: Shake lightly to allow the thickening or sediment to return to its original state.

C: A thickening or sediment is recognized that does not return to strong shaking.

(Development margin of resist pattern)

The pigment dispersion resist compositions for black matrices of Examples 1 to 8 and Comparative Example 5 were applied onto a glass substrate with a spin coater to a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. Thereafter, using a mask obtained by obtaining a lattice pattern having a line width of 25 μm such that the area ratio of the cured portion and the uncured portion was 20:80, the exposure was performed using a high pressure mercury lamp at a UV accumulated light amount of 400 mJ / cm 2. The obtained coating film was developed using 0.05% potassium hydroxide aqueous solution, and the development margin was evaluated by measuring the time from the removal of the resist composition of the unexposed part to the removal of the resist composition of the hardened part. The results are shown in Table 2.

(Dissoluble)

The black pigment dispersion resist composition for each color filter of Examples 1-8 and Comparative Example 5 was apply | coated on the glass substrate so that it might become 1 micrometer of film thickness with a spin coater, and it prebaked at 100 degreeC for 3 minutes. When the obtained coating film was immersed for 10 minutes or more in PGMEA solution for 5 minutes, the time until a coating film melt | dissolved was measured, and re-dissolution was evaluated according to the following evaluation criteria. The results are shown in Table 2 (the pigment dispersing resist composition is coated with a spin coater, and if the re-dissolution property deteriorates, the coating ability is lowered).

○: The coating film is completely redissolved

(Triangle | delta): It melt | dissolves except a part of coating film.

×: not re-dissolved

The pigment dispersion for color filters of this invention and the pigment dispersion resist composition for color filters containing it are applicable to a color liquid crystal display device suitably.

Claims (3)

The pigment dispersion for color filters containing a pigment, a pigment dispersant, and the organic solvent, The said pigment dispersant is a compound which satisfy | fills following condition 1, The pigment dispersion for color filters characterized by the above-mentioned. Condition 1: A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule with an active hydrogen group of a compound having an active hydrogen group in a molecule and having a carbazole ring and / or an azobenzene skeleton. The number of carbazole rings and azobenzene skeletons relative to the sum of three numbers of isocyanate groups derived from isocyanate compounds having isocyanurate rings and urethane bonds and urea bonds produced by the reaction of the isocyanate groups with active hydrogen groups is 15 To 85%. The pigment dispersion for color filters of Claim 1 which further contains a pigment dispersion adjuvant. The pigment dispersion resist composition for color filters containing the pigment dispersion for color filters of Claim 1 or 2.