Pigment dispersant, pigment dispersion composition containing the same and colored photosensitive composition

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a pigment dispersant, a pigment dispersion composition containing the same, and a colored photosensitive composition. More specifically, a pigment dispersant that effectively prevents agglomeration of pigments and realizes good dispersion of the pigment. A pigment dispersion composition containing the pigment dispersant, having excellent dispersibility, fluidity, etc. of the pigment, excellent coloring power, and suitably usable in a wide range such as paints, printing inks, color display boards, and the like. The present invention relates to a colored photosensitive composition containing a pigment dispersion composition and which can be suitably used for forming a multicolor image on a substrate such as a color proof and for producing a color filter used for a liquid crystal color display or the like.

【0002】

[Conventional technology]

Traditionally, pigments have been widely used in many fields because of their vivid color tone and high tinting strength. Among these pigments, those that are practically important are generally those of fine particles, and a clear color tone and high coloring power can be obtained by preventing agglomeration of the pigment and making the pigment finer. However, as the pigment becomes finer, the dispersion liquid of the pigment often exhibits a high viscosity. Therefore, when this pigment dispersion is prepared on an industrial scale, it becomes difficult to take out the pigment dispersion from the disperser, it cannot be transported by a pipeline, or it gels during storage. There are problems such as being unusable.

【0003】

By the way, the colored photosensitive composition containing the pigment is useful as a material for a color filter used for a liquid crystal display or the like, and when a color filter is manufactured using the colored photosensitive composition, quality and production stability The pigment dispersion method, which is excellent in terms of the above, is widely adopted. In this pigment dispersion method, a coating liquid of the colored photosensitive composition is applied onto a transparent substrate to provide a colored photosensitive layer, and after pattern exposure, development is performed to form a pixel pattern of the first color. Is repeated a plurality of times to form a pixel pattern of a plurality of colors on the transparent substrate.

【0004】

However, since a pigment is used as a coloring material here, if the pigment is not sufficiently miniaturized, light is scattered and absorbed by the pigment, and the light transmittance is lowered. Furthermore, there are problems such as the polarization axis rotating due to light scattering and birefringence by the pigment, and the contrast of the liquid crystal display device also decreasing (1990 7th Color Optical Conference, 512 color display 10.4 ". Size TFT-LCD color filter, Ueki, Ozeki, Fukunaga, Yamanaka). Therefore, in the colored photosensitive composition, it is necessary to disperse the pigment in a highly fine state.

【0005】

Therefore, conventionally, it is known to use various dispersants in order to obtain a pigment dispersion liquid or a colored photosensitive composition having excellent fluidity, dispersibility and the like. The dispersant can be roughly classified into a polymer-based dispersant and a low-molecular-weight compound dispersant. Examples of the polymer-based dispersant include polyacrylate, sodium maleate olefin copolymer, and terminal carboxyl group-containing polyester (Tokukosho). 54-34009), polyester having an acidic group and / or a basic group starting from tetrakis (2-hydroxyalkyl) ethylenediamine (Japanese Patent Laid-Open No. 2-245231), macromonomer (ethylenic unsaturated at the terminal) A copolymer having four kinds of a group-containing oligomer, a hydroxyl group-containing monomer, a carboxy group-containing monomer, and other monomers (Japanese Patent Laid-Open No. 8-259876) and the like are known. Further, as the low molecular weight compound dispersant, sorbitan fatty acid ester, polyoxyethylene alkylamine, alkyldiamine, alkanolamine derivative (US Patent No. 3536510) and the like are known, and the dispersant having a pigment matrix introduced therein. Examples are described in Japanese Patent Application Laid-Open No. 5-72943 and Japanese Patent Application Laid-Open No. 8-48890.

【0006】

On the other hand, a colored photosensitive composition containing a pigment exhibiting a vivid color tone and high coloring power is useful as an image forming material for producing, for example, a color proof or a color filter. When a colored image is formed using the colored photosensitive composition, generally, a coating solution of the colored photosensitive composition is applied onto a substrate to form a layer of the colored photosensitive composition, and then exposure / development is performed. However, as the developing solution used in this development, an alkaline aqueous solution having little influence on the environment is often used, and the layer made of the colored photosensitive composition is, that is, the binder (that is, the binder in the colored photosensitive composition). The binder) is required to be soluble in the alkaline aqueous solution. On the other hand, as a solvent (dispersion medium for pigments) used in the coating liquid of the colored photosensitive composition, an organic solvent is effective because it is easy to dry after coating. Therefore, the binder in the colored photosensitive composition needs to have an acidic group and have a property of being soluble in an appropriate organic solvent. In the colored photosensitive composition, the organic pigment is used. It has such properties and is dispersed in the binder having an acidic group.

【0007】

Since the layer made of such a colored photosensitive composition is generally required to be extremely thin, thin and exhibit a high coloring concentration, an organic pigment is contained in a binder having an acidic group soluble in an organic solvent. It is necessary to disperse in a highly miniaturized state. However, the present situation is that a pigment dispersion having excellent dispersibility, fluidity, etc. of the pigment, a pigment dispersion composition containing the same, and a colored photosensitive composition have not yet been provided.

【0008】

[Problems to be Solved by the Invention]

An object of the present invention is to solve the above-mentioned conventional problems and to achieve the following object. That is, an object of the present invention is to provide a pigment dispersant that does not agglomerate a pigment, realizes stable and good dispersibility and fluidity of the pigment, and has excellent light transmission. Further, the present invention contains the pigment dispersant, has excellent dispersibility, fluidity, etc. of the pigment, has high coloring power, has excellent alkali development suitability, and has a wide range of paints, printing inks, color display boards, and the like. It is an object of the present invention to provide a pigment dispersion composition which can be preferably used in the above. Further, the present invention contains the pigment dispersion composition, has high coloring power, is excellent in alkali development suitability, forms a multicolor image on a substrate such as a color proof, and is a color filter used for a liquid crystal color display or the like. It is an object of the present invention to provide a colored photosensitive composition that can be suitably used for the production of the above.

【0009】

[Means for solving problems]

As a result of diligent studies by the present inventors in order to solve the above problems, the following findings were obtained. That is, when an organic pigment is dispersed in a binder having an acidic group soluble in an organic solvent, an intermolecular force acts between the acidic group and the organic pigment to increase the viscosity. Although the dispersion stability is improved by this thickening, the handleability, workability and the like are deteriorated, and the organic pigment tends to be difficult to be finely divided. Therefore, a dispersant capable of promoting dispersion without thickening is desired, and as such a dispersant, a low molecular weight compound dispersant, particularly an amine compound and the like are known. However, in the case of this amine compound or the like, an acidic group and a salt are formed, and the photosensitive resin layer is easily dissolved in the developing solution, which may adversely affect the subsequent development. It is a finding that alkaline dispersants and water-soluble dispersants have the same tendency as those of the amine compounds.

【0010】

The present invention is based on the above-mentioned findings by the present inventor and the like, and the means for solving the above-mentioned problems are as follows. That is, <1> A pigment dispersant characterized by containing a compound represented by the following general formula (I).

【0011】

[Chemical 4]

<img file="JP2000239554A_D0001.tif" />【0012】

(In the general formula (I), A represents a component capable of forming an azo dye together with XY. X represents a single bond or a group selected from a divalent linking group represented by the following structural formula. Y represents a group represented by the following general formula (II).

【0013】

[Chemical 5]

<img file="JP2000239554A_D0002.tif" />【0014】

[Chemical 6]

<img file="JP2000239554A_D0003.tif" />【0015】

(In general formula (II), Z represents a lower alkylene group-NR.₂Represents a lower alkylamino group or a 5- to 6-membered saturated heterocycle containing a nitrogen atom. a represents 1 or 2. ) &lt;2&gt; A pigment dispersion composition characterized by dispersing the pigment dispersant according to &lt;1&gt; and the pigment in an organic solvent. &lt;3&gt; The pigment dispersion composition according to &lt;2&gt; above, which contains a binder polymer having an acidic group. &lt;4&gt; The pigment dispersion composition according to &lt;2&gt;, a binder polymer having an acidic group, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator are contained. It is a colored photosensitive composition characterized by.

【0016】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. &lt;&lt; Pigment Dispersant &gt;&gt; The pigment dispersant of the present invention contains a compound represented by the following general formula (I), and contains other components appropriately selected as necessary. (Compound represented by general formula (I)) [0017]

[Chemical 7]

<img file="JP2000239554A_D0004.tif" />【0018】

In the general formula (I), A represents a component capable of forming an azo dye together with XY. The A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited to these specific examples.

【0019】

[Chemical 8]

<img file="JP2000239554A_D0005.tif" />【0020】

[Chemical 9]

<img file="JP2000239554A_D0006.tif" />【0021】

In the general formula (I), X is selected from a single bond (meaning that Y is directly linked to -N = N-) or a divalent linking group represented by the following structural formula. Represents a group.

【0022】

[Chemical 10]

<img file="JP2000239554A_D0007.tif" />【0023】

In the general formula (I), Y represents a group represented by the following general formula (II).

【0024】

[Chemical 11]

<img file="JP2000239554A_D0008.tif" />【0025】

In general formula (II), Z represents a lower alkylene group. Z is-(CH₂)_{b b}Although expressed as-, the b represents an integer of 1 to 5, preferably 2 or 3. In general formula (II), -NR₂Represents a lower alkylamino group or a 5- to 6-membered saturated heterocycle containing a nitrogen atom. The-NR₂Represents a lower alkylamino group, -N (C)_nH_{2n + 1})₂, N represents an integer from 1 to 4, preferably 1 or 2. On the other hand, the -NR₂When representing a 5- to 6-membered saturated heterocycle containing a nitrogen atom, a heterocycle represented by the following structural formula is preferable.

【0026】

[Chemical 12]

<img file="JP2000239554A_D0009.tif" />【0027】

Z and -NR in the general formula (II)₂May have a lower alkyl group and an alkoxy group as substituents, respectively. In the general formula (II), a represents 1 or 2, preferably 2.

【0028】

Specific examples of the compound represented by the general formula (I) will be shown below, but the present invention is not limited to these specific examples.

【0029】

[Chemical 13]

<img file="JP2000239554A_D0010.tif" />【0030】

[Chemical 14]

<img file="JP2000239554A_D0011.tif" />【0031】

[Chemical 15]

<img file="JP2000239554A_D0012.tif" />【0032】

[Chemical 16]

<img file="JP2000239554A_D0013.tif" />【0033】

An example of synthesis of the compound represented by the general formula (I) is shown below.

[Synthesis example 1] -Synthesis of Compound Example 5- (1) 50 parts of dimethyl 5-nitroisophthalate and 130 parts of N, N-diethyl-1,3-propanediamine were reacted at 80 to 100 ° C for about 4 hours under weak depressurization. After confirming the disappearance of the raw materials dimethyl 5-nitroisophthalate and the monoamide compound, excess N, N-diethyl-1,3-propanediamine was removed under reduced pressure, and 92 parts of bis-3-diethylamino 5-nitroisophthalate was removed. Propylamide was obtained. (2) 92 parts of the obtained 5-nitroisophthalic acid bis-3-diethylaminopropylamide was refluxed and reduced in 200 parts of isopropanol and 35 parts of water together with 112 parts of reduced iron and 12 parts of ammonium chloride to reduce 5-amino-. 86 parts of bis-3-diethylaminopropylamide isophthalate was obtained. (3) 18.3 parts of the obtained 5-amino-isophthalic acid bis-3-diethylaminopropylamide was added to 250 parts of methanol, and 32 parts of hydrochloric acid was added under ice-cooling. The mixture was further cooled to -15 ° C. NaNO to this₂3.4 parts of an aqueous solution (35 parts of water) was added dropwise to diazotize (preparation of diazo solution). Separately, 5-acetoacetylamino-benzimidazolone 9.3 parts, methanol 400 parts, water 800 parts, and Na₂CO₃A 19-part coupling component solution was prepared and cooled to 10 ° C or below. The diazo solution obtained above was added dropwise thereto for diazo coupling. K₂CO₃Was added to make the system basic, and the precipitated yellow product was collected by filtration. This was recrystallized from chloroform and acetonitrile to obtain 19 parts of the above-mentioned Exemplified Compound 5. The maximum absorption wavelength of the obtained compound is λmax 380 nm (CHCl).₃It was (middle).

【0034】

[Synthesis example 2] -Synthesis of Compound Example 7- (1) 18.5 parts of 5-nitroisophthalic acid bis-3-diethylaminopropylamide and 5.1 parts of triethylamine obtained in (2) of Synthesis Example 1 were dissolved in 60 parts of DMF and ice-cooled. A solution of 9.3 parts of 4-nitrobenzoyl chloride in 60 parts of acetone was added thereto for amidation. After the reaction, 800 parts of water was added and the crystals were collected by filtration and recrystallized from ethyl acetate to obtain 14 parts of 4-nitrobenzoyl-4- [3,5-bis (3-diethylaminopropylcarbamoyl)] phenylamide. It was. (2) The obtained compound was reduced in the same manner as in (2) of Synthesis Example 1 to obtain 13.2 parts of an aniline derivative. (3) 13.2 parts of the obtained aniline derivative was added to 120 parts of methanol, and 18 parts of hydrochloric acid was added under ice-cooling. The mixture was further cooled to -15 ° C. NaNO to this₂1.8 parts of an aqueous solution (20 parts of water) was added dropwise to diazotize (preparation of diazo solution). Separately, 5-acetoacetylaminobenzimidazolone 5.9 parts, methanol 260 parts, water 530 parts, and NaCO₃A coupling component solution consisting of 10.8 parts was prepared and cooled to 10 ° C or lower. The diazo solution obtained above was added dropwise to this so as not to exceed 10 ° C, and the reaction was carried out. K₂CO₃Was added to make the system basic, and the precipitated yellow product was collected by filtration and recrystallized from DMF and acetonitrile to obtain 19 parts of Exemplified Compound 7 shown above. The maximum absorption wavelength of the obtained compound is λmax 391 nm (CHCl).₃It was (middle).

【0035】

[Synthesis example 3] -Synthesis of Exemplified Compound 22- (1) Using 22.9 parts of the aniline derivative in the same manner as in (3) of Synthesis Example 2, 180 parts of methanol, 31 parts of hydrochloric acid, and NaNO₂A diazo solution consisting of 3.1 parts and 30 parts of water was prepared. (2) 5.6 parts of barbituric acid, 600 parts of methanol, 1100 parts of water, and Na₂CO₃A coupling component solution consisting of 19 parts was prepared. The diazo solution obtained in (1) was added dropwise thereto to cause a reaction. After the reaction, K₂CO₃Was added to make the system basic, and the precipitated crystals were collected by filtration and recrystallized from DMF and acetonitrile to obtain 16.3 parts of Exemplified Compound 22 shown above. The maximum absorption wavelength of the obtained compound is λmax 378 nm (CHCl).₃It was (middle).

【0036】

(Other Ingredients) The pigment dispersant of the present invention may contain only the compound represented by the general formula (I), or may further contain other components appropriately selected as necessary. .. Examples of the other components include known dispersants, and specifically, nonanoamide, decaneamide, dodecaneamide, N-dodecylhexadecaneamide, N-octadecylpropioamide, N, N-dimethyldodecaneamide and N, Amide compounds such as N-dihexylacetamide, amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N', N'-tetramethylmethaneamine, triethylamine, tributylamine and trioctylamine, monoethanol Amine, diethanolamine, triethanolamine, N, N, N', N'-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N'-tri (hydroxyethyl) -1,2-diaminoethane , N, N, N', N'-tetra (hydroxyethyl polyoxyethylene) -1,2-diaminoethane, 1,4-bis (2-hydroxyethyl) piperazin and 1- (2-hydroxyethyl) piperadisi, etc. Examples of amines having a hydroxy group of the above include compounds such as pecotamide, isonipecotamide, and nicotinic acid amide. These may be commercially available products or may be appropriately synthesized, and examples of the commercially available products include Shigenox-105 (trade name, manufactured by Hackor Chemical Co., Ltd.) and the like.

【0037】

The content of the other components in the pigment dispersant is preferably 1 to 90% by weight, more preferably 1 to 70% by weight. If the content is less than 1% by weight, the increase in viscosity of the pigment dispersion composition may not be suppressed, and if it exceeds 90% by weight, the performance as a pigment dispersant may not be sufficiently exhibited.

【0038】

Further, the pigment dispersant of the present invention may further contain an amine compound represented by the following general formula (III) or (IV). General formula (III) [0039]

[Chemical 17]

<img file="JP2000239554A_D0014.tif" />【0040】

In the general formula (III), R³¹And R³²Represents a hydrogen atom or an alkyl group or an aralkyl group which may have a substituent, and these may be bonded to each other to form a 5- to 6-membered saturated ring containing a nitrogen atom. The saturated ring may further contain 1 to 3 atoms selected from oxygen, sulfur and nitrogen atoms. R³³Represents an alkylene group or an alkylene group containing an ether bond. X³Is -CON (Y³¹) (Y³²), -OCON (Y³¹) (Y³²), -N (Y³³) CO (Y³⁴) Or -N (Y)³³) CON (Y³¹) (Y³²). Y³¹, Y³², Y³³And Y³⁴Represents a hydrogen atom or an alkyl group, an aralkyl group or an aryl group which may have a substituent. General formula (IV) [0041]

[Chemical 18]

<img file="JP2000239554A_D0015.tif" />【0042】

In the general formula (IV), R⁴¹, R⁴², R⁴⁶And R⁴⁷Represents a hydrogen atom or an alkyl group or an aralkyl group which may have a substituent, and these may be bonded to each other to form a 5- to 6-membered saturated ring containing a nitrogen atom. The saturated ring may further contain 1 to 3 atoms selected from oxygen, sulfur and nitrogen atoms. R⁴⁴And R⁴⁵Represents an alkylene group or an alkylene group having an ether bond. Z⁴Is -CON (Y⁴¹)-, -OCON (Y⁴¹)-Or-N (Y⁴²) CON (Y⁴³)-Represents. Y⁴¹, Y⁴²And Y⁴³Is Y in the general formula (III)³¹, Y³²And Y³³Is synonymous with.

【0043】

Specific examples of the amine compound represented by the general formula (III) or (IV) include bis (2- (1-morpholino) ethyl) terephthalamide and the like.

【0044】

Further, the pigment dispersant of the present invention may contain various surfactants, and the inclusion of the surfactant is effective in improving the dispersion stability. Examples of the surfactant include alkylnaphthalene sulfonates, anionic surfactants typified by phosphoric acid ester salts, cationic surfactants typified by amine salts, aminocarboxylic acids, and betaine types. Amphoteric surfactants, etc. may be mentioned.

【0045】

(Dispersion) Next, the dispersion of the pigment by the pigment dispersant of the present invention will be described. When the pigment dispersant of the present invention is used, the pigment dispersant is adsorbed on the surface of the pigment particles. At this time, nitrogen atoms in the pigment dispersant are adsorbed on the surface of the pigment particles. The pigment particles are covered with the compound represented by the general formula (I). Since the compound represented by the general formula (I) is adsorbed on the surface of each pigment particle, the pigment particles do not adsorb to each other and aggregate, and remain in a finely divided state. It is uniformly dispersed by the compound represented by I) and becomes easy to flow.

【0046】

When a normal pigment dispersant is used in the colored photosensitive composition, the acidic group in the binder polymer having an acidic group contained in the colored photosensitive composition and the nitrogen atom in the pigment dispersant are formed. It often forms a salt or binds with a strong intermolecular force, but in the case of the pigment dispersant of the present invention, since it has a pigment matrix, it has a better affinity with the pigment. Since it is high, it is possible to suppress such behavior, improve the stability after dispersion, and enhance the effect of improving the dispersibility by the nitrogen atom. Further, according to the compound represented by the general formula (I), when the organic pigment is dispersed, the organic pigment is not accompanied by thickening, the dispersibility of the organic pigment is good, and the dispersibility to the acidic organic pigment is particularly high. It is good.

【0047】

The dispersion by the pigment dispersant of the present invention means that the pigment particles generally existing in the state of secondary particles are loosened into the state of primary particles to prevent reaggregation. The pigment dispersant of the present invention has an adsorption site on the pigment, and in order to prevent reaggregation after the pigment is dispersed in the form of primary particles, a binder having an acidic group is allowed to coexist to cause steric repulsion. Gender can be imparted. Dispersion of the pigment by the pigment dispersant of the present invention is effectively achieved by direct mixing of the pigment dispersant with the pigment, and is preferably carried out in a state where there are as few particles as possible to be dispersed other than the pigment. When the pigment is dispersed in such a state, the pigment dispersant of the present invention is instantly adsorbed around the pigment particles, the pigment particles are well dispersed and flow well, and the pigment particles are aggregated with each other. Is effectively suppressed. On the other hand, when the pigment is dispersed in the presence of particles that can be dispersed other than the pigment particles, the pigment dispersant of the present invention is not adsorbed on the surface of the target pigment particles but is adsorbed on the surface of other particles. The pigment dispersion effect of the pigment dispersant may be impaired. Therefore, for example, in the case of producing a photosensitive material or the like, in order to contain the pigment in the photosensitive material or the like in a well-dispersed state, the pigment and the pigment dispersant of the present invention are mixed at an early stage. It is preferable to add a binder polymer having an acidic group before or during dispersion, and it is preferable to add and mix the pigment dispersant of the present invention at a late time such as when preparing a coating liquid for a photosensitive layer or the like. Absent.

【0048】

The pigment dispersant of the present invention can be suitably used for dispersing known pigments, and can be particularly preferably used for the pigment dispersion composition and the colored photosensitive composition of the present invention described later.

【0049】

&lt;&lt; Pigment Dispersion Composition &gt;&gt; The pigment dispersion of the present invention comprises the pigment dispersant of the present invention and a pigment dispersed in an organic solvent, and more preferably a binder polymer having an acidic group. Become.

【0050】

(Pigment) Examples of the pigment include organic pigments. Examples of the organic pigment include yellow pigment, orange pigment, red pigment, violet pigment, blue pigment, green pigment, brown pigment, black pigment and the like.

【0051】

Examples of the yellow pigment include CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 12, CI Pigment Yellow 17, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 109, and CI Pigment. Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 185, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 153, CI Pigment Examples include yellow, CI pigment yellow 154, CI pigment yellow 166, CI pigment yellow 168, CI pigment yellow 185, and the like.

【0052】

Examples of the orange pigment include CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 71, and the like.

【0053】

Examples of the red pigment include CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, and CI. Pigment Red 192, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 217, CI Pigment Red 220, CI Pigment Red 223, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 227, CI Pigment Red 228, CI Pigment Red 240, CI Pigment Red 48: 1, CI Pigment Red 209, CI Pigment Red 146, CI Pigment Red 11, CI Pigment Red 81, CI Pigment Red 213, CI Pigment Red 272, CI Pigment Red 270, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 254, etc. can be mentioned.

【0054】

Examples of the violet pigment include CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 30, CI Pigment Violet 37, CI Pigment Violet 40, CI Pigment Violet 50, and the like.

【0055】

Examples of the blue pigment include CI Pigment Blue 15, CI Pigment Blue 15: 6, CI Pigment Blue 22, C, I. Pigment Blue 60, CI Pigment Blue 64, and the like.

【0056】

Examples of the green pigment include CI Pigment Green 7, CI Pigment Green 36, and the like. Examples of the brown pigment include CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, and the like. Examples of the black pigment include CI Pigment Black 7, and the like.

【0057】

These pigments may be used alone or in combination of two or more. In the present invention, among these, pigments having an acidic group such as Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 185, Pigment Yellow 83, etc. are preferable, and Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 185, Pigment Red 254. , Pigment Green 36, Pigment Blue 15, etc. are particularly preferable.

【0058】

(Organic Solvent) The organic solvent is not particularly limited and may be appropriately selected from known ones. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other (poly) alkylene glycol monoalkyl ethers and their acetate esters; ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate and the like. Acetate esters; aromatic hydrocarbons such as benzene, toluene, xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, etc. Alcohols, etc. These may be used alone or in combination of two or more. Among these, alkylene glycol monoalkyl ethers, acetic acid esters thereof, acetic acid esters, methyl ethyl ketone, and the like are preferable.

【0059】

The content of the pigment in the pigment dispersion composition is usually 5 to 80% by weight, preferably 10 to 70% by weight. If the content is less than 5% by weight, the coloring power may not be sufficient, and if it exceeds 80% by weight, the viscosity of the pigment dispersion composition may increase.

【0060】

The content of the pigment dispersant in the pigment dispersion composition is usually 0.1 to 100 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the pigment. If the content is less than 0.1 parts by weight, the viscosity of the pigment dispersion composition may increase, and if it exceeds 100 parts by weight, it becomes difficult to adjust the chromaticity when producing a color filter or the like. Sometimes.

【0061】

The content of the organic solvent in the pigment dispersion composition is usually 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, based on 100 parts by weight of the pigment. If the content is less than 10 parts by weight, the viscosity of the pigment dispersion composition may increase, and if it exceeds 1000 parts by weight, it may be difficult to secure a space during storage.

【0062】

(Binder Polymer Having an Acid Group) The pigment dispersion composition of the present invention preferably contains a binder polymer having an acidic group. The binder polymer having an acidic group can impart both the dispersion stability of the pigment and the alkali developability when used as a colored photosensitive composition, for example, with (meth) acrylic acid. Examples thereof include a copolymer with a (meth) acrylic acid ester, a styrene / maleic anhydride copolymer, and a reaction product of a styrene / maleic anhydride copolymer and alcohols. These may be used alone or in combination of two or more. Among these, it has excellent pigment dispersibility, excellent compatibility with polyfunctional monomers and photopolymerization initiators when used as a colored photosensitive composition, alkali-developing solution solubility, organic solvent solubility, strength, and softening. Those having an appropriate temperature and the like are preferable, and specifically, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

【0063】

The weight average molecular weight of the binder polymer having an acidic group is preferably 5000 to 200,000. If the weight average molecular weight is less than 5000, there may be a problem in forming a coating film when used as a colored photosensitive composition, and if it exceeds 200,000, the viscosity of the colored photosensitive composition becomes high. Sometimes.

【0064】

The content of the binder polymer having an acidic group in the pigment dispersion composition is usually 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the pigment. If the content is less than 10 parts by weight, the steric repulsion effect may not be obtained, and if it exceeds 200 parts by weight, the viscosity of the dispersion liquid may increase.

【0065】

The pigment dispersion composition of the present invention can be prepared, for example, by the following method. 1) A method in which a composition obtained by premixing the pigment and the pigment dispersant is added to the organic solvent (or vehicle) and dispersed. 2) A method in which the pigment and the pigment dispersant are separately added and dispersed in the organic solvent (or vehicle). 3) A method in which the pigment and the pigment dispersant are separately dispersed in the organic solvent (or vehicle) in advance and the obtained dispersion is mixed (in this case, the pigment dispersant is dispersed only in the organic solvent). May) 4) A method of dispersing the pigment in the organic solvent (or vehicle) and then adding the pigment dispersant to the obtained dispersion. [0066]

The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and a component (binder) that is liquid and binds to the pigment to harden the coating film and dissolves and dilutes the component (binder). Contains the component (the organic solvent).

【0067】

The disperser used when dispersing the pigment is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill.

【0068】

To form a colored image using the pigment dispersion composition, for example, a coating liquid containing the pigment dispersion composition is applied onto a support and dried to form a layer of the pigment dispersion composition, or is temporarily supported. A layer of this pigment dispersion composition formed on the body is transferred onto a support, on which a layer of a known positive or negative photosensitive resin composition is formed, exposed, developed, and then undeveloped. It can be carried out by a method of removing the layer of the pigment dispersion composition in the same region together with the layer of the photosensitive resin composition for exposure.

【0069】

&lt;&lt; Colored Photosensitive Composition &gt;&gt; The colored photosensitive composition contains at least the pigment dispersion composition and the photosensitive composition.

【0070】

(Photosensitive Composition) Examples of the photosensitive composition include the photosensitive composition described in JP-A-3-282404, and specifically, the photosensitive composition comprises a negative diazo resin and a binder. Examples thereof include a photosensitive composition, a photopolymerizable composition, a photosensitive composition composed of an azide compound and a binder, and a cinnamon acid type photosensitive composition. As the photosensitive composition, one that can be developed with an alkaline aqueous solution and one that can be developed with an organic solvent are known. However, in terms of pollution prevention, occupational safety, etc., those that can be developed with an alkaline aqueous solution are known. preferable.

【0071】

-Photopolymerizable composition- In the present invention, the photopolymerizable composition is particularly preferable among the photosensitive compositions. The photopolymerizable composition contains at least a binder polymer having an acidic group, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator.

【0072】

--Binder polymer with acidic group-- The binder polymer having an acidic group contained in the photopolymerizable composition is a binder polymer having an acidic group preferably contained in the pigment dispersion composition of the present invention.

【0073】

The content of the binder polymer having an acidic group in the colored photosensitive composition is about 20 to 80% by weight based on the total solid content. If the content is less than 20% by weight, problems may occur in the formation of the coating film, and if it exceeds 80% by weight, the ability of other materials may be difficult to be exhibited.

【0074】

--A polyfunctional monomer having two or more ethylenically unsaturated double bonds-- Examples of the polyfunctional monomer having two or more ethylenically unsaturated double bonds include known (meth) acrylic acid esters and urethane (meth) acrylates as described in JP-A-60-258539. , (Meta) acrylic acid amide, allyl compound, vinyl ester, etc. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid ester is preferable.

【0075】

The content of the polyfunctional monomer having an ethylenically unsaturated double bond in the colored photosensitive composition is preferably 10 to 60% by weight based on the total solid content. If the content is less than 10% by weight, the curing power at the time of exposure may be insufficient, and if it exceeds 60% by weight, the ability of other materials may be difficult to be exhibited.

【0076】

--Photopolymerization initiator-- As the photopolymerization initiator, it is preferable to use at least one compound having a molecular absorption coefficient of at least about 50 at a wavelength of about 300 to 500 nm, and examples of such a compound include JP-A-2-48664. Examples thereof include aromatic ketones, loffin dimers, benzoins, benzoin ethers, polyhalogens, etc., as described in JP-A-1-152449 and JP-A-2-153353. .. These may be used alone or in combination of two or more. Among these, the combination of 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and 4- [pN, N-di (ethoxycarbonylmethyl)- 2,6-di (trichloromethyl) -s-triazine] is preferred.

【0077】

The content of the photopolymerization initiator in the colored photosensitive composition is preferably 0.2 to 10% by weight based on the total solid content of the colored photosensitive composition. If the content is less than 0.2% by weight, the exposure sensitivity may be low, and if it exceeds 10% by weight, the exposure sensitivity may be too high (difficult to control).

【0078】

The colored photosensitive composition can be prepared, for example, by mixing the pigment dispersion composition and the photosensitive composition according to appropriately selected conditions and methods.

【0079】

The formation of a colored image using the colored photosensitive composition can be basically carried out by the following steps (1) to (3). (1) A step of preparing the colored photosensitive composition using the pigment dispersion composition after preparing the pigment dispersion composition. (2) The obtained colored photosensitive composition is applied onto a substrate and dried, or a layer formed by applying and drying on another temporary support is transferred onto the substrate to obtain a colored photosensitive composition. The process of forming a layer of material (3) A step of exposing and developing a layer of a colored photosensitive composition formed on a substrate to form a pattern. [0080] [0080]

The color filter used for the liquid crystal display or the like can be manufactured by repeating the steps (2) and (3) above and combining the patterns of the second and subsequent colors. A method for producing a color filter by a transfer method is described in, for example, JP-A-4-208940, JP-A-5-72724, JP-A-5-80503, JP-A-5-13320 and the like.

【0081】

As the substrate, a transparent material such as a glass plate or a transparent plastic plate is generally used. In order to improve the adhesion between the substrate and the colored photosensitive composition, various commercially available silane coupling agents or the like are added to the colored photosensitive composition, or the substrate is previously coupled. You may.

【0082】

The coating liquid of the colored photosensitive composition can be applied to the substrate by using a known coating means such as a spin coater, a roll coater, a bar coater, and a curtain coater.

【0083】

As a method of transferring the layer of the colored photosensitive composition formed on the temporary support onto the substrate, a method of using a heat roll laminator under normal pressure or reduced pressure is preferable.

【0084】

Examples of the developing solution used in the development include hydroxides or carbonates of alkali metals or alkaline earth metals, hydrogen carbonates, asimonia water, aqueous solutions of quaternary ammonium salts, and the like. These may be used alone or in combination of two or more. Of these, an aqueous sodium carbonate solution is particularly preferable.

【0085】

[Example]

Examples of the present invention will be described below, but the present invention is not limited to these examples.

【0086】

(Example 1) A red pigment dispersion composition having the following composition was prepared. CI Pigment Red 254 6.4g Pigment Dispersant of Synthesis Example 2 0.6g Methacrylic acid / benzyl methacrylate copolymer 15.8g (Mole ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-pro Pill acetate solution) 1-Methoxy-2-propyl acetate 57.2g [0087]

The red pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours to prepare a red pigment dispersion composition.

【0088】

The obtained pigment dispersion composition was evaluated as follows. (1) Viscosity measurement: The viscosity of the obtained pigment dispersion composition was measured using an E-type viscometer to evaluate the degree of thickening. The results are shown in Table 1.

【0089】

(2) Contrast measurement: The obtained pigment dispersion composition was applied onto a glass substrate so as to have a thickness of 6 μm to prepare a sample. This sample was placed between two polarizing plates, and the amount of transmitted light when the polarization axes were parallel and vertical was measured, and the ratio was used as the contrast ("1990 7th Color Optical Conference, 512 Color Display 10.4". "Color filter for size TFT-LCD, Ueki, Ozeki, Fukunaga, Yamanaka" was referred to). The results are shown in Table 1.

【0090】

(Example 2) In Example 1, a red pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant of Synthesis Example 2 was replaced with the pigment dispersant of Synthesis Example 1. The same evaluation as in Example 1 was performed.

【0091】

(Example 3) In Example 1, a red pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant of Synthesis Example 2 was replaced with the pigment dispersant of Synthesis Example 3. The same evaluation as in Example 1 was performed.

【0092】

(Example 4) In Example 1, a red pigment dispersion composition was prepared in the same manner as in Example 1 except that CI Pigment Red 254 was replaced with CI Pigment Red 177, and the evaluation was the same as in Example 1. Was done.

【0093】

(Example 5) In Example 1, a yellow pigment dispersion composition was prepared in the same manner as in Example 1 except that CI Pigment Red 254 was replaced with CI Pigment Yellow 139, and the evaluation was the same as in Example 1. Was done.

【0094】

(Example 6) In Example 1, a yellow pigment dispersion composition was prepared in the same manner as in Example 1 except that CI Pigment Red 254 was replaced with CI Pigment Yellow 138, and the same evaluation as in Example 1 was performed. Was done.

【0095】

(Example 7) In Example 1, a green pigment dispersion composition was prepared in the same manner as in Example 1 except that CI Pigment Red 254 was replaced with CI Pigment Green 36, and the same evaluation as in Example 1 was performed. Was done.

【0096】

(Example 8) In Example 1, a blue pigment dispersion composition was prepared in the same manner as in Example 1 except that CI Pigment Red 254 was replaced with CI Pigment Blue 15: 6, and the same as in Example 1. Was evaluated.

【0097】

(Comparative Example 1) In Example 1, a red pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant of Synthesis Example 2 was not added at all, and the same evaluation as in Example 1 was performed. Was done.

【0098】

(Example 9) The following compositions were mixed to prepare a colored photosensitive composition for producing a color filter. The red pigment dispersion composition of Example 1 32.4g Methacrylic acid / benzyl methacrylate copolymer 9.0g (Mole ratio 28/72, weight average molecular weight 30,000, 30% 1-methoxy-2-propi Luacetate solution) Pentaerythritol tetraacrylate 5.2g 4- [pN, N-di (ethoxycarbonylmethyl)] -2,6-di (trichloromethyl) -5-triazine 0.2g Hydroquinone monomethyl ether 0.01g 1-Methoxy-2-propyl acetate 62g [0099]

The mixing was carried out on a motor mill M50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours. The viscosity of the obtained colored photosensitive composition for producing a color filter was measured in the same manner as in Example 1, a color filter was prepared as described below, and the contrast was measured in the same manner as in Example 1. The results are shown in Table 1.

【0100】

That is, the colored photosensitive composition for producing a color filter was applied onto a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Then, it was exposed to an ultra-high pressure mercury lamp under a nitrogen stream and then developed with a 1% aqueous sodium carbonate solution. The contrast of the obtained color filter was measured in the same manner as in Example 1.

【0101】

(Example 10) A colored photosensitive composition in the same manner as in Example 9 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Example 2 in Example 9. Was prepared and evaluated in the same manner as in Example 9.

【0102】

(Example 11) A colored photosensitive composition in the same manner as in Example 9 except that the red pigment dispersion composition of Example 1 was replaced with the red pigment dispersion composition of Example 3 in Example 9. Was prepared and evaluated in the same manner as in Example 9.

【0103】

(Example 12) In Example 9, 32.4 g of the red pigment dispersion composition of Example 1, 25.9 g of the red pigment dispersion composition of Example 4, and 6.5 g of the yellow pigment dispersion composition of Example 5. A colored photosensitive composition was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9.

【0104】

(Example 13) In Example 9, 32.4 g of the red pigment dispersion composition of Example 1, 13.0 g of the yellow pigment dispersion composition of Example 6, and 19.4 g of the green pigment dispersion composition of Example 7. A colored photosensitive composition was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9.

【0105】

(Example 14) A colored photosensitive composition in the same manner as in Example 9 except that the red pigment dispersion composition of Example 1 was replaced with the blue pigment dispersion composition of Example 8 in Example 9. Was prepared and evaluated in the same manner as in Example 9.

【0106】

[table 1]

<img file="JP2000239554A_D0016.tif" />【0107】

From the results in Table 1, it is clear that the pigment dispersion composition of the present invention containing the pigment dispersant of the present invention and the colored photosensitive composition using the same have low viscosity and high contrast can be obtained. It is presumed that the high contrast is obtained because the pigment particles are dispersed in a finely divided state. On the other hand, in the case of the pigment dispersion composition of the comparative example, the viscosity was high and dispersion was not possible.

【0108】

[Effect of the invention]

According to the present invention, the above-mentioned conventional problems can be solved. Further, according to the present invention, it is possible to provide a pigment dispersant which realizes stable and good dispersibility and fluidity of the pigment without agglomerating the pigment and also has excellent light transmittance. Further, according to the present invention, the pigment dispersant is contained, the pigment has excellent dispersibility, fluidity, etc., high coloring power, excellent alkali development suitability, and a wide range of paints, printing inks, color display boards, etc. It is possible to provide a pigment dispersion composition that can be suitably used in the range. Further, according to the present invention, the pigment dispersion composition is contained, the coloring power is high, the suitability for alkaline development is excellent, the formation of a multicolor image on a substrate such as a color proof, and the color used for a liquid crystal color display or the like. It is possible to provide a colored photosensitive composition that can be suitably used for manufacturing a filter or the like.