KR100812280B1 - Pigments dispersion compositions, colored photosensitive composition using the same and color filter - Google Patents

Abstract

Provided is a pigment dispersion composition which is excellent in dispersion stability and color tone, and can produce a color filter having high light transmittance, especially when used in the production of a color filter.

It is a pigment dispersion composition which comprises disperse | distributing a pigment, the dispersing wavelength of the transmission spectrum of 400-550 nm, and an average particle diameter of 100 nm or less, and resin in an organic solvent. Preferably, the resin is the pigment dispersion composition, characterized in that the polymer having an acid group having an acid value of 60 to 130.

Description

Pigment dispersion composition, coloring photosensitive composition and color filter using the same {PIGMENTS DISPERSION COMPOSITIONS, COLORED PHOTOSENSITIVE COMPOSITION USING THE SAME AND COLOR FILTER}

1 is a conceptual diagram used to explain the rising wavelength of the transmission spectrum according to the present invention.

2 is a diagram schematically showing the transmission spectrum of the pigment and the transmission spectrum of the dispersant according to the pigment dispersion composition of the present invention.

3 is a view schematically showing the transmission spectrum of the green pigment according to the pigment dispersion composition of the present invention and the transmission spectrum of the green pigment containing the dispersant.

The present invention relates to a pigment dispersion composition, a coloring photosensitive composition and a color filter using the same.

Conventionally, since pigments exhibit vivid color tone and high coloring power, they are widely used in many fields such as paints, printing inks and color display plates. Moreover, since the photosensitive composition containing a pigment can form the image which has a vivid color tone by light irradiation, it is a material of color filters, such as formation of multicolored images on base bodies, such as a color proof, and a liquid crystal color display, for example. It is widely used. In these various uses, a pigment is normally used as a pigment dispersion composition disperse | distributed to the medium, such as an organic solvent.

In the pigment dispersion composition, when the dispersion stability of the pigment is insufficient, the pigment may aggregate and fluidity as a coating may not be obtained. Moreover, when forming a colored coating film, such as when using for manufacture of a color filter, there exists a problem that a uniform coating film cannot be formed. In addition, when the pigment aggregates, a desired color tone and light transmittance may not be obtained, which may adversely affect the display characteristics of the color filter. A dispersant is often added to the pigment dispersion composition for the purpose of improving the dispersion stability of the pigment in the pigment dispersion composition. The dispersant is roughly divided into a polymer dispersant and a low molecular weight dispersant, and the polymer dispersant is a polyacrylate, a sodium maleate olefin copolymer, a terminal carboxyl group-containing polyester (Japanese Patent Publication No. 54-34009), tetrakis Polyester having an acidic group and / or basic group having (2-hydroxyalkyl) ethylenediamine as a starting material (Japanese Patent Laid-Open Publication No. 2-245231), a macromonomer (an oligomer having an ethylenically unsaturated group at the end), The copolymer which consists of four types of a monomer which has a hydroxyl group, a carboxyl group-containing monomer, and monomers other than these (Japanese Unexamined-Japanese-Patent No. 8-259876), etc. are known. As the low molecular weight compound dispersant, sorbitan fatty acid ester, polyoxyethylene alkylamine, alkyldiamine, alkanolamine derivatives (US Patent No. 3536510), and the like are known. Japanese Patent Application Laid-Open No. 5-72943 and Japanese Patent Application Laid-Open No. Hei 8-48890.

When the conventional dispersing agent is used, the dispersion stability of a pigment improves to some extent. However, for example, when used for the production of color filters, color proofs and the like, a very thin colored coating film is formed, and the vivid coloring property is required for the coating film. Therefore, the pigment needs to be highly refined. When the pigment is miniaturized, the pigment dispersion composition becomes high viscosity, and as a result, the quality of the color filter and the color proof produced may be reduced. On the other hand, by adding a pigment derivative having the same skeleton as the pigment, a pigment dispersion composition which improves the dispersion stability of the pigment is, for example, US Patent No. 4,664,714, US Patent No. 4,310,359, US Patent No. 3,973,981 and Patent Publication No. 59-96175, and the like. Moreover, the pigment dispersion composition which improved the dispersibility of a pigment by using together the pigment derivative which has a skeleton same as a pigment to disperse, and a urethane type pigment dispersant is described in Unexamined-Japanese-Patent No. 62-295966. When the dispersant having the same skeleton as the pigment is used, the dispersion stability of the pigment is improved, but since the dispersant is colored, the color tone originally possessed by the pigment may be impaired. As a result, it may be difficult to adjust a pigment dispersion composition to a desired color tone.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a pigment dispersion composition which is excellent in dispersion stability and color tone and which can produce a color filter with high contrast stably, especially when used in the production of a color filter. . Moreover, an object of this invention is to provide the coloring photosensitive composition which can form the image which has vivid color tone and high light transmittance, and can produce stably the color filter with high contrast, especially when used for manufacture of a color filter. . Moreover, this invention makes it a subject to provide the color filter which has vivid color tone, high light transmittance, and high contrast.

Means for solving the above problems are as follows.

A pigment dispersion composition comprising a <1> pigment, a dispersant having a rising wavelength of 400 to 550 nm and an average particle diameter of 100 nm or less, and a resin dispersed in an organic solvent.

The pigment dispersion composition as described in <2> <1> whose said resin is a polymer which has an acidic group.

It is a pigment dispersion composition as described in <3> <2> whose acid value of the polymer which has the said acidic group is 60-130.

<4> The pigment dispersion composition according to any one of <1> to <3>, wherein the dispersant and the pigment have an azo pigment skeleton.

<5> The pigment dispersion composition according to any one of <1> to <4>, wherein the dispersant is a compound represented by the following general formula (I).

In general formula (I), A represents the component which can form an azo pigment with X-Y. X represents a group selected from a single bond or a divalent linking group represented by the following structural formula. Y represents a group represented by the following general formula (II).

In General Formula (II), Z represents a lower alkylene group. -NR ₂ represents a lower alkylamino group or a 5-6 membered saturated hetero ring containing a nitrogen atom. a represents 1 or 2.

It is a coloring photosensitive composition characterized by containing the pigment dispersion composition in any one of <6> <1>-<5>, the polyfunctional monomer which has 2 or more of ethylenically unsaturated double bonds, and a photoinitiator.

<7> A color filter having two or more patterned colored layers having different colors on a substrate, wherein the colored layer is made of the colored photosensitive composition according to <6>.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.                     

Pigment Dispersion Composition

The pigment dispersion composition of the present invention is characterized by dispersing a pigment, a dispersant having a rising wavelength of 400 to 550 nm and an average particle diameter of 100 nm or less, and a resin in an organic solvent. Here, the rising wavelength of the transmission spectrum refers to the wavelength indicated by the arrow in the graph of FIG. 1 and refers to the wavelength at which the transmittance starts to increase rapidly in the transmission spectrum curve. More specifically, it means the wavelength of the intersection of the tangent line at the bottom of the transmission spectrum curve and the tangent line at the rising part.

In the present invention, the transmission spectrum of the dispersant is composed of a composition consisting of a dispersant (concentration 10%), an acrylic resin (concentration 20%), and a solvent (concentration 70%), and a transmission spectrum of a coating film having a thickness of 3 µm. It means.

Conventionally, when a dispersant having a pigment skeleton is used, the dispersion stability of the pigment can be improved, but the dispersant has a significant effect on the color tone of the pigment, and in some cases, the color tone of the pigment cannot be sufficiently exhibited. In the present invention, the increase in the transmission spectrum as a dispersant improves the dispersion stability of the pigment while improving the dispersion stability of the pigment while suppressing the influence of the dispersant on the color tone of the pigment dispersion composition, thereby fully exhibiting the color tone of the pigment original. . In particular, even in the case of supplying a color filter for which the pigment needs to be refined, it is possible to stably produce a color filter having a small increase in viscosity due to the miniaturization of the pigment, having a vivid color tone and high light transmittance, and high contrast. Can be.

It is preferable that it is 400-550 nm, and, as for the rise wavelength of the transmission spectrum of the dispersing agent used by this invention, it is more preferable that it is 410-500 nm. The dispersant is preferably a compound having a pigment skeleton in which the rising wavelength of the transmission spectrum is in the above range and the peak of the transmission spectrum is present in the near infrared region, specifically 450 to 700 nm, from the visible portion.

2, the blue pigment (B) having a peak at a wavelength of 450 nm, the green pigment having a peak at a wavelength of 550 nm (G), the red pigment having a peak at a wavelength of 650 nm (R), and the dispersant (D) having a rising wavelength of 475 nm. An example of the spectrum is typically shown.

In Fig. 2, attention is paid to the transmission spectrum of the green pigment and the transmission spectrum of the dispersant. It can be seen that the green pigment is particularly affected by the position of the rising wavelength of the dispersant and its color tone and its transmittance. If the rising wavelength of the dispersant exceeds 550 nm, the transmittance significantly decreases. Moreover, if the rise wavelength of a dispersing agent is less than 400 nm, the target chromaticity will not be acquired and the usage-amount of the other pigment (for example, yellow pigment) used as a complementary color will increase. 3 shows an example of the transmission spectrum (G) of the green pigment and the transmission spectrum (G + D) of the green pigment when the dispersant is added. As shown in Fig. 3, when a dispersant having a rise in the wavelength range is used, the green pigment dispersion composition can be prepared without impairing the color tone of the original green pigment.

Focusing on the transmission spectrum of the red pigment of FIG. 2 and the spectrum of the dispersant, it can be seen that the effect of the transmission spectrum of the red pigment is small by adding the dispersant. The dispersant exhibiting a rising wavelength in the above range shows a peak of the transmission spectrum at the same position as the yellow pigment, but generally, since the yellow pigment is often added to adjust the color of the red pigment, the effect is small. Moreover, it has the advantage that the addition amount of the yellow pigment added for color tone adjustment can be reduced.

 When the transmission spectrum of the dispersant is combined with the transmission spectrum of the blue pigment of FIG. 2, the transmittance of the transmission spectrum of the blue pigment tends to decrease, so that the dispersion composition of the blue pigment is compared with that of the pigment dispersion composition of other colors. Less is desirable.

The dispersant used for this invention is 100 nm or less in average particle diameter. Preferably it is 80 nm or less, More preferably, it is 60 nm or less. If the particle diameter of a dispersing agent is the said range, light transmittance can be made higher and especially, when used for preparation of a color filter, the color filter which has high light transmittance can be manufactured.

As a dispersing agent used for this invention, the compound which has a pigment skeleton is preferable, and the compound which has an azo pigment skeleton is preferable. In particular, the compound represented by the following general formula (I) is preferable. When the dispersant is used, the dispersant is adsorbed on the surface of the pigment particles by the nitrogen atom of the dispersant, the surface of the pigment particles is covered with the dispersant, and the pigment particles are suppressed from adsorbing to each other, and the pigments are aggregated. It becomes difficult to do it. As a result, the pigment particles are uniformly dispersed in a refined state, and the dispersibility of the pigment is particularly good.

In general formula (I), A represents the component which can form an azo pigment with X-Y.                     

The said A can be arbitrarily selected as long as it is a compound which can form an azo pigment by coupling with a diazonium compound.

Although the specific example of said A is shown below, this invention is not limited to these specific examples at all.

In the general formula (I), X represents a group selected from a single bond (Y means directly connected to -N = N-) or a divalent linking group represented by the following structural formula.

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

In General Formula (II), Z represents a lower alkylene group. Z is represented by-(CH ₂ ) _b- , but _b represents an integer of 1 to 5, preferably 2 or 3.

In General Formula (II), -NR ₂ represents a 5-6 membered saturated hetero ring containing a lower alkylamino group or a nitrogen atom. In the case where -NR ₂ represents a lower alkylamino group, -N (C _n H _{2n + 1} ) ₂ is represented, n represents an integer of 1 to 4, and preferably 1 or 2. On the other hand, when said -NR ₂ represents a 5-6 membered saturated hetero ring containing a nitrogen atom, the hetero ring represented by the following structural formula is preferable.

Wherein Z and -NR ₂ in the formula (II) may optionally each have a lower alkyl group, an alkoxy group as a substituent.

In said general formula (II), a represents 1 or 2, Preferably it represents 2.

Although the specific example of a compound represented by the said general formula (I) is shown below, this invention is not limited to these specific examples at all.

Amine compound and / or general formula (IV) represented by general formula (III) as described in Japanese Patent Application Laid-open No. Hei 2000-239554, and 0043 to 0043 together with the compound represented by the general formula (I). It is preferable to use together the amine compound represented by (). The compound represented by the said general formula (I) can be synthesize | combined according to the method as described in the column of 0033-0035 of Unexamined-Japanese-Patent No. 2000-239554. Moreover, as a compound represented by the said General formula (I), you may use a commercial item, for example, "Solpers 22000" of Abin Asa.

Although the preferable range of content of the said dispersing agent in the pigment dispersion composition of this invention changes also with the kind of dispersing agent to be used, As a preparation of the dispersion composition of green and red pigment, it is generally 0.1-100 mass mass with respect to 100 mass parts of pigments. It is preferable that it is denier, and it is more preferable that it is 1-30 mass parts. In preparation of the dispersion composition of a blue pigment, it is preferable that it is generally 10 mass parts with respect to 100 mass parts of pigments, and it is more preferable that it is 2-5 mass parts. When the said content is the said range, while adjusting the chromaticity at the time of preparation of a color filter etc., it is preferable, preventing the viscosity of a pigment dispersion composition from raising excessively.

An organic pigment is mentioned as a pigment which can be used for the pigment dispersion composition of this invention. As said organic pigment, yellow pigment, orange pigment, red pigment, violet pigment, blue pigment, green pigment, brown pigment, black pigment, etc. are mentioned, for example.

Moreover, when a dispersing agent is a compound which has an azo pigment skeleton (for example, the compound represented with the said general formula (I)), it is preferable that the pigment used in combination is also a pigment which has an azo pigment skeleton.

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, 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 CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow, CI Pigment Yellow 154, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 185 Etc. can be mentioned.

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. Can be mentioned.                     

As said red pigment, 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, 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 242, CI Pigment Red 148: 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 and the like.

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. Can be mentioned.

As said blue pigment, C.I. pigment blue 15, C.I. pigment blue 15: 6, C.I. pigment blue 22, C.I. pigment blue 60, C.I. pigment blue 64, etc. are mentioned, for example.

As said green pigment, C.I. pigment green 7, C.I. pigment green 36, etc. are mentioned, for example.

As said brown pigment, C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment brown 26, etc. are mentioned, for example. As said black pigment, C.I. pigment black 7 etc. are mentioned, for example.                     

These pigments may be used individually by 1 type, and may use 2 or more types together. In this invention, the pigment which has acidic groups, such as pigment yellow 138, pigment yellow 139, pigment yellow 185, pigment yellow 83, is preferable, and pigment yellow 138, pigment yellow 139, pigment yellow 185, Pigment Red 254, Pigment Green 36, Pigment Blue 15, and the like are particularly preferred.

Although the preferable range also changes with content of the pigment in the pigment dispersion composition of this invention according to the kind used, Generally 5-80 mass% is preferable and 10-70 mass% is more preferable. If the said content is the said range, since it can prevent that a viscosity rises excessively, maintaining coloring power high, it is preferable.

As resin which can be used for the pigment dispersion composition of this invention, the polymer which has an acidic group is preferable. When the polymer having an acid group is used as the resin, steric repellency can be imparted, dispersion stability of the pigment is improved, and alkali developability is improved when used as a color photosensitive composition. As a polymer which has the said acidic group, the copolymer of (meth) acrylic acid and (meth) acrylic acid ester, a styrene / maleic anhydride copolymer, and the reaction product of a styrene / maleic anhydride copolymer, and alcohol etc. are mentioned, for example. These may be used individually by 1 type and may use 2 or more types together. Among these, those having excellent pigment dispersibility, excellent compatibility with a polyfunctional monomer and a photopolymerization initiator when used as a coloring photosensitive composition, suitable for alkali developer solubility, organic solvent solubility, strength, softening temperature, and the like are preferred. As a copolymer (for example, methacrylic acid / methacrylic acid benzyl copolymer) of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

It is preferable that the acid value of the polymer which has the said acidic group is 60-130. If acid value is the said range, dispersion stability is favorable and since a viscosity is suppressed low, it is preferable. In addition, the acid value unit is represented by milligrams of potassium hydroxide required for neutralizing 1 g of the polymer. In addition, the acid value of the said polymer can be adjusted with the molar ratio of the monomer which comprises a polymer.

As a weight average molecular weight of the polymer which has the said acidic group, 5000-200000 are preferable. When the said weight average molecular weight is less than 5000, when using as a coloring photosensitive composition, there may exist a problem in formation of a coating film, and when it exceeds 200000, the viscosity of a coloring photosensitive composition may increase.

Although the preferable range also changes with content of the said resin in the pigment dispersion composition of this invention by the kind used, Generally, 10-200 mass parts is preferable normally with respect to 100 mass parts of said pigments, and 20-150 mass Addition is more preferable. When the said content is the said range, since a steric repulsion effect is obtained and the viscosity of a dispersion liquid can be prevented from rising excessively, it is preferable.

The pigment dispersion composition of this invention may contain other components, such as surfactant, as needed. If it contains surfactant, since dispersion stability of a pigment improves more, it is preferable. Examples of the surfactants include alkylnaphthalene sulfonates, anionic surfactants represented by phosphate ester salts, cationic surfactants represented by amine salts, aminocarboxylic acids, and amphoteric surfactants represented by betaine type. .

The pigment dispersion composition of this invention can obtain a pigment dispersion composition by disperse | distributing a pigment (for example, red, green, a blue pigment), a dispersing agent, and resin with a disperser, such as a sand mill, with a solvent. At this time, the pigment and the dispersant may be mixed in advance and refined, and then the mixture may be dispersed in an organic solvent (or vehicle), or the pigment and the dispersant may be finely treated separately in advance and then dispersed in an organic solvent (or vehicle). Alternatively, the obtained dispersion and solution may be mixed with each other, or the finely treated pigment and dispersant may be separately added to an organic solvent (or vehicle) and dispersed. In particular, it is preferable to refine | miniaturize simultaneously a pigment and a dispersing agent previously or respectively. Here, the vehicle refers to the part of the medium in which the pigment is dispersed when the paint is in the liquid state, and includes a component (binder resin) which is liquid and binds to the pigment to harden the coating film in addition to the organic solvent.

There is no restriction | limiting in particular as a disperser used when disperse | distributing a refined pigment | dye and a dispersing agent to an organic solvent, For example, well-known dispersers, such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, a sand mill, Can be mentioned.

In the pigment dispersion composition of the present invention, there is no restriction | limiting in particular as an organic solvent which disperse | distributes the said dispersing agent, a pigment, and resin, It can select from a well-known thing suitably, For example, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, and ethylene glycol monoethyl ether and these acetate esters; ethyl acetate, n-propyl acetate, Acetate esters, such as i-propyl acetate, n-butyl acetate, and i-butyl acetate; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Kenones, such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers, its acetate esters, acetate esters, methyl ethyl ketone, etc. are preferable.

As content in the said pigment dispersion composition of the said organic solvent, it is 10-1000 mass parts normally with respect to 100 mass parts of said pigments, and 20-500 mass parts is preferable. If the said content is the said range, since the viscosity of a pigment dispersion composition can be prevented from raising excessively, and securing space etc. at the time of storage will not become difficult, it is preferable.

In the present invention, the dispersant has an average particle diameter of 100 nm or less. In order to make the average particle diameter of a dispersing agent into the said range, by disperse | distributing a dispersing agent and a pigment for a long time with a high speed sand mill etc., it is possible to make a primary particle fine simultaneously with dispersing a dispersing agent and a pigment, but it requires a lot of energy. And fine pigment particles and dispersants obtained by this method are liable to cause weak aggregation generally called procurement, and the dispersion tends to be high viscosity and thixotropic, so that the coating film of a uniform color filter There is a problem that is difficult to obtain. Therefore, the method of disperse | distributing after refine | purifying primary particle for both a pigment and a dispersing agent is preferable.

The refinement | miniaturization process of the said dispersing agent and the said pigment may be performed simultaneously, and may be performed respectively. It is preferable to carry out the micronization treatment simultaneously in the state where the pigment and the dispersant coexist, because the manufacturability is good. As the above miniaturization treatment, a method of mechanically pulverizing pigments and dispersants to reduce the particle size (called a grinding method), and a method of depositing a pigment and a molecular agent having a small particle diameter by adding a solution dissolved in a good solvent into a poor solvent (precipitation method). And the method of producing particles having a small particle size at the time of synthesis (called a synthetic precipitation method). A suitable method can be selected and performed by the synthesis | combining method, chemical property, etc. of the pigment to be used and a dispersing agent. You may perform refinement | miniaturization process combining two or more types of methods. In addition, when performing refinement | miniaturization process of a pigment and a dispersing agent, respectively, refinement | miniaturization process may respectively differ.

The grinding method is a method of grinding a pigment and / or dispersant together with a grinding agent such as a salt using a ball mill, a sand mill or a kneader, and then removing the grinding agent to make the primary particles fine. And / or dispersed particles are obtained.

The precipitation method is a method in which a pigment and / or dispersant is dissolved in a suitable good solvent and then mixed with a poor solvent to precipitate fine crystal grains. The type and amount of the solvent, the precipitation temperature, and the deposition rate The size of the primary particle can be controlled according to the like. Examples of the solvent used may include strong acid solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or basic solvents such as a liquid ammonia and a dimethylformamide solution of sodium methylate.

Among the precipitation methods, there is a Loico method as a special precipitation method. Phenol dye-based pigments such as pravantron, perinone, perylene, and indanthrone are reduced to alkaline hydrosulfide, whereby the quinone group becomes a sodium salt (hydroco compound) of hydroquinone and becomes water-soluble. A fine pigment and a dispersing agent can be precipitated by adding and oxidizing a suitable oxidizing agent to this aqueous solution.

The synthetic precipitation method is a method of synthesizing pigments and / or dispersants and simultaneously depositing fine crystal grains. However, when the produced micropigment and / or microdispersant is taken out from the solvent, filtration, which is a general separation method, becomes difficult unless the particles aggregate and become large secondary particles. It is applied to pigments, such as a crude type.

Although the above-mentioned method may be used for the said refinement | miniaturization process, since the material is not limited among these methods, the grinding method is preferable. The grinding method will be described in detail below. In the present grinding method, the pigment and dispersant are mechanically kneaded together with a water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it (hereinafter referred to as salt milling), and then the inorganic salt and organic solvent are removed, It is a method of obtaining the fine pigment and dispersant of a primary particle by washing with water and drying. However, since a pigment and a dispersing agent may crystallize by a salt milling process, the method of preventing crystal growth by adding the solid resin or pigment dispersant which melt | dissolves at least partially in the said organic solvent at the time of a process is effective.

The ratio of the pigment, the dispersant, and the inorganic salt increases the finer efficiency of the pigment and the dispersant when the ratio of the inorganic salt increases, but the productivity decreases because the throughput of the pigment and the dispersant decreases. Generally, it is good to use 1-20 weight part of inorganic salts, Preferably 2-10 weight part with respect to 1 weight part of pigments and a dispersing agent. In addition, the said wetting agent is added so that a pigment, a dispersing agent, and an inorganic salt may become uniform hardening, Although it depends also on the compounding ratio of a pigment, a dispersing agent, and an inorganic salt, the quantity of 50 weight%-300 weight% of a pigment is used normally.

More specifically, for the salt milling, a small amount of water-soluble organic solvent is added to the mixture of the pigment, the dispersant, and the water-soluble inorganic salt as a wetting agent, mixed vigorously with a kneader, etc., and then the mixture is poured into water to give a high speed mixer, or the like. The mixture is stirred to form a slurry. Subsequently, this slurry is filtered, washed with water and dried to obtain a pigment and / or a dispersant in which the primary particles have been refined.

The pigment dispersion composition of this invention can be used as a coating material, a printing ink, etc. For example, the coating liquid containing the said pigment dispersion composition is apply | coated and dried on a support body, and the layer of this pigment dispersion composition is formed, or the layer of this pigment dispersion composition formed on the temporary support body is transferred onto a support body, And a layer of a known positive or negative photosensitive resin composition formed thereon, exposed, developed, and subsequently removing the layer of the pigment dispersion composition in the same area together with the unexposed layer of the photosensitive resin composition, or the like. Formation can be performed. Moreover, it can supply to image formation as a coloring photosensitive composition which can be image-formed by light irradiation by mixing with a photosensitive composition. This will be described later.

<Coloring Photosensitive Composition>

The coloring photosensitive composition of this invention contains the pigment dispersion composition of this invention, the polyfunctional monomer which has 2 or more of ethylenically unsaturated double bonds, and a photoinitiator, It is characterized by the above-mentioned. Since the coloring photosensitive composition of this invention contains the said pigment dispersion composition, it is excellent in color tone and excellent also in dispersion stability of a pigment. In particular, when used for the production of a color filter, it is possible to stably produce a color filter having vivid color tone and high light transmittance and high contrast.

As a polyfunctional monomer which has 2 or more of said ethylenically unsaturated double bonds, well-known (meth) acrylic acid ester, urethane (meth) acrylate, and (meth) which are described, for example in Unexamined-Japanese-Patent No. 60-258539. ) Acrylic acid amide, allyl compound, vinyl ester, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, (meth) acrylic acid ester is preferable.

As content in the said coloring photosensitive composition of the polyfunctional monomer which has the said ethylenically unsaturated double bond, 10-60 mass% is preferable with respect to a total solid. If the said content is the said range, since the ability of the other material is not suppressed while maintaining the hardening force at the time of exposure enough, it is preferable.

As the photopolymerization initiator, it is preferable to use at least one compound having a wavelength of about 300 to 500 nm and a molecular extinction coefficient of at least about 50. Examples of such compounds include, for example, Japanese Patent Application Laid-Open No. 2-48664, Japan Aromatic ketones, ropin dimers, benzoin, benzoin ethers, polyhalogens, etc. which are described in Unexamined-Japanese-Patent No. 1-152449 and Unexamined-Japanese-Patent No. 2-153353 are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among them, a combination of 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and 4- [pN, N-di ( Oxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine] is preferred.

As content in the said coloring photosensitive composition of the said photoinitiator, 0.2-10 mass% is preferable with respect to the total solid of a coloring photosensitive composition. If the said content is the said range, since it can prevent that exposure sensitivity becomes too high and control becomes difficult, keeping exposure sensitivity high, it is preferable.

The coloring photosensitive composition of this invention can be prepared by mixing the pigment dispersion composition of this invention, the polyfunctional monomer which has two or more ethylenically unsaturated double bonds, and a photoinitiator. Moreover, at the time of preparation, you may add resin further, and the said polymer which has the said acidic group which can be used for a pigment dispersion composition is preferable. It is preferable to use the same resin as the resin used when the pigment dispersion composition is prepared. In the coloring photosensitive composition of this invention, as content of resin (especially the polymer which has an acidic group), about 20-80 mass% is preferable with respect to a total solid. If the said content is the said range, since it can prevent that the capability of another material is hard to be exhibited, maintaining the intensity | strength of a coating film high, it is preferable.

The coloring photosensitive composition of this invention can be used for image formation by light irradiation. Formation of the colored image using the said coloring photosensitive composition can be basically performed by the process of following (1)-(3).

(1) After preparing the said pigment dispersion composition, the process of preparing the said coloring photosensitive composition using this

(2) A step of forming the layer by the photosensitive composition by transferring the obtained photosensitive composition onto a substrate and drying it or by applying the dried photosensitive composition onto another temporary support and drying the formed layer on the substrate.

(3) Process of exposing and developing layer by coloring photosensitive composition formed on board | substrate and forming a pattern

As the substrate, transparent materials such as glass plates and transparent plastic plates are generally used. In order to improve the adhesive force of the said board | substrate and the said coloring photosensitive composition, you may add various commercially available silane coupling agents etc. to the said coloring photosensitive composition, or may carry out the coupling process of the said board | substrate beforehand.

Coating of the coating liquid of the said coloring photosensitive composition to the said board | substrate can be performed using well-known coating means, such as a spin coater, a roll coater, a bar coater, and a curtain coater.

As a method of transferring the layer by the said coloring photosensitive composition formed on the said temporary support body on the said board | substrate, the method of using a heating roll laminator under normal pressure or reduced pressure is mentioned preferably.

As an example of the developing solution used at the time of the said image development, the alkali metal or alkaline-earth metal hydroxide or carbonate, hydrogencarbonate, aqueous ammonia, the quaternary ammonium salt, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, aqueous sodium carbonate solution is particularly preferred.

<Color filter>

The color filter of the present invention is a color filter having two or more patterned colored layers having different colors on a substrate, wherein the colored layer is made of the coloring photosensitive composition of the present invention. Since the colored layer of the present invention is formed by the coloring photosensitive composition of the present invention, the color filter of the present invention has a clear color tone, high light transmittance, and high contrast.

The color filter of this invention can be produced by repeating the process of said (2) and (3), and combining a pattern of multiple colors (usually three colors of R, G, and B). The color filter of this invention can also be produced using the transfer method. As a method for manufacturing a color filter using a transfer method, for example, Japanese Patent Application Laid-Open Publication Nos. Hei 4-208940, Hei 5-72724, Hei 5-80503, Hei 5-173320, and the like. Details are described and applicable to the present invention.

In the color filter of the present invention, the color layer is directly formed on a transparent substrate such as glass, and the color layer is formed on a substrate on which an active element such as TFT is formed (color filter on array: form of COA). Etc. are included.

The color filter of the present invention can be widely used for display devices such as personal computers, word processors, engineering workstations, navigation systems, televisions, and video.

Although the Example of this invention is described below, this invention is not limited at all by these Examples.

Example 1

The red pigment dispersion composition of the following composition was prepared.

Pigment Red 254 ------------------- 6.4g

Pigment dispersant 1 ----------- 0.6 g shown below

Methacrylic acid / methacrylic acid benzyl copolymer--15.8 g                     

(Molar ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution, acid value 105)

1-methoxy-2-propyl acetate ----------- 57.2 g

The maximum absorption wavelength lambda max (in CHCl ₃ ) of the following pigment dispersion composition was 391 nm, and the rising wavelength of the transmission spectrum was 445 nm. In addition, the said pigment dispersant (1) was used for preparation, after performing the following salt milling process (micronization process).

500 g of sodium chloride, 5 g of hydrogenated rosin ester (product of Arakawa Kagaku Co., Ltd., brand name ester rubber HP), 50 g of the following pigment dispersant 1, and 300 g of polyethylene glycol were kneaded with an oven kneader (Moriyama Seisakusho Co., product name S1-1) for 5 hours did. The kneaded product was poured into 2 liters of warm water and stirred vigorously with a resolver at about 70 ° C for 2 hours. Thereafter, the obtained dispersion was filtered, and the remainder of the filter was washed with water to remove sodium chloride and polyethylene glycol, and dried in a dry oven at about 40 ° C. for 2 days. The average particle diameter of the fine powder of the obtained pigment dispersant was 80 nm.

The pigment composition of the pigment | dye of the said composition was disperse | distributed at the circumferential speed of 9 m / s for 9 hours using the zirconia beads of 0.65 mm in diameter by the motor mill M-50 (made by the company), and the red pigment dispersion composition was prepared.                     

Example 2

In Example 1, the red pigment dispersion composition was prepared like Example 1 except having replaced the said pigment dispersant 1 with the following pigment dispersants 2.

Example 3

In Example 1, the red pigment dispersion composition was prepared like Example 1 except having replaced the said pigment dispersant 1 with the pigment dispersant of "Solpers 22000".

Example 4

In Example 1, the red pigment dispersion composition was prepared like Example 1 except having replaced C.I. pigment red 254 with C.I. pigment red 177.

Example 5

In Example 1, a yellow pigment dispersion composition was prepared in the same manner as in Example 1 except that C.I. Pigment Red 254 was replaced with C.I. Pigment Yellow 139.

Example 6

In Example 1, a yellow pigment dispersion composition was prepared in the same manner as in Example 1 except that C.I. Pigment Red 254 was replaced with C.I. Pigment Yellow 138.

Example 7                     

In Example 1, except for replacing C.I. Pigment Red 254 with C.I. Pigment Green 36, a green pigment dispersion composition was prepared in the same manner as in Example 1.

Example 8

In Example 1, the blue pigment dispersion composition was prepared in the same manner as in Example 1 except that the CI pigment red 254 was replaced with the CI pigment blue 15: 6, and the content of the pigment dispersant 1 was replaced with 0.3 g. Prepared.

(Comparative Example 1)

In Example 1, the red pigment dispersion composition was prepared like Example 1 except not having added the said pigment dispersant 1 at all.

(Comparative Example 2)

In Example 7, it carried out similarly to Example 7 except having used the commercially available dispersing agent "EFKA-745" (Efka Chemicals make, the rising wavelength of a transmission spectrum is 400 nm or less) instead of the said pigment dispersant 1, A pigment dispersion composition was prepared.

(Comparative Example 3)

In Example 1, the red pigment dispersion composition was prepared like Example 1 except having used the said pigment dispersant 1 (average particle diameter 120nm) which did not carry out the salt milling process.

The following evaluation was performed about the pigment dispersion composition of obtained Examples 1-8 and Comparative Examples 1-3. Moreover, about the pigment dispersion compositions of Examples 1 and 7 and Comparative Examples 2 and 3, chromaticity was measured. Table 1 shows the results of evaluation and measurement of chromaticity.                     

(1) Viscosity Measurement:

About the obtained pigment dispersion composition, the viscosity was measured using the E-type viscosity meter and the degree of viscosity increase was evaluated.

(2) Contrast measurement:

The obtained pigment dispersion composition was applied on a glass substrate so as to have a thickness of 6 μm, and a sample was prepared. This sample was placed between two polarizing plates, and the amount of transmitted light when the polarization axes were parallel and perpendicular was measured, and the ratio was made into contrast. ("7th Chromatic Optical Conference, 512 Color Display 10.4" Size TFT, 1990.) I referred to a color filter for LCD, Ueki, Koseki, Fukunaga, Yamanaka.)

From the results of Table 1, it was found that the pigment dispersion composition of the example had a low viscosity, was excellent in dispersion stability, and a high contrast was obtained. On the other hand, in the case of the pigment dispersion composition of the comparative example, the viscosity was high and could not be dispersed.

In Example 7, the same method was used as the methacrylic acid / methacrylic acid benzyl copolymer, except that a copolymer having an acid value of 50 (molar ratio of methacrylic acid / methacrylic acid benzyl copolymer was 14/86) was used. As a result of preparing the pigment dispersion composition, the viscosity was slightly higher than that of Example 7, and the dispersibility was inferior. Similarly, in Example 7, except that a copolymer of acid value 145 (molar ratio of methacrylic acid / benzyl methacrylic copolymer was 37/63) was used as methacrylic acid / methacrylic acid benzyl copolymer. As a result of preparing the pigment dispersion composition, the viscosity was slightly higher than that of Example 7, and the dispersibility was inferior.

Example 9

The following composition was mixed and the color filter preparation coloring photosensitive composition was prepared.

Pigment Dispersion Composition of Red Example 1 -------------- 32.4g

Methacrylic acid / methacrylic acid benzyl copolymer --------- 9.0 g

(Molar ratio 28/72, weight average molecular weight 30,000, 30% 1-methoxy-2-propyl acetate solution)

Pentaerythritol tetraacrylate ------------- 5.2 g

4- [p-N, N-di (ethoxycarbonylmethyl)]

-2,6-di (trichloromethyl) -5-triazine ----------- 0.2 g

Hydroquinone monomethyl ether ------------------- 0.01 g

1-methoxy-2-propyl acetate ------------------ 62 g

The mixing was performed for 9 hours at a circumferential speed of 9 m / s using zirconia beads having a diameter of 0.65 mm with a motor mill M50 (manufactured by Aigas Co., Ltd.).

About the obtained color filter action coloring photosensitive composition, the viscosity was measured like Example 1, the color filter was produced as follows, and the contrast was measured similarly to Example 1. The results are shown in Table 2.

That is, the color filter-forming coloring photosensitive composition was applied onto a glass substrate using a spin coater, dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Subsequently, after exposing with ultra-high pressure mercury lamp under nitrogen stream, it developed by the 1% sodium carbonate aqueous solution. The contrast of the obtained color filter was measured similarly to Example 1.

Example 10

In Example 9, the coloring photosensitive composition was prepared like Example 9 except having replaced the red pigment dispersion composition of Example 1 with the red pigment dispersion composition of Example 2, and is the same as Example 9 Let's evaluate.

Example 11

In Example 9, the coloring photosensitive composition was prepared like Example 9 except having replaced the red pigment dispersion composition of Example 1 with the red pigment dispersion composition of Example 3, and same as Example 9 Evaluated.

Example 12

Example 9, except that 32.4 g of the red pigment dispersion composition of Example 1 was replaced with 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, In the same manner as described above, a coloring photosensitive composition was prepared and evaluated in the same manner as in Example 9.

Example 13

Example 9, except that 32.4 g of the red pigment dispersion composition of Example 1 was replaced with 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, In the same manner as in Example, a coloring photosensitive composition was prepared and evaluated in the same manner as in Example 9.

Example 14

In Example 9, except that the red pigment dispersion composition of Example 1 was replaced with the blue pigment dispersion composition of Example 8, the coloring photosensitive composition was prepared like Example 9, and it carried out similarly to Example 9, Evaluated.

Contrast (color photosensitive composition film) Example 9 1300 Example 10 1200 Example 11 1250 Example 12 1100 Example 13 1250 Example 14 1300

According to the present invention, it is possible to provide a pigment dispersion composition which is excellent in dispersion stability and color tone, and in particular capable of stably producing a color filter with high contrast when used for the production of a color filter. Moreover, according to this invention, the image which has a vivid color tone and high light transmittance can be formed, and especially when it is used for manufacture of a color filter, the coloring photosensitive composition which can stably produce a color filter with high contrast can be provided. All. Moreover, according to this invention, the color filter which has vivid color tone and high light transmittance, and has high contrast can be provided.

Claims (10)

A pigment dispersion composition obtained by dispersing a pigment, a dispersant, and a resin in an organic solvent, wherein the dispersant has a rising wavelength of 400 to 550 nm and an average particle diameter of 100 nm or less, and the resin is a polymer having an acidic group and having the acidic group. The acid value of a polymer is 60-130, The pigment dispersion composition characterized by the above-mentioned. delete delete The pigment dispersion composition according to claim 1, wherein the dispersant and the pigment have an azo pigment skeleton. The pigment dispersion composition according to claim 1, wherein the dispersant is a compound represented by the following general formula (I).

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

(In General Formula (II), Z represents a lower alkylene group. -NR ₂ represents a lower alkylamino group or a 5-6 membered saturated hetero ring containing a nitrogen atom. A represents 1 or 2.) The pigment | dye dispersion composition of Claim 1, the polyfunctional monomer which has two or more ethylenically unsaturated double bonds, and a photoinitiator are contained, The coloring photosensitive composition characterized by the above-mentioned. A color filter having two or more patterned colored layers having different colors on a substrate, wherein the colored layer is made of the coloring photosensitive composition according to claim 6. The pigment dispersion composition according to claim 4, wherein the dispersant is a compound represented by the following general formula (I).

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

(In General Formula (II), Z represents a lower alkylene group. -NR ₂ represents a lower alkylamino group or a 5-6 membered saturated hetero ring containing a nitrogen atom. A represents 1 or 2.) The pigment | dye dispersion composition of Claim 4, the polyfunctional monomer which has two or more ethylenically unsaturated double bonds, and a photoinitiator are contained, The coloring photosensitive composition characterized by the above-mentioned. The pigment | dye dispersion composition of Claim 5, the polyfunctional monomer which has 2 or more of ethylenically unsaturated double bonds, and a photoinitiator are contained, The coloring photosensitive composition characterized by the above-mentioned.

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