TW518430B - Pigment-dispersed composition, colored photosensitizing composition using it, and color filter - Google Patents

Abstract

Provided is a pigment-dispersed composition having excellent dispersion stability and color tone and especially suitable for the production of a color filter having high transmittance of light. The pigment-dispersed composition is obtained by dispersing a pigment, a dispersing agent having a rise wavelength of transmission spectrum in the range of 400 to 550 nm and an average particle size of less than 100 nm, and a resin in an organic solvent. Preferably, the resin is a polymer containing acidic group which has an acid value in the range of 60 to 130.

Description

518430 V. Description of the invention (1) TECHNICAL FIELD The present invention relates to a pigment dispersion composition, a coloring photosensitive composition using the same, and a color filter. Prior art In the past, pigments have a bright hue and a high tinting power, and therefore they can be widely used in many fields such as paints, printing inks, and color display panels. In addition, since a photosensitive composition containing a pigment can form an image having a clear hue by being irradiated with light, it can be widely used, for example, to form a multi-color image on a substrate such as color resistance, or as a color filter for a liquid crystal color display Of materials. In these applications, pigments are usually dispersed using a pigment dispersed composition in a solvent such as an organic solvent. In this pigment dispersion composition, when the dispersion stability of the pigment is insufficient, the pigment aggregates and the fluidity of the pigment cannot be obtained. In addition, when it is used in the production of a color filter or the like, there is a problem that a uniform coating film cannot be formed when a colored coating film is formed. In addition, the desired color tone and light transmittance cannot be obtained due to pigment aggregation, which adversely affects the display characteristics of the color filter. In order to improve the dispersion stability of the pigment of the pigment dispersion composition, a dispersant is added to each of the pigment dispersion and the composition. The above dispersants can be divided into polymer-based dispersants and low-molecular compound dispersants. The above-mentioned polymer-based dispersants include polypropylene salt, sodium maleate olefin copolymer, and polytetrafluoroethylene containing terminal carboxylic acid. No. 54-3 4009), (2-hydroxyalkyl) ethylenediamine as a starting material, a polyacetic acid having an acidic group and / or a test group (Japanese Unexamined Patent Publication No. 2-245231), rough list Copolymers (such as oligomers with ethylenically unsaturated groups at the ends), 518430 monomers, monomers containing carboxyl groups, carboxyl-containing monomers, and other monomers (Japanese Patent Application Laid-Open No. 8-259876) is known. In addition, the low-molecular compound dispersant includes sorbitol fatty acid ester, polyethylene oxide alkylamine, alkanediamine, alkanolamine derivative (US Patent No. 35365 1 0), etc., and a pigment mother core is introduced. Dispersants are described in, for example, Japanese Patent Publication No. 5-72943 and Japanese Patent Application Publication No. 8-48890. When a conventional dispersant is used, the dispersion stability of the pigment can be improved to some extent. However, for example, when it is used in the production of color filters or color-blocking sheets, it is necessary to make pigments highly fine because extremely thin coloring films are formed and clear coloring properties are required in the coating film. When the pigment is made finer, the viscosity of the pigment-dispersed composition becomes higher, and as a result, the quality of the produced color filters and anti-color sheets is lowered. In addition, by adding a pigment derivative having the same skeleton as the pigment, a pigment dispersion composition having improved dispersion stability of the pigment, for example, U.S. Patent No. 4,664,714, U.S. Patent No. 4,310,359, and U.S. Patent No. 3,973 No. 98, No. 1 and JP 59-96 1 75. Furthermore, a pigment dispersion composition having a pigment dispersion having the same skeleton as a dispersed pigment and a urethane-based pigment dispersant is used, and a pigment dispersion composition having improved pigment dispersibility is disclosed in JP 6 2-2 9 5 9 6 Record. When a dispersant having the same skeleton as the pigment is used, the dispersibility of the pigment is modified, but the discoloration of the dispersant will damage the original hue of the pigment. As a result, it is difficult to adjust the pigment dispersion composition to the desired hue. In view of the above problems, the present invention is to provide excellent dispersion stability and hue, especially when used in the production of color filters. It can be stable and produce a high contrast of -4- 518430. 5. Description of the invention (3) Pigment dispersion of color filters The composition is a problem. Another object of the present invention is to provide a color-sensitive photosensitive composition capable of forming an image with a vivid color tone and high light transmittance, and in particular, when used for producing a color filter, it is possible to stably produce a color filter with a high contrast. Moreover, this invention aims at providing the color filter which has a vivid color tone, high light transmittance, and high contrast. Disclosure of the Invention A method for solving the above-mentioned problems is as follows. < 1> A pigment dispersion composition characterized by dispersing a pigment, a dispersant having a rising wavelength of transmission spectrum of 400 to 5 50 nm and an average particle diameter of 100 nm or less, and a resin in an organic solvent. < 2 > The pigment dispersion composition according to < 1 >, wherein the resin is a polymer having an acidic group. < 3 > The pigment dispersion composition according to < 2 >, wherein the acid value of the polymer having an acidic group is 60 to 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 (1), AN = N —XY general formula (1) (Wherein A is a component that forms XY and forms an azo pigment, X is a single bond or a group selected from the group consisting of a divalent bond shown in the following structural formula, and Y is a component represented by the following general formula (II) Illustrated base) 518430 V. Description of the invention (4)

< Q > -so2nh-i-< 〇) -〇-

(CONH-Z-NR2) a General formula (II) (wherein Z is a lower carbon alkylene group, -NR2 is a lower carbon alkylamino group, or a 5 or 6 carbon saturated heterocyclic ring containing nitrogen atom, a Department means 1 or 2). < 6 >-A colored photosensitive composition characterized by containing a pigment dispersion composition as described in any one of < 1 > to < 5> and having as many as two or more ethylenically unsaturated double bonds Functional monomers and photopolymerization initiators. < 7 > A color filter, which is a color filter having two or more coloring layers with different patterns on a substrate, wherein the coloring layer is a pigment dispersion composition as described in < 6 > Made. Exemplary Embodiments The present invention will be described in detail below. < Pigment dispersing composition > The pigment dispersing composition of the present invention is characterized by dispersing a pigment and a dispersant having a transmission wavelength of 400 to 550 nm and an average particle diameter of 100 nm or less, and dispersing the resin in an organic solvent. . Here, the ascending wavelength above the transmission spectrum refers to the wavelength shown by the arrow in the first figure, and the transmission spectrum curve is transparent 518430 V. Description of the invention (5) The wavelength at which the emissivity starts to change rapidly. More specifically, it refers to the intersection wavelength of the wiring at the bottom of the transmission spectrum curve and the wiring at the beginning. 1 In the present invention, the transmission spectrum of a dispersant refers to the transmission of a coating film consisting of a dispersant (concentration 10%), acrylic resin (concentration 20%), and solvent (concentration 70%) and a thickness of 3 μm. spectrum. When a dispersant with a pigment skeleton is used, the dispersion stability of the pigment can be improved, but the dispersant slightly affects the color tone of the pigment and cannot fully express the original color tone of the pigment. In the present invention, by using a compound having a transmission spectrum rising wavelength in the above range as a dispersant, the dispersion stability of the pigment can be improved and the influence of the dispersant on the hue of the pigment dispersion composition can be suppressed, and the hue originally possessed by the pigment can be fully exerted. . In particular, when it is used to make color filters that must be miniaturized, it is possible to produce color filters that have little increase in viscosity accompanied by miniaturization of pigments, have bright colors and high light transmittance, and have a contrast tube. The rising wavelength of the transmission spectrum of the dispersant used in the present invention is preferably 400 5 50 nm, and more preferably 410 to 500 nm. In addition, the dispersant is preferably a compound having a pigment skeleton when the peak of the transmission spectrum is within the above range, and the peak of the transmission spectrum is from the visible part to the infrared part, specifically 450 to 700 nm. Figure 2 shows a blue pigment (B) with a peak at a wavelength of 450 nm Λ a green pigment (G) with a peak at a wavelength of 550 nm, a red pigment (R) with a peak at a wavelength of 650 nm, and a rising wavelength 47 Typical example of the transmission spectrum of a 5nm dispersant (D). -7- 518430 V. Explanation of the invention (6 :) Figure 2 focuses on the transmission spectrum of the green pigment and the transmission spectrum of the dispersant. It can be seen that the green pigment especially varies depending on the rising wavelength position of the dispersant, its hue and its transmittance. affected. The rise of the dispersant; when the wave length is greater than 550 nm, the transmittance will be greatly reduced. When the rising wavelength of the dispersant is less than 400nm, the intended chromaticity cannot be obtained, and the amount of other pigments (such as yellow pigment) used as a complementary color is too much. Figure 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 an ascending wavelength in the above-mentioned wavelength range is used, not only the original color tone of the green pigment is not damaged, but also the green pigment dispersion composition can be modulated. Focusing on the transmission spectrum of the red pigment in Figure 2 and the spectrum of the dispersant > It can be seen that when the red pigment is added with the dispersant described above, the influence of the transmission spectrum is small. Although the dispersant with the rising wavelength in the above range has the peak of the transmission spectrum at the same position as the yellow pigment, in general, the effect of adding a yellow pigment when adjusting the hue of the red pigment is small. Furthermore, it has the effect of adding The addition of yellow pigment has the advantage that it can be as small as possible. The blue and the transmission spectrum of the pigment in Figure 2 are fully combined with the transmission spectrum of the dispersant because the transmittance tends to decrease the transmission spectrum of the blue pigment. 5 The content of the dispersant and dispersant of the blue pigment is less than that of pigment dispersant compositions of other colors. Therefore, the dispersant used in the present invention has an average particle diameter of 100 nm or less. 80 nm or less, more preferably 60 nm or less. -8- The particle diameter of the dispersant is above 518430. 5. When the range of the invention (7) is described, the light transmittance can be improved, especially when it is used in the production of color filters. It can produce green sheets with high light transmittance. . The dispersant used in the present invention is preferably a compound having a pigment skeleton, and more preferably a compound having an azo pigment skeleton. In particular, a compound represented by the following general formula (I) is preferred. When the dispersant is used, the dispersant is adsorbed on the surface of the pigment particles by the nitrogen atom of the dispersant, and the surface of the pigment particles is covered with the dispersant, which suppresses mutual adsorption between the pigment particles and makes it difficult for the pigments to aggregate. As a result, the pigment particles are uniformly dispersed in a finer state, and the dispersibility of the pigment is particularly good. A-N = N-X-Y General formula (1) wherein A is a component that represents X-Y and forms an azo pigment. A may be any compound that couples with a diazophosphonium salt compound to form an azo pigment, and can be arbitrarily selected. The following are specific examples of A, but the present invention is not limited by these specific examples. 518430 V. Description of the invention (8) ch3cochconh

Cl OCH3

Η CH3COCHCONH

〇

COCHCONH

H COCHCONH

〇 H

NCCHCONH

-10- 518430 V. Description of the invention (9

, 〇Η, CONH

In the general formula (I), X represents a single bond (Y means -N = N-direct bonding), or a group selected from the group consisting of a divalent bonding group shown in the structure below.

— ≪ Q ^ -S02NH-i In the general formula (I), Y is a group represented by the following general formula (II). General formula (II) nCONH-Z-NR ^, -11- 518430 V. Description of the invention (10) In the general formula (I I), Z is a low-carbon alkylene. Z is represented by _ (CH2) b-, where b is an integer of 1 to 5, preferably 2 or 3. In the general formula (II), -NR2 represents a lower alkylamino group or a 5 or 6 carbon saturated heterocyclic ring containing a nitrogen atom. The -N (CnH2n + 1) 2 is represented, and η is an integer of 1 to 4, preferably 1 or 2. When 11-2 represents a 5- or 6-carbon saturated heterocyclic ring containing a nitrogen atom, a heterocyclic ring represented by the following structural formula is preferred.

Pyrrolidine ring Piperidine ring Morpholine ring In the above general formula (II), ζ and -NR2 each may have a lower alkyl group and an alkoxy group as a substituent. In the general formula (II), a represents 1 or 2 ′, and 2 is preferred. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited to these specific examples. -12- 518430 V. Description of the invention (11

2.

C

0CH3 OCH3 (jiOCH: NHCOCH one punch

CONH (CH2) 3N (C2hy2 CONH (CH2) 3N (C2H5) 2 3. 3. ==

CON -CONH (CH2) 2N (C2H5) 2 • CONH (CH2) 2N (C2H5 > 2 5.

9OCH3 / ^ t--CONH (CH2) 3N (C2H5) 2 NHCOCH-N = N ~ (()> ^ = ^ C〇NH (CH2) 3N (C2H5) 2

6. H 〇 《jP〇 ^ nhc 』h— CONH (CH2) 2N {CaH5) 2 CONH (CH2 > 2N (C2H5) 2 〇 = <

N

NHC0CH-r ^ Nh-^^ > ~ C0NHH ^ 2 C〇NH (CH2) 3N (C2H5) 2 • CONhKCH ^ hKC ^ H ^ -13- 518430 V. Description of the invention (12 8. Η -CONH (CH2) 3N (C2Hs) 2 ~ 〇ΟΝΗ (ΟΗ2) 3N (^ 2 ^ δ) 2 9.

CONH -ο CONH (CH2) 3M (C2H5) 2 -conh (ch2 > 3n (c2h5) 2 ο.

cK

9〇chs NHCOCH-N = N *

CONH (CH2) 3N (C2H5) 2 CONH (CH2 > 3N (C2H5) 2

cK

NHCOCH-N =

CONH

-Q CONH (CH2) 3N (C2H5) 2 CONH (CH2) 3N (C2H5) 2

2βcKK

? N NHCOCH-N = N- < | ^ CONH (CH2) 3N (CH3) 2 CONH (CH2) 3N (CH3) 2 3c

ch3 i ^ OCH NHCOCH * OCH3, υη3

-14- 518430 V. Description of the invention (13) 4.

5.

CI

OCH3

Pch3 (pOCH NHCOCH-N = i 3θ

CONH (CH2 > 3 Ο

Η < p〇CH NHCOCH-N =

CONH

CONHiCHa);

CONH (CH2);

〇K

nhcoch-n ^ nH ^^-conh

CONH (CH2):

CONH (CH2) 3 o

8.J1 I H

90c NHCOCH- CONH (CH2) 4N (C2H5) 2 OONH (CH2) 4N (C2H5 > 2

(pOCHs NHCOCH-N ^

n ^ Q ^ c〇nh ^ O • CONH (CH2) 5N (CH3) 2 -CON ^ QH ^ sNfCH ^ g -15- 518430 V. Description of the invention (14) 2 0.

CONH (CH2) 3N (C2H5) 2 conh (ch2) 3n (c2h5) 2 CONH- 2 1

CONH (CH2) 3N (C2H5) 2 conh (ch2 > 3n (c2h5) 2 2 2 ·

CON • CONH (CH2) 3N (C2H5 > 2 -CONH (CH2) 3N (C2H5 > 2) i: Compounds represented by the general formula (I) and the application of Japanese Patent Application Laid-Open No. 2000-2395 No. 54 to No. The amine compound represented by the general formula (III) and / or the amine compound represented by the general formula (IV) described in column 0043 is preferable. The compound represented by the general formula (I) may be column 0033 in Japanese Patent Application Laid-Open No. 2000-239554. It is synthesized by the method described in No. 003. In addition, the compound represented by the general formula (1) may be a commercially available product, such as "Soluthboth 22000" of the pigment dispersion composition of the present invention by Acryl Corporation. The content varies depending on the type of dispersant used, and varies within a preferred range, but when preparing a dispersion composition of green and red pigments, it is generally 0.1 to 100 parts by mass for 100 parts by mass of the pigment. The preferable and more preferable amount is 1 to 30 parts by mass. In preparing the dispersion composition of the blue pigment, 10 parts by mass of 100 parts by mass of the pigment is generally preferable, and the more preferable amount is 2 to 5 parts by mass. If the content is in the range of -16-518430 V. Description of the invention (15) The above range can prevent the pigment dispersion composition The viscosity is excessively increased, and it is preferable because it is easy to adjust the chromaticity when making a color filter. The pigment that can be used in the pigment dispersion composition of the present invention is, for example, an organic pigment. Examples of the organic pigment include a yellow pigment, an orange pigment, and a red color. Pigments, purple pigments, blue pigments, green pigments, brown pigments, black pigments, etc. When the dispersant is a compound having an azo pigment skeleton (for example, the compound represented by the general formula (I)), the pigments used in combination are Pigments having an azo pigment skeleton are preferred. The above-mentioned yellow pigments are, for example, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C. I. Pigment Yellow 1 2, C. I. Pigment Yellow 1 7, C. I. Pigment Yellow 8 3. C. I. Pigment Yellow 86, CI. Pigment Yellow 93, CI Pigment Yellow 10, CI Pigment Yellow 11 10, C. I. Pigment Yellow 117, C. I. Pigment Yellow 125, C. I Pigment Yellow 137, C. I. Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 185, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 166, CI Pigment Yellow 168, (: .I.Pigment Yellow 18 5. The above orange pigments are, for example, C.I. Pigment Orange 36, C.I. Pigment Orange 43, C. I. Pigment Orange 5 1, C. I. Pigment Orange 5 5, C. I. Pigment Orange 5 9 , C. I. Pigment Orange 61, C. I. Pigment Orange 71 and so on. The aforementioned red pigments are, for example, C. I. Pigment Red 9, C. I. Pigment Red 97, C. I. Pigment Red 1 22, C. I. Pigment Red 1 23, C. I. Pigment Red 1 49, C. I · Pigment Red 168, CI · Pigment Red Π7, CI Pigment Red 180, cI Pigment Red-17 · 518430 V. Description of the Invention (1 6) 1 9 2, C. I · Pigment Red 2 1 5, C · I. Pigment Red 2 1 6, C. I · Pigment Red 2 1 7, C. I. Pigment 220, C. I. Pigment Red 223, C. I · Pigment Red 224, C · I · Pigment Red 2 2 6, C · I. Pigment Red 2 2 7, C · I · Pigment Red 2 2 8, C. I. Pigment Red 240, C · I · Pigment Red 242, C · I · Pigment Red 48: 1, C.I.Pigment Red 209, (: .1. Pigment Red 146, (: .1. Pigment Red 11, 0.1. Pigment Red 81, C. I. Pigment Red 213, C. I. Pigment Red 272, C · I · Pigment Red 270, C. I. Pigment Red 25 5, C. I. Pigment Red 264, C. I. Pigment Red 254, etc. The above-mentioned purple pigments are, for example, C. I. Pigment Violet 19, C. I. Pigment Violet 23, C. I. Pigment Violet 29, CI Pigment Violet 30, CI Pigment Violet 37, CI Pigment Violet 40, C. I. Pigment Violet 50, etc. The above blue pigments are, for example, C. I. Pigment Blue 1 5. C. I. Pigment Blue 1 5: 6, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64, etc. The above green pigments are, for example, CI Pigment Green 7, CI · Pigment Green 36, etc. The above-mentioned brown pigments are, for example, C · I · Pigment Coffee 23, C.I., Pigment Coffee 25, C.I · Pigment Coffee 26, etc. The above-mentioned black pigments are, for example, C · I · Pigment Black 7, etc. etc. Pigments can be used alone or in combination of two or more. In the present invention, ci · pigment yellow uic ·〗 · pigment yellow 139, C I. pigment yellow 185, CI · pigment yellow 83 and other acid-based pigments Better, even better is ^. Factory pigment yellow 138, CK pigment yellow 139, C > 1 pigment yellow 丨 85, ^. Pigment red 2 5 4, C · I. pigment green 3 6, c ·〗. Pigment blue 丨5. etc. The content of the pigment in the pigment dispersion composition of the present invention varies within its preferred range depending on the kind used, in general, 5 to 80% by mass is better than -18 to 518430. 5. Description of the invention (17) The better and more preferably 10 to 70% by mass. When the content is within the above range, a high color strength can be maintained and an excessive increase in viscosity can be prevented, so it is preferable. The resin usable in the pigment dispersion composition of the present invention is preferably a polymer having an acidic group. When a polymer having an acidic group is used as the above-mentioned resin, it is preferred because it can provide three-dimensional retroreflectivity, improve dispersion stability of the pigment, and improve alkali developability when used as a coloring photosensitive composition. Examples of the polymer having an acidic group include copolymers of (meth) acrylic acid and (meth) acrylates, styrene / maleic anhydride copolymers, and reactants of styrene / maleic acid copolymers and alcohols. . These can be used alone or in combination of two or more. Among these, excellent pigment dispersibility, excellent compatibility with polyfunctional monomers and photopolymerization initiators when used as colored photosensitive resins, solubility in alkali developing solutions, solubility in organic solvents, strength, and softening The temperature is appropriate, and specifically, a copolymer of (meth) acrylic acid and (meth) acrylate (for example, a copolymer of methacrylic acid / benzyl methacrylate) is preferable. The acid value of the polymer having an acidic group is preferably 60 to 130. When the acid value is in the above range, dispersion stability is good, and viscosity can be controlled to be low, so it is better. The unit of the acid value is expressed in milligrams of potassium hydroxide required to neutralize 1 gram of the polymer. In addition, the acid value of the polymer may be appropriately adjusted depending on the molar ratio of the monomers constituting the polymer. The weight average molecular weight of the polymer having an acidic group is preferably 5,000 to 200,000. If the weight-average molecular weight is less than 5,000, the formation of a coating film may be problematic when used as a coloring photosensitive composition, and if it is more than 200,000, the viscosity of the colored photosensitive composition becomes high. -19-518430 V. Description of the invention (18) The content of the above-mentioned resin in the pigment dispersion composition of the present invention depends on the kind used and varies within a preferable range, but generally speaking, for 100 parts by weight of the above-mentioned pigment, It is usually 10 to 200 parts by mass, and more preferably 20 to 150 parts by mass. When the content is within the above range, it is preferable to obtain a three-dimensional reverse hair effect and prevent the viscosity of the dispersion from increasing too much. The pigment dispersion composition of the present invention may contain other ingredients such as a surfactant, if necessary. Containing a surfactant can improve the dispersion stability of the pigment, so it is desirable. The aforementioned surfactants include, for example, typical anionic surfactants such as alkylnaphthalenesulfonate and phosphate salts, typical cationic surfactants such as amine salts, aminocarboxylic acids, and typical amphoteric surfactants of the choline type, etc. . The pigment dispersion composition of the present invention can be obtained by dispersing pigments (for example, red, green, and blue pigments), dispersants, and resins with a disperser such as a solvent and a sand mill. In this case, the pigment and the dispersant may be mixed in advance, and after being miniaturized, the mixture may be dispersed in an organic solvent (or a vehicle), or the pigment and the dispersant may be individually refined, dispersed or dissolved in advance. The obtained dispersion or solution is mixed in an organic solvent (or vehicle), and the pigment and dispersant which are subjected to micronization treatment may be individually added to the organic solvent (or vehicle) and dispersed. Here, the vehicle refers to the part of the medium in which the pigment is dispersed when the paint is in a liquid state. In addition to the organic solvent, it also includes a part (adhesive resin) that is liquid and combines with the pigment to harden the coating film. -20- 518430 used for dispersing finely-treated pigments and dispersants in organic solvents V. Disperser of the invention (19), for example, a kneader. Conventional dispersers such as roller mills, super mixer mills, τ roller bars, homogenizers, and sand mills. In the pigment dispersion composition of the present invention, the organic solvent in which the dispersant, pigment, and resin are dispersed is not particularly limited, and may be appropriately selected from conventional substances such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether. (Poly) alkanediol monoalkane ethers such as diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like, and acetates thereof; ethyl acetate, n-propyl acetate Esters, isopropyl acetate, n-butyl acetate, isobutyl acetate, etc .; ketones such as benzene, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, hexanol, cyclic Alcohols such as hexanol, ethylene glycol, diethylene glycol, glycerol, etc. These can be used alone or in combination of two or more. Of these, 'ethanediol monoalkane ethers, and their acetates, acetates, methyl ethyl ether, and the like are preferred. The content of the pigment-dispersed composition of the organic solvent is usually 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass, for 100 parts by mass of the pigment. When the content is within the above range, the pigment dispersion composition can be prevented from rising excessively, and it is not difficult to secure the space during storage, so it is desirable. The average particle diameter of the dispersant in the present invention is 100 nm or less. When the average particle diameter of the dispersant is in the above range, the dispersant and pigment are dispersed for a long time by high-speed sanding, etc., so that the dispersant and pigment can be dispersed into fine particles at the same time, but it requires a lot of energy, And the fine pigment particles and dispersants obtained by this method are likely to cause a weak agglomeration situation commonly known as flocculation, the dispersion will have local viscosity and tend to be thixotropic, and it is not easy to make -21-518430. 5. Description of the invention (2〇 ) The problem of coating film of uniform color filter. Therefore, a method of dispersing the pigment and the dispersant after miniaturizing the primary particles is preferred. The miniaturization treatment of the dispersant and the pigment may be performed simultaneously or individually. Refinement is performed simultaneously in a state where a pigment and a dispersant coexist, and it is desirable because of its good manufacturability. The above-mentioned micronization treatment includes, for example, a method of mechanically pulverizing a pigment and a dispersant to refine particles (referred to as a pulverization method), and a person dissolved in a good solvent is put into a poor solvent to crystallize the finely pigmented pigment and dispersant. Methods (known as crystallization), and methods for producing fine particles during synthesis (called synthetic crystallization). An appropriate method can be selected according to the synthesis method or chemical properties of the pigment and dispersant used. A combination of two or more methods may be used to perform the miniaturization process. When the pigment and the dispersant are individually refined, each of the refinements may be different. The above grinding method is a method in which the pigment and / or dispersant are ground using a ball mill, a sand mill, a kneader, or the like, and a grinding agent such as salt is removed, the grinding agent is removed, and the primary particles are refined. Obtain relatively uniform pigment particles and / or dispersed particles. The above crystallization method is based on dissolving the pigment and / or dispersant in an appropriate good solvent! After 1 ′, it is mixed with a poor solvent to crystallize fine crystal particles. Speed and so on to control the size of the primary particles. Examples of the solvent to be used include strong acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorinated sulfonic acid, and alkaline solvents such as liquid ammonium, sodium formate, and methylformamide solutions. -22- 518430 V. Description of the invention (21) In the above crystallization method, a colorless method is used as a special crystallization method. Xanthone-based, perone-based, perylene-based, and standard-reducing blue-based dyes are reduced with basic hydrogen sulfide, and the sodium salt of quinone-based hydroquinone (colorless compound) is water-soluble. By adding an appropriate oxidant to this aqueous solution and oxidizing it, fine pigments and dispersants can be crystallized. The synthetic crystallization method is a method of crystallizing into fine crystal particles while synthesizing a pigment and / or a dispersant. However, when the fine pigments and / or fine dispersants produced are taken out from the solvent, the particles are aggregated into large secondary particles, and it is not easy to filter by general separation methods. They are usually used for synthesis in water systems that easily cause secondary aggregation. Azo-based pigments. Any of the above methods can be used for the above-mentioned miniaturization treatment. Among these methods, a grinding method without limitation of the comparative material is preferred. The pulverization method is detailed below. This method involves mechanically kneading pigments and dispersants, water-soluble inorganic salts such as table salt, and water-soluble organic solvents that will not dissolve them (hereinafter referred to as the process of salt milling), removing inorganic salts and organic solvents, and applying Method of washing and drying with water to obtain fine pigment and dispersant of primary particles. However, in the case of salt milling treatment, since pigments and dispersants crystallize and grow, at least a partially dissolved resin or pigment dispersant is added to the above-mentioned organic solvent during processing to prevent crystal growth from being extremely effective. When the ratio of the pigment and the dispersant to the inorganic salt is too large, the micronization efficiency of the pigment and the dispersant is good, but when the processing materials of the pigment and the dispersant are reduced, the productivity is reduced. In general, the inorganic salt is 1 to 20 parts by weight, and preferably 2 to 10 parts by weight for 1 part by weight of the pigment and the dispersant. Moreover, the above-mentioned wetting-23-518430 V. Description of the invention (22) The agent is added in order to uniformly harden the pigment, dispersant and inorganic salt. Therefore, depending on the mixing ratio of the pigment, dispersant and inorganic salt, pigment is usually used. The amount is 50 to 300% by weight. More specific examples of the above-mentioned salt milling method include adding a small amount of a water-soluble organic solvent as a wetting agent to a mixture of a pigment, a dispersant, and a water-soluble inorganic salt, and kneading it vigorously with a kneading machine, etc., and then putting the mixture into water and mixing the mixture at high speed. Wait for a slurry. Then, the slurry can be filtered, washed with water, and dried to obtain a pigment and / or a dispersant in which the primary particles are made finer. The pigment dispersion composition of the present invention can be used as a coating material, a printing ink, and the like. In addition, for example, a coating liquid containing a pigment dispersion composition is coated on a carrier and dried to form a layer of the pigment dispersion composition, or a layer of the pigment dispersion composition formed on a dummy carrier is copied on A method for forming a conventional positive or negative photosensitive resin composition on a carrier, exposing, developing, and removing a layer of the above-mentioned photosensitive resin composition that is not exposed, and the above-mentioned pigment dispersion composition in the same range For image formation. In addition, by mixing the photosensitive composition, a colored photosensitive composition that can form an image can be image-formed by light irradiation. This point is described below. < Colored photosensitive composition > The colored photosensitive composition of the present invention is characterized by containing the pigment-dispersed composition of the present invention, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and photopolymerization. Initiator. Since the coloring photosensitive composition of the present invention contains the pigment dispersion composition described above, it has excellent color tone and excellent dispersion stability of the pigment. Especially when used for making color filters, it can be produced stably

-24- 518430 V. Description of the invention (23) It is a color filter with vivid color tone, high light transmittance and high contrast. The above-mentioned polyfunctional monomer having two or more ethylenically unsaturated double bonds is, for example, the conventional (meth) propionate, urethane (fluorenyl) acrylic acid described in JP-A-60-258539. Esters, ammonium (meth) acrylate, allyl compounds, vinyl esters, and the like. These can be used alone or in combination of two or more. Among these, (meth) acrylate is preferred. The content of the colored photosensitive composition of the polyfunctional monomer having an ethylenically unsaturated double bond is preferably 10 to 60% by mass based on the solid content. When the content is within the above range, it is desirable because the hardening power during exposure can be sufficiently maintained and the ability of other raw materials is not suppressed. The photopolymerization initiator is preferably at least one compound having a molecular absorption coefficient of at least about 50 at a wavelength of about 300 to 500 nm. For example, the compound is disclosed in Japanese Patent Application Laid-Open No. 2-48664 and Japanese Patent Application Laid-Open No. 1-52449. And aromatic ketones, lofenine dimers, phenylene, phenylene ethers, polyhalogenated hydrocarbons, and the like described in JP-A No. 2-1 5 3 3 5 3. These can be used singly or in combination of two or more. Among these, a combination of 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazoline dimer, And 4- [p-N, N-bis (ethoxycarbonylmethyl) -2,6-bis (trichloromethyl) -three-three farming] is preferred. The content of the colored photosensitive composition of the photopolymerization initiator is preferably 0.2 to 10% by mass based on the total solid content of the colored photosensitive composition. When the content is within the above range, it is desirable to maintain high exposure sensitivity and prevent situations where it is difficult to control when the exposure sensitivity is too high. -25- 518430 V. Description of the invention (24) The colored photosensitive composition of the present invention can be formed by photopolymerization of the pigment dispersion composition of the present invention, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and photopolymerization. The initiator is mixed and prepared. In addition, a resin may be added during the preparation. The resin is preferably a polymer having an acidic group which can be used in a pigment dispersion composition. It is preferable to use the same resin as that used when preparing the pigment dispersion composition. In the coloring photosensitive composition of the present invention, the content of the resin (especially a polymer having an acidic group) is preferably 20 to 80% by mass based on the total solid content. When the content is within the above range, it is desirable to maintain the coating film with high strength and prevent the ability to suppress the use of other raw materials. The colored photosensitive composition of the present invention can form an image by light irradiation. The image formation using the colored photosensitive composition described above can basically be performed by the processes (1) to (3) described below. (1) After preparing the pigment dispersion composition, the process of using it to prepare the above-mentioned colored photosensitive composition (2) The colored photosensitive composition obtained by coating on a substrate is dried, or coated on another dummy carrier and dried The process of copying the formed layer on a substrate and coloring the layer formed by the photosensitive composition (3) The process of exposing, developing, and patterning the layer formed on the substrate by the coloring photosensitive composition. The above substrates are generally transparent materials such as glass plates or transparent plastic plates. In order to increase the adhesion between the substrate and the colored photosensitive composition, various commercially available free radical couplings-26-518430 may be added to the colored photosensitive composition. 5. Description of the Invention (25) or the like The above-mentioned substrate coupling process. When the coating solution of the colored photosensitive composition is applied to the substrate, it can be performed by a conventional coating method such as a spin coater, a roll coater, a bar coater, or a curtain coater. A method of copying a layer made of the colored photosensitive composition formed on the dummy carrier onto the substrate, for example, a method using a heating roller base layer under normal pressure or reduced pressure is preferred. The developing solution used in the above development is, for example, an hydroxide or carbonate of an alkali metal or an alkaline earth metal, a bicarbonate, an ammonium water, an aqueous solution of a grade 4 ammonium salt, or the like. These can be used singly or in combination of two or more kinds. Among these, sodium carbonate aqueous solution is more preferable. < Color filter > The color filter of the present invention is a color filter having two or more coloring layers with different patterns on the substrate, and the coloring layer is made of the coloring photosensitive composition of the present invention. to make. Since the color filter of the present invention has a colored layer formed of the colored photosensitive composition of the present invention, it has a clear hue, high light transmittance, and high contrast. The color filter of the present invention can be repeatedly performed the processes (2) and (3) above, and can be produced by combining patterns of several colors (usually 3 colors such as R, G, and B). The color filter of the present invention can be produced by a copying method. A method for manufacturing a color filter by a copy method is described in detail in, for example, Japanese Patent Application Laid-Open No. 4-208940, Japanese Patent Application Laid-Open No. 5-72724, Japanese Patent Application Laid-Open No. 5-80503, Japanese Patent Application Laid-Open No. 5-1 73 320, and the like. In the present invention. -27- 518430 V. Description of the invention (26) The color filter of the present invention includes a type in which a colored layer is directly formed on a transparent substrate such as glass, and a type in which the above-mentioned colored layer is formed on a substrate on which a dynamic element such as TFT is formed. State (color filter, Yu, array: C0A type). The color filter of the present invention can be widely used for display elements of computers, typewriters, engineering stations, navigation systems, televisions, video recorders, and the like. Examples The present invention is described below by way of examples, but the present invention is not limited by these examples. [Example 1] A red pigment dispersion composition having the following composition was prepared. c. I. Pigment Red 254 ......... 6.4 grams of pigment dispersant shown below ... 0.6 grams of methacrylic acid / methacrylic acid Benzyl methyl ester copolymer 15.8 g (Molar ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propylpropionate solution, acid value 105) Oxy-2-propylacetate ..... The maximum absorption wavelength λ max (in CHC13) of 57.2 g of the following pigment dispersion composition is 39 1 nm, and the rising wavelength of the transmission spectrum is 44 5nm. The pigment dispersant 1 is prepared after a salt milling treatment (refinement treatment) as described below. 500 g of sodium chloride, 5 g of hydrogenated rosin ester (manufactured by Arakawa Chemical Co., Ltd .: ester gum HP), 50 g of the following pigment dispersant 1 and 300 g of polyethylene glycol were mixed in an oven mixer (Moriyama Manufacturing Co., Trade name S1-1) for 5 hours. Put the kneaded product into 2 liters of warm water, and use a T-roller -28- 518430 at about 70 ° C. 5. Description of the invention (27) Stir vigorously for 2 hours. Then, the obtained dispersion was filtered, the residue on the filter was washed with water, sodium chloride and polyethylene glycol were removed, and the resultant was dried in a drying oven at about 40 ° C for 2 days. The average particle diameter of the powder particles of the obtained pigment dispersant was 80 nm. Pigment dispersant 1

(p〇CH3 NHCOCH-N = N

CONH

-CONH (CH2) 3N (C2H5) 2 -C〇NH (CHa) 3N (C2H5) 2 Make the red pigment composition of the above composition in an electric mixer M-50 (manufactured by Aika), use a diameter of 0.6 5nm The zirconium beads were dispersed at a peripheral speed of 9 m / s for 9 hours to prepare a red pigment dispersion composition. [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 2 described below was used instead of the pigment dispersant. Pigment dispersant

! CONH

-conh (ch2) 3n (c2h5) 2 -CONH (CH2) 3N (C2Hs) 2 [Example 3] In Example 1, the pigment dispersant divided by "Sorus Boss 22000" was substituted for the pigment dispersant. A red pigment dispersion composition was prepared in the same manner as in Example 1. [Example 4]

-29- 518430 V. Description of the invention (28) In Example 1, except that C · I · Pigment Red 1 7 7 was substituted for c.〗. Pigment Red 2 54 was prepared in the same manner as in Example 1 to prepare a red pigment dispersion. , Composition. [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 Yellow 1 39 was substituted for C. 丨. Pigment Red 254. [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 Yellow 1 3 8 was substituted for c.I.Pigment Red 2 54. [Example 7] In Example 1, a green pigment dispersion composition was prepared in the same manner as in Example 1, except that C.I.Pigment Green 3 6 was substituted for c.I.Pigment Red 254. [Example 8] In Example 1, except that C. I. Pigment Blue 15: 6 was substituted for C. I. Pigment Red 2 5 4. The content of the pigment dispersant 1 described above was 0.3 g, and In Example 1, a blue pigment dispersion composition was prepared in the same manner. [Comparative Example 1] A red pigment dispersion composition was prepared in the same manner as in Example 1 except that the pigment dispersant 1 was not added at all. [Comparative Example 2] In Example 7, a commercially available dispersant "EFKA-745" (manufactured by Yves Chemical Co., Ltd., with a transmission wavelength rising wavelength of 40 nm) was used instead of the pigment dispersant 1 described above. 7 Similarly, a green pigment dispersion composition was prepared. -30- 518430 V. Description of the invention (29) [Comparative Example 3] In Example 1, the same as Example 1 except that the above-mentioned pigment dispersant 1 (average particle diameter: 120 nm) was used without any salt milling treatment. A red pigment dispersion composition is prepared. The obtained pigment dispersion compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated as described below, and the pigment dispersion compositions of Examples 1 and 7 and Comparative Examples 2 and 3 were measured for chromaticity. The evaluation results and measurement results of the chromaticity are shown in Table 1. (1) Viscosity measurement Regarding the obtained pigment dispersion composition, regular viscosity on the side of the E-type viscometer was used to evaluate the degree of viscosity increase. (2) Comparative measurement The obtained pigment dispersion composition was coated on a glass substrate with a thickness of 6 m to prepare a sample. This sample was placed between two polarizing plates, and the transmitted light amount when the polarizing axes were parallel and perpendicular were measured 'using this ratio as a comparison. Color filters for TFT-LCD, Ukiki, Koki, Fuyong, Yamanaka "). -31-518430

V. Description of the invention (30) Table 1 Viscosity comparison --- ---__-chromaticity (cp) X-yz Example 1 30 1350 0.628 〇ns o Example 2 40 1300 ^ J · 〇 Example 3 70 1200 '----- ----- Example 4 50 1250 ----- Example 5 30 300 --------- Example 6 70 400-Example 7 100 1200 0.247 0.400 67 5 Example 8 150 1250 Comparative Example 1 High viscosity w — ---- Comparative Example 2 205 1050 '———. 0.240 0.398 63.7 Comparative Example 3 35 1200 0.629 r \ 〇〇n ---- JU. 333 22.4 *) Dispersion becomes extremely high viscosity and Unable to disperse From the results in Table 1, it can be seen that the pigment dispersion composition of the example has low viscosity, excellent dispersion stability, and high contrast. In addition, in Example 7, a copolymer having an acid value of 50 (the molar ratio of the methacrylic acid / benzyl methacrylate copolymer is 14/86) was used as the methacrylic acid / benzoic acid benzoic acid. Except for the ester copolymer, when the pigment dispersion composition was prepared in the same manner, the viscosity was higher than that of the example, and the dispersibility was not good. Similarly, in Example 7, except that the copolymer having an acid value of 1 45 (the molar ratio of the methacrylic acid / benzyl methacrylate copolymer is 37/63) was used as the methacrylic acid-32-518430. 2. Description of the invention When the pigment dispersion composition is prepared in the same manner as in the (31) / benzyl methacrylate copolymer, the viscosity is higher than that of the example and the dispersibility is not good. [Example 9] The following composition was mixed and a coloring photosensitive composition for preparing a color filter was prepared. The red dispersion composition of Example 1 ... 3 2.4 g of methacrylic acid / benzyl methacrylate copolymer · · · · 9.0 g (Molar ratio 28/72, weight average molecular weight: 30,000, 30% 1-methoxy-2-propylpropionate solution) Pentaerythritol tetraacrylate ... 5.2 g 4- [p-N, N_di (ethyl Oxycarbonylmethyl)]-2,6-bis (trichloromethyl) -5-trioxo ... 0.2 g of hydroquinone monomethyl ether ... ... O.Olg 1-methoxy-2-propyl acetate ......... 62 g The above-mentioned mixture is mixed with an electric mixer M-50 (manufactured by Aika Corporation), Zirconium beads with a diameter of 0.65 nm were used and dispersed at a peripheral speed of 9 m / s for 9 hours. About the obtained coloring photosensitive composition for color filter manufacture, viscosity measurement was performed similarly to Example 1, and the color filter was produced as follows, and it measured and compared with Example 1 similarly. The results are shown in Table 2. In other words, the above-mentioned colored photosensitive composition for color filter plate production was coated on a substrate using a spin coater, and dried at 100 ° C for 2 minutes to form a film of about 2 µm. Then, after exposure under a high-pressure mercury lamp in a nitrogen atmosphere, development was performed with a 1% sodium carbonate aqueous solution. The obtained filter was carried out in the same manner as in Example 1. 33-518430 V. Comparison of color chips of the invention description (32). [Example 10] In Example 9, except that the above-mentioned pigment dispersant 2 was replaced by the pigment dispersant 2 described below, a colored photosensitive composition was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9. [Example Π] In Example 9, except that the red pigment dispersion composition of Example 3 was used instead of the red pigment dispersion composition of Example 1 ', a colored photosensitive composition was prepared in the same manner as in Example 9, and was the same as in Example. 9 Perform the same evaluation. [Example 12] In Example 9, except that 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 were substituted for 3 2 · 4 g of Example 1 A colored photosensitive composition was prepared in the same manner as in Example 9 except for the red pigment dispersion composition, and the same evaluation was performed as in Example 9. [Example 1 3] In Example 9, except that 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 were substituted for 3 2.4 g of the red pigment dispersion composition of Example 1. A colored photosensitive composition was prepared in the same manner as in Example 9, and the same evaluation was performed as in Example 9. [Example 14] In Example 9, except that the blue pigment dispersion composition of Example 8 was used in place of the red pigment dispersion composition of Example 1, a colored photosensitive composition was prepared and implemented in the same manner as in Example 9. Example 9 performs the same evaluation. -34- 518430 V. Description of the invention (μ) Table 2 Comparison (colored photosensitive composition film) Example 9 1300 Example 10 1200 Example 11 1250 Example 12 1100 Example 13 1250 Example 14 1300 Effect of the invention The present invention can provide a pigment dispersion composition having excellent dispersion stability and color tone, and in particular, a color filter having a high contrast ratio for stable color filter production. In addition, the present invention can provide a pigment dispersion composition for forming an image with a vivid color tone and high light transmittance, and in particular, a color filter having a high contrast ratio for stable color filter production. In addition, the present invention can provide a color filter having a vivid color tone, high light transmittance, and high contrast. Brief Description of the Drawings Figure 1 is a graph illustrating the rising wavelength of the transmission spectrum of the present invention. Figure 2 is a typical diagram of the transmission spectrum of the pigment of the pigment dispersion composition of the present invention and the transmission spectrum of the dispersant. Fig. 3 is a typical diagram of the transmission spectrum of the color filter pigment of the pigment dispersion composition of the present invention and the transmission spectrum of the color filter pigment containing a dispersant. -35-

Claims (1)

518430-Said Zheng Zheng / ^ _ VI. Patent Application No. 90 1 29 644 "Pigment dispersion composition, coloring photosensitive composition and color filter using it" patent (Amended on August 30, 91) Patent application scope: 1. A pigment dispersion composition characterized by dispersing a pigment and a dispersant with an increase in the transmission spectrum of 400 to 550 nm and an average particle size of 100 nm or less and a resin in an organic solvent , Where the dispersant is a compound represented by the following general formula (1), AN = NX —Y general formula (1) (where A is a component of XY and an azo pigment, and X is a bond, or A group selected from the group consisting of a non-divalent bonding group of 75 in the following structure, and Y represents a group represented by the following general formula (II)) CON Η— C0NH ~ '»/ s〇2NH-. ~ O ~ S0_- (CONH—Z-NR ^ a general formula (II) (wherein z is a lower carbon alkylene group, and -NR2 is a lower carbon alkylamino group or a 5 or 6 carbon saturated heterocyclic ring containing a nitrogen atom, a means 1 or 2). 2 · The pigment dispersion composition according to item 1 of the patent application scope, in which the resin is a polymer with an acidic group. 518430 (P month ^ amendment / 矣 基 / 补 _ / gr VI. Application Patent scope 3 • The pigment dispersion composition according to item 2 of the patent scope, wherein the acid value of the polymer having an acidic group is 60 to 130. 4. The pigment dispersion composition according to the scope of patent application, wherein The dispersant and pigment have an azo pigment skeleton. 5 · —A colored photosensitive composition characterized by containing a pigment dispersion composition such as any one of claims 1 to 4 in the patent application scope, and having two or more ethylene Polyfunctional monomers with unsaturated double bonds and photopolymerization initiators. 6. A color filter, which is a color filter with two or more different coloring layers on the substrate. The coloring layer is made of a colored photosensitive composition as described in claim 5 of the scope of patent application.