JP2016170370A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter that is excellent in various resistances (heat resistance and solvent resistance) and is stable; and a color filter that has excellent color characteristics, high contrast, high heat resistance and solvent resistance using the same.SOLUTION: A coloring composition for a color filter contains a coloring agent, a dispersant containing a specific dispersant (Xa) and a vinyl resin type dispersant (Xb) having a tertiary amino group, a binder resin, and a solvent.SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for color filter used for manufacturing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  A color filter has two or more kinds of fine band (striped) filter segments (pixels) arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are vertically and horizontally. It consists of things arranged in a fixed arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Quality items required for the color filter include contrast ratio and brightness. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, to achieve a high-quality liquid crystal display device, high contrast is essential.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  Furthermore, as described above, since color liquid crystal devices have been used for televisions, personal computer monitors, etc., there is a demand for a wide color reproduction region and high reliability as well as higher contrast and higher brightness for color filters. It is high.

  In addition, color image pickup tube elements typified by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device: Charge Coupled Device), etc. have B (blue), G on the light receiving element. In general, color separation is performed by disposing color filters each having an additive mixed primary color filter segment of (green) and R (red). In recent years, there is an increasing demand for transmittance, that is, brightness and high reliability in color filters used in color image pickup tube elements.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitizer and additives in a pigment in which pigment particles as a colorant are dispersed in a transparent resin, and this color resist is applied on a substrate such as a spin coater. It is a method for forming a color filter by forming a coating film with an apparatus, selectively exposing through a mask with an aligner, a stepper, etc., patterning by alkali development and thermosetting, and repeating this operation. .

  In general, the pigment particles are refined and the pigment composition (pigment dispersion) in which the refined pigment is made as close as possible to the primary particles is produced, thereby suppressing light scattering by the pigment and increasing the contrast. Can be achieved. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  When producing a pigment composition, it is known that it is difficult to disperse the pigment stably at a high concentration, which causes various problems to the production process and the product itself. Therefore, in general, a dispersant is used in order to keep the dispersion state good. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites. Various dispersants are used according to the surface state of the pigment to be dispersed. However, for pigments having a surface that is biased toward basicity, the dispersant has an acidic functional group that performs electrostatic adsorption. Is generally used. In this case, the acidic functional group becomes the adsorption site of the pigment. Dispersants having a carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

However, on the other hand, dispersants having acidic functional groups are often not effective for pigments having acidic surfaces. Therefore, basic dispersants are used for pigments having an acidic surface, and the basic dispersants often have a comb structure. In the case of a comb structure, at the time of production, a portion that becomes a comb tooth having a functional group such as a carboxyl group or an acryloyl group is grafted to a polyamine compound having a primary and / or secondary amine, and the remaining primary and There is a method of making secondary amines a functional group that adsorbs to the pigment surface (see Patent Documents 5 and 6), but primary and / or secondary amines have highly reactive active hydrogen, Depending on the case, the chemical structure may be changed to change the hue, which is not preferable. In addition, since the basic dispersant contains a highly basic amine moiety, the resin is yellowed by heat. This reduces the brightness of the color filter.

  Further, as described above, a wide color reproduction region is required for recent color filters, and the pigment concentration in the coloring composition tends to be high. Further, in various resistances (solvent resistance, heat resistance, light resistance), the required quality is increased, and further quality improvement is required. With the increase in pigment concentration, it is no longer possible to add a large amount of photosensitive components such as photopolymerization initiators, providing sufficient curability and resistance to the color filter coating film, and supporting high definition. It is difficult to obtain a pattern shape.

  Further, in the color image pickup device, the pixels are similarly made thinner, and the pigment concentration is high in the coloring composition for use in the color image pickup device. For this reason, the amount of materials other than coloring components that can be added is small, and it is difficult to obtain a coloring composition that is a thin film and that can cope with the reduction in pixels.

JP-A-61-61623 JP-A-1-141968 Japanese Patent Laid-Open No. 2-219866 JP 11-439842 A Japanese Patent Laid-Open No. 08-038875 Japanese Patent Application Laid-Open No. 08-143813

  In view of the above situation, an object of the present invention is to provide a stable color filter coloring composition having excellent resistance (heat resistance, solvent resistance), and color characteristics using the same, and exhibit high contrast, high heat resistance, and resistance. It is to provide a color filter having a solvent property.

  As a result of intensive studies to solve the above problems, the present inventors have developed a specific dispersant (Xa) containing a thermally crosslinkable functional group and a color containing a specific dispersant (Xb). It has been found that the composition has high heat resistance, light resistance and solvent resistance, and a good pattern shape can be obtained.

  That is, the present invention is a color filter coloring composition containing a colorant, a dispersant, a binder resin, and a solvent, the dispersant containing the dispersant (Xa) and the dispersant (Xb), The agent (Xa) is an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) and a hydroxyl group in the hydroxyl group-containing compound (a). A polyester part Xa1 ′ having a carboxyl group, and a vinyl polymer part Xa2 ′ having a thermally crosslinkable functional group obtained by radical polymerization of an ethylenically unsaturated monomer (c). A dispersant having at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group. There, dispersing agent (Xb) is a color filter for coloring composition, which is a vinyl resin type dispersant having a tertiary amino group.

  The present invention also relates to the color filter coloring composition, wherein the dispersant (Xb) has a piperidyl skeleton.

  The present invention also relates to the color composition for color filters, wherein the colorant contains at least one of a zinc halide phthalocyanine pigment and an aluminum phthalocyanine pigment.

  The present invention also relates to the coloring composition for a color filter, wherein the dispersant (Xb) has an amine value of 50 to 500 mgKOH / g.

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerization initiator and / or a photopolymerizable monomer.

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

  The color filter coloring composition of the present invention has excellent dispersibility, storage stability, heat resistance, solvent resistance, and color filter color composition using the same, and has good color characteristics, heat resistance, light resistance And a color filter excellent in solvent resistance can be provided.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” mentioned below means a color index (CI).

The coloring composition for a color filter of the present invention is a coloring composition for a color filter containing a colorant, a dispersant, a binder resin, and a solvent, and the dispersant is the dispersant (Xa) and the dispersant (Xb). And the dispersant (Xa) is an acid anhydride group and a hydroxyl group-containing compound (b) in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) ( a) a vinyl polymer obtained by radical polymerization of a polyester part Xa1 ′ having a carboxyl group and an ethylenically unsaturated monomer (c) obtained by reacting a hydroxyl group in a) and having a thermally crosslinkable functional group At least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group. A dispersing agent which is a species, dispersing agent (Xb), characterized in that a vinyl resin type dispersant having a tertiary amino group.
Hereinafter, each component which comprises the coloring composition for color filters of this invention is explained in full detail.

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.
Especially as a pigment, the amount of acidic functional groups on the surface of the pigment obtained when measured using n-hexylamine as a basic substance by the method described in Coloring Materials, 67 [9], 547-554 (1994). Those of 100 μmol / g or more, further 200 μmol / g or more are preferable because the effects of the present application can be remarkably exhibited.

  The content of the colorant is preferably 10% by weight or more, more preferably 15% by weight or more from the viewpoint of obtaining sufficient color reproducibility, based on the total nonvolatile components of the coloring composition (100% by weight), and most preferably Preferably it is 20 weight% or more. Further, from the viewpoint of the stability of the coloring composition, the preferred colorant content is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

<Organic pigment>
Specific examples of pigments that can be used when forming color filter pixels as colorants are shown.
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, patent 4893859 etc. can also be used, It is not limited to these in particular.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58. Moreover, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can also be used, and the invention is not particularly limited thereto.

  Among these blue pigments or green pigments, in particular, a halogenated zinc phthalocyanine pigment or an aluminum phthalocyanine pigment can obtain a high spectral transmittance and a wide color reproduction range that cannot be obtained with other green pigments. These pigments have a problem that heat resistance and solvent resistance are slightly inferior to those conventionally used. However, even coloring compositions using these pigments should be dispersed using the dispersant (Xa) of the present invention and the vinyl resin type dispersant (Xb) having a tertiary amino group. Therefore, a colored composition having good stability and excellent heat resistance and solvent resistance can be obtained.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and the like. Among them, C.I. I. It is preferable to use one or more selected from CI Pigment Yellow 138, 139, 150, and 185.

  That is, the colorant used as the green coloring composition preferably contains at least one of a halogenated zinc phthalocyanine pigment and an aluminum phthalocyanine pigment, and further contains a yellow pigment to provide excellent color characteristics. can do.

  Particularly preferred pigment ratios include, for example, when a halogenated zinc phthalocyanine pigment and a yellow pigment are used, based on the total weight of the pigment component, the halogenated zinc phthalocyanine pigment is 50 to 100% by weight, and the yellow pigment is 0 to 50%. More preferably, the zinc halide phthalocyanine pigment is 50 to 90% by weight and the yellow pigment is 5 to 45% by weight, based on the total weight of the pigment component.

  Further, when an aluminum phthalocyanine pigment and a yellow pigment are used, the aluminum phthalocyanine pigment is 5 to 70% by weight and the yellow pigment is 30 to 95% by weight, more preferably the pigment component based on the total weight of the pigment component. Based on the total weight, the aluminum phthalocyanine pigment is 15 to 60% by weight, and the yellow pigment is 40 to 85% by weight.

  When a wider color reproduction region is desired, three types of halogenated zinc phthalocyanine pigment, aluminum phthalocyanine pigment, and yellow pigment are used in combination. Preferred pigment ratios are 50 to 100% by weight of the halogenated zinc phthalocyanine pigment, 0 to 50% by weight of the aluminum phthalocyanine pigment, and 0 to 50% by weight of the yellow pigment, based on the total weight of the pigment component.

  More preferably, based on the total weight of the pigment component, the zinc halide phthalocyanine pigment is 50 to 90% by weight, the aluminum phthalocyanine pigment is 5 to 45% by weight, and the yellow pigment is 5 to 45% by weight. The chromaticity region can be expanded by such a composition ratio of the pigment.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

[Miniaturization of pigment]
When the pigment is used in the present invention, it is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples are given in the present invention. Thus, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Further, it is preferably 100 nm or less because a color filter having a high contrast ratio can be formed. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.
The coloring composition of the present invention contains two specific dispersants, so that even when such a finely-treated pigment is used, it has excellent durability, a high brightness and contrast ratio, and a stable color. It can be set as the coloring composition for filters.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dispersant>
The dispersant of the present invention contains a dispersant (Xa) and a dispersant (Xb), and the dispersant (Xa) is one or more selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2). A polyester portion Xa1 ′ having a carboxyl group obtained by reacting an acid anhydride group in the acid anhydride (b) with a hydroxyl group in the hydroxyl group-containing compound (a), and an ethylenically unsaturated monomer (c). And a vinyl polymer portion Xa2 ′ having a thermally crosslinkable functional group, wherein the thermally crosslinkable functional group is a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and ( It is a dispersant that is at least one selected from the group consisting of (meth) acryloyl groups, and the dispersant (Xb) is a vinyl resin type dispersant having a tertiary amino group.
By using two kinds of such specific dispersants, it is possible to obtain a colored composition having not only stability but also excellent durability, high luminance, and high contrast ratio.

  As a ratio of the dispersant (Xa) and the dispersant (Xb), the dispersant (Xb) is 5 to 500 parts by weight, more preferably 25 to 400 parts by weight with respect to 100 parts by weight of the dispersant (Xa). Preferably it is 50-250 weight part. When the ratio of the dispersing agent (Xa) is high, the resistance of the colored composition coating film becomes higher, and when the ratio of the dispersing agent (Xb) is high, the brightness of the coloring composition coating film tends to be high. When the ratio of the dispersant (Xa) and the dispersant (Xb) is within this range, a coating film excellent in dispersibility and resistance can be obtained.

In general, a dispersant has a structure of a site that adsorbs to a colorant and a site that has a high affinity for a colorant carrier and a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance between these two sites.
That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the colorant and the affinity to the colorant carrier and the solvent as the dispersion medium are very important. The colorant carrier referred to here comprises a resin and its precursor or a mixture thereof obtained by removing the colorant component and the dispersant from the solid content.

<< Dispersant (Xa) >>
The dispersant (Xa) is an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) and a hydroxyl group-containing compound (a). A polyester portion Xa1 ′ having a carboxyl group obtained by reacting with a hydroxyl group;
A vinyl polymer portion Xa2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group;
The heat-crosslinkable functional group is a dispersant that is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group.
Moreover, when a crosslinkable functional group is a hydroxyl group, an oxetane group, a blocked isocyanate group, or a (meth) acryloyl group, it is preferable because it becomes excellent in solvent resistance.

  Here, the polyester portion Xa1 ′ of the main chain acts as a colorant adsorbing group, and the vinyl polymer portion Xa2 ′ of the side chain acts as a colorant carrier affinity group, thereby suppressing aggregation of the colorant and improving stability. An excellent dispersion can be obtained. Further, the side chain vinyl polymer portion Xa2 ′ in the dispersant (Xa) has a thermally crosslinkable group, so that the coloring composition contained together with the dispersant (Xa) and the epoxy compound is cured. It has excellent chemical resistance and solvent resistance.

  The content of the dispersant (Xa) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and still more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the colorant. When content of a dispersing agent (Xa) exists in this range, it can be set as the thing excellent in the dispersibility and tolerance.

Further, the weight average molecular weight of the dispersant (Xa) is preferably 2,000 to 100,000.
If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease, and if it exceeds 100,000, the interaction between the resins may become strong and the coloring composition may increase in viscosity. . Further, the acid value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. If the acid value is less than 5 mgKOH / g, the ability to adsorb to the colorant may be reduced, and there may be a problem in dispersibility. There is a case.

Subsequently, each component of the dispersant (Xa) will be described.
[Hydroxyl-containing compound (a)]
The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is preferably a polyol having two or more hydroxyl groups in the molecule, and in particular, two hydroxyl groups and one in the molecule. It is preferable that it is a compound (a1) which has a thiol group.

[Compound having two hydroxyl groups and one thiol group in the molecule (a1)]
Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1, 2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, Examples include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[Other polyols (a2)]
As other polyols (a2) that can be used, there are those belonging to the following groups (1) to (7) as long as only typical ones are exemplified. By using these polyol compounds in combination, it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent-dissolving part.

  (1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

  (2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Kind;

  (3) Various polyhydric alcohols as described above, and (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether; Modified polyether polyols obtained by ring-opening polymerization of

  (4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, etc. Resulting polyols;

  (5) Lactone obtained by polycondensation reaction of one or more of the various polyhydric alcohols described above with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Lactone-based polyester polyols, or lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols, polycarboxylic acids, and various lactones;

  (6) Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, Epoxy-modified polyester polyols obtained by combining one or more of the polyester polyols during synthesis; or

  (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin And other polymer polyols.

  The other polyol (a2) optionally added shown in (1) to (7) may be used alone or in combination of two or more, but the weight average molecular weight is From the viewpoint of solubility and dispersion stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, the effect of improving the compatibility and dispersion stability is small, and when the weight average molecular weight is 10,000 or more, the compatibility may be deteriorated.

  The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the intended dispersant can be synthesized, but a diol is preferable. In particular, by reacting with tetracarboxylic dianhydride (b1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. When many polyols having more than two hydroxyl groups are used, the main chain of the polyester may be branched and complicated and bulky, and it may be difficult to obtain a dispersion effect. For the purpose of adjusting the molecular weight of the polyester (Xa) and adjusting the viscosity of the dispersion, it should be minimized from the viewpoint of design.

[Acid anhydride (b)]
The acid anhydride (b) of the present invention contains one or more selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2).
The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the hydroxyl group-containing compound (a), whereby the carboxyl groups that become pigment adsorption groups are regularly formed on the main chain of the dispersant (Xa). This is advantageous for pigment dispersion.
When tricarboxylic anhydride (b2) is used, it can react with a hydroxyl group to form an ester bond, leaving a carboxyl group.

  In addition, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), dicarboxylic acid anhydrides, and anhydrides of compounds having 5 or more carboxylic acids can be used in combination. .

[Tetracarboxylic acid anhydride (b1)]
As tetracarboxylic dianhydride (b1) used in the present invention,
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo Aliphatic tetracarboxylic dianhydrides such as [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol Dimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4 , 4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride Anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4, 4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxy) Enoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4 -Aromatic tetracarboxylic dianhydrides such as tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

  The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since tetracarboxylic dianhydride forms a dispersant having two carboxyl groups in one unit of polyester by reaction with a polyol, the constitution of the dispersant (Xa) of the present invention from the viewpoint of pigment adsorptivity. Preferred as an element.

  Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to a colorant, and more preferably a tetracarboxylic dianhydride having two or more aromatic rings. It is a thing. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for pigment adsorption and have high heat resistance.

  Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (1) or general formula (2).

General formula (1):

[In General Formula (1), k is 1 or 2. ]

General formula (2):

[In General Formula (2), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (3) :

Or a group represented by the general formula (4):

It is group represented by these. ]

[Tricarboxylic anhydride (b2)]
Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydride and the like. Of these, aromatic tricarboxylic acid anhydrides are preferably used in the present invention from the viewpoint of adsorptivity to pigments.

The ratio of the acid anhydride group in one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydride (b1) and the tricarboxylic acid anhydride (b2) to the hydroxyl group in the hydroxyl group-containing compound (a) is:
The acid anhydride group / hydroxyl group is preferably 0.5 to 1.5.
When it is smaller than 0.5 or larger than 1.5, there are many portions that do not react, and the intended dispersant is often not obtained.

[Ethylenically unsaturated monomer (c)]
The dispersant (Xa) of the present invention has a vinyl polymer site Xa2 ′ formed by radical polymerization of the ethylenically unsaturated monomer (c).
[Ethylenically unsaturated monomer (c1)]
The ethylenically unsaturated monomer (c1) is an ethylenically unsaturated monomer having a thermally crosslinkable group or an ethylenically unsaturated monomer for introducing a thermally crosslinkable group.
Such an ethylenically unsaturated monomer having a hydroxyl group (c1-1), an ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group ( c1-3), an ethylenically unsaturated monomer containing a blocked isocyanate group (c1-4), and then copolymerizing the vinyl polymer portion Xa2 ′ with heat crosslinkability. Groups can be introduced.
Or a hydroxyl group in a hydroxyl group-containing polymer obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer having a hydroxyl group (c1-1),
A (meth) acryloyl group is introduced into the vinyl polymer portion Xa2 ′ by reacting with an isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group. be able to.

  Moreover, content of such an ethylenically unsaturated monomer (c1) shall be 5-70 weight% on the basis (100 weight%) of the sum total of all the ethylenically unsaturated monomers (c). Is more preferable, and more preferably 10 to 50% by weight. When the content is 5% by weight or more, the cross-linking property is excellent and the resistance is better. When the content is less than 70% by weight, the stability is excellent.

(Ethylenically unsaturated monomer having a hydroxyl group (c1-1))
As the ethylenically unsaturated monomer (c1-1) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. Is a (meth) acrylate monomer having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate and cyclohexanedimethanol mono (meth) acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having hydroxyl groups For example, N- (2-hydroxyethyl) (meth) acrylami N- (2-hydroxypropyl) (meth) acrylamide, N- (hydroxyalkyl) (meth) acrylamide such as N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomer having a hydroxyl group, For example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether, or an allyl ether monomer having a hydroxyl group, for example, , 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

  Also obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl ether. The ethylenically unsaturated monomer obtained can also be used as an ethylenically unsaturated monomer having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

(Ethylenically unsaturated monomer having oxetane group (c1-2))
Examples of the ethylenically unsaturated monomer (c1-2) having an oxetane group include methacrylic acid (3-ethyloxetane-3-yl) methyl.
Examples of commercially available products include ETERNACOLL OXMA (methacrylic acid (3-ethyloxetane-3-yl) methyl) (manufactured by Ube Industries).

(Ethylenically unsaturated monomer having t-butyl group (c1-3))
Examples of the ethylenically unsaturated monomer (c1-3) having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

(Ethylenically unsaturated monomer having a blocked isocyanate group (c1-4))
Examples of the ethylenically unsaturated monomer (c1-4) having a blocked isocyanate group include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethyl). And pyrazolyl) carbonylamino] ethyl methacrylate.
Examples of commercially available products include Karenz MOI-BM (2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(3, 5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate) (made by Showa Denko) and the like.

(Has isocyanate group and (meth) acryloyl group
Ethylenically unsaturated monomer (c1-5))
The ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is a compound having one isocyanate group and one or more (meth) acryloyl groups, and one isocyanate group , And a compound having one or two (meth) acryloyl groups are preferred. Specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, or 1,1-bis (acryloyloxymethyl) ethyl isocyanate is preferable.
The ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group used in the present invention is not limited to the compounds exemplified above, but an isocyanate group and one or more (meth) acryloyl groups. As long as it has a group, it may have any structure. These may be used alone or in combination.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl, in addition to the above ethylenically unsaturated monomer (c1). (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) Alkyl (meth) acrylates such as acrylate and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted type (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile. Here, (meth) acrylate refers to methacrylate or acrylate, and (meth) acrylamide refers to methacrylamide or acrylamide.

  Examples of monomers that can be used in combination with the acrylic monomer include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and acetic acid. And fatty acid vinyls such as vinyl and vinyl propionate.

[Method of synthesizing dispersant (Xa)]
Examples of the synthesis method of the dispersant (Xa) include, but are not limited to, the following synthesis methods (1) to (3).

[Synthesis Method (1)]
In the presence of the hydroxyl group-containing compound (a),
An ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group (c1-3), and an ethylenically unsaturated monomer having a blocked isocyanate group ( a hydroxyl group in a vinyl polymer having two hydroxyl groups in one terminal region obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing at least one selected from the group consisting of c1-4);
By reacting with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), an oxetane group, t A dispersant having a butyl group or a blocked isocyanate group is obtained.

  When the ethylenically unsaturated monomer (c1-1) having a hydroxyl group is used in such synthesis method 1, the acid anhydride group in the acid anhydride (b) is converted into an ethylenically unsaturated monomer (c1- Since it also reacts with the hydroxyl group of 1), the purpose of reacting with the hydroxyl group at one end of the vinyl polymer cannot be achieved, and the desired structure may not be obtained.

  At this time, an ethylenically unsaturated monomer (c1-2) having an oxetane group, an ethylenically unsaturated monomer (c1-3) having a t-butyl group, and an ethylenically unsaturated monomer having a blocked isocyanate group The content of the monomer (c1-4) is preferably 5 to 90% by weight, particularly preferably 20 to 60% by weight, based on the entire ethylenically unsaturated monomer (c). If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 90% by weight or less, it is preferable because the stability of the composition is also good.

[Synthesis method (2)]
A hydroxyl group in the hydroxyl group-containing compound (a) is reacted with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2). In the presence of the compound produced by
Ethylenically unsaturated monomer having a hydroxyl group (c1-1), ethylenically unsaturated monomer having an oxetane group (c1-2), ethylenically unsaturated monomer having a t-butyl group (c1-3) ) And an ethylenically unsaturated monomer (c) containing at least one selected from the group consisting of an ethylenically unsaturated monomer (c1-4) having a blocked isocyanate group, thereby being crosslinkable. A dispersant having a hydroxyl group, an oxetane group, a t-butyl group, or a blocked isocyanate group as a group is obtained.

  At this time, an ethylenically unsaturated monomer having a hydroxyl group (c1-1), an ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group ( The content of the ethylenically unsaturated monomer (c1-4) having c1-3) and the blocked isocyanate group is 5 to 90% by weight in the whole ethylenically unsaturated monomer (c). It is preferable to use 20 to 60% by weight. If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 90% by weight or less, it is preferable because the stability of the composition is also good.

[Synthesis Method (3)]
A hydroxyl group in the hydroxyl group-containing compound (a) is reacted with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2). In the presence of the compound produced by
A hydroxyl group in a hydroxyl group-containing compound obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (c1-1);
A dispersant having a (meth) acryloyl group as a crosslinkable group is obtained by reacting one isocyanate group with an isocyanate group in the compound (c1-5) having one or more (meth) acryloyl groups. .

  The content of the ethylenically unsaturated monomer (c1-1) having a hydroxyl group is preferably 5 to 70% by weight, preferably 10 to 50% by weight, based on the entire ethylenically unsaturated monomer (c). It is particularly preferable to do this. If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 70% by weight or less, it is preferable because the stability of the composition is good.

At this time, the molar ratio of the hydroxyl group in the copolymer after radical polymerization to the isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is determined after radical polymerization. The isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is 0.2 to 1.0 mol with respect to 1 mol of the hydroxyl group in the hydroxyl group in the copolymer. The amount is preferably 0.3, more preferably 0.3 to 1.0 mol, and most preferably 0.5 to 1.0 mol. If the amount is less than 0.2 mol, the amount of (meth) acryloyl groups may be reduced, so that the curability may be insufficient. If the amount exceeds 1.0 mol, unreacted isocyanate groups are present in the resin. It may remain and storage stability may deteriorate.
The reaction temperature is 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 150 ° C, the urethane group produced by the reaction may be decomposed.

[Synthesis of polyester part Xa1 ′]
The synthesis of the polyester portion Xa1 ′ is carried out in the acid anhydride group and hydroxyl group-containing compound (a) in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2). This is a step of reacting with the hydroxyl group.

(Reaction catalyst)
As the catalyst used for the production of the polyester portion Xa1 ′ of the present invention, a known catalyst can be used. As a catalyst, for example,
Triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, or 1,5-diazabicyclo- [4.3.0] A tertiary amine compound such as -5-nonene, or mono-n-butyltin (IV) oxide may be used.

(Reaction solvent)
In the production of the polyester part Xa1 ′ of the present invention, it is possible to produce only with the raw materials listed so far, but a solvent is used in order to avoid problems such as high viscosity and non-uniform reaction. Is preferred. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, or propylene glycol monomethyl ether acetate (PGMAc). After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

(Reaction temperature)
The reaction temperature for the synthesis of the polyester part Xa1 ′ is 50 ° C. to 180 ° C., preferably 80 ° C. to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction may be stopped when 97% or more of the acid anhydride is half-esterified by acid value measurement.

[Synthesis of vinyl polymer portion Xa2 ′]
In the dispersant (Xa), the vinyl polymer portion Xa2 ′ is obtained by radical polymerization of the ethylenically unsaturated monomer (c), and has a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and (meta ) It has at least one thermally crosslinkable functional group selected from the group consisting of acryloyl groups. Since this vinyl polymer part Xa2 ′ functions as an affinity site for the solvent and the colorant carrier as a side chain of the dispersant (Xa), it is stable even when a fine pigment is used or when a dye is used. It can be made excellent in properties.

  The weight average molecular weight of the vinyl polymer portion Xa2 'is preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 2000 to 12000, and particularly preferably 3000 to 8000. This portion Xa2 'becomes an affinity portion for the solvent that is the dispersion medium. When the weight average molecular weight of the vinyl polymer portion Xa2 'is less than 1000, the effect of steric repulsion due to the solvent affinity portion is reduced, and it is difficult to prevent aggregation of the pigment, which may result in insufficient dispersion stability. On the other hand, if it exceeds 20000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Further, the viscosity of the dispersion may increase.

  The content of the ethylenically unsaturated monomer (c) is preferably 3 to 100 parts by weight with respect to 1 part by weight of the hydroxyl group-containing compound (a), and bulk polymerization or solution polymerization is preferably performed. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part. If it exceeds 100 parts by weight, the molecular weight of the vinyl polymer site Xa2 ′ is too high, and the absolute amount increases as an affinity site for the pigment carrier and the solvent, and the dispersibility effect itself may decrease, When the weight is less than 10 weight, the molecular weight of the vinyl polymer portion Xa2 ′ is too low, and the steric repulsion effect is lost as an affinity portion for the pigment carrier and the solvent, and it is difficult to suppress the aggregation of the pigment. There is.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxynedecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, or propylene glycol monomethyl ether acetate (PGMAc) is used as the polymerization solvent. It is not limited to. These polymerization solvents may be used as a mixture of two or more.

  As the dispersant (Xa), known techniques described in International Publication No. 2008/007776 pamphlet, JP 2009-155406 A, JP 2011-157416 A, and the like can be used.

<< Dispersant (Xb) >>
The dispersant (Xb) of the present invention is a vinyl resin type dispersant having a tertiary amino group, and preferably has an amine value of 50 to 500 mgKOH / g, more preferably 100 to 400 mgKOH / g, 200 -350 mg KOH / g is most preferred. When the amine value is within this range, the viscosity and viscosity stability of the colorant dispersion are good and the dispersibility is excellent, so that a high contrast ratio can be obtained.

  The content of the dispersant (Xb) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and still more preferably 1 to 40 parts by weight with respect to 100 parts by weight of the colorant. When the content of the dispersant (Xb) is in this range, the dispersibility can be improved.

  The number average molecular weight of the vinyl resin having a tertiary amino group of the present invention is preferably 500 to 30,000. When the number average molecular weight is in this range, the viscosity and stability of the colorant dispersion are good and preferable.

  The vinyl resin having a tertiary amino group of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a tertiary amino group and, if necessary, other ethylenically unsaturated monomers. . In addition, a vinyl resin-type dispersant having a piperidyl skeleton is preferable because of its excellent stability and resistance, and an ethylenically unsaturated monomer having a piperidyl skeleton and, if necessary, other ethylenically unsaturated monomers. It can be obtained by polymerizing the monomer.

[Ethylenically unsaturated monomer having tertiary amino group]
Examples of the ethylenically unsaturated monomer having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meta) ) Acrylate or N, N-dialkylamino group-containing (meth) acrylates such as N, N-diethylaminopropyl (meth) acrylate; or N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl N, N-dialkylamino group-containing (meth) acrylamides such as (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, or N, N-diethylaminopropyl (meth) acrylamide may be mentioned.
Alternatively, an ethylenically unsaturated monomer having a piperidyl skeleton is also preferable.

  Of these, N, N-dialkylamino group-containing (meth) acrylates are preferable, and N, N-dimethylaminoethyl (meth) acrylate is more preferable. The ethylenically unsaturated monomer having a piperidyl skeleton will be described later.

[Ethylenically unsaturated monomer having piperidyl skeleton]
The ethylenically unsaturated monomer having a piperidyl skeleton is not limited as long as it has a piperidyl skeleton. Is preferred.

General formula (5)

[In the formula (5), R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or —OR ⁴ . R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ² and R ³ Each independently represents a methyl group, an ethyl group, or a phenyl group. “*” Indicates a bond. ]

In the general formula (5), examples of the alkyl group having 1 to 18 carbon atoms of R ¹ and R ⁴ include linear, branched, and cyclic alkyl groups. Specifically, a methyl group, an ethyl group, Examples thereof include normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.

Moreover, as a C6-C20 aryl group of R < ¹ > and R < ⁴ > in General formula (5), a phenyl group, 1-naphthyl group, 2-naphthyl group etc. can be mentioned, for example.

In the general formula (5), examples of the aralkyl group having 7 to 12 carbon atoms of R ¹ and R ⁴ include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group and the like.

In the general formula (5), examples of the acyl group of R ¹ and R ⁴ include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group, and specific examples include an acetyl group and a benzoyl group. I can do it.
In the present invention, R ¹ is preferably an alkyl group having 1 to 5 carbon atoms or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

  The ethylenically unsaturated monomer having a piperidyl skeleton should be contained in an amount of 1% by weight to 100% by weight with respect to the total solid content of the ethylenically unsaturated monomer from the viewpoint of viscosity and viscosity stability of the pigment dispersion. It is preferable to further contain 25% to 100% by weight, and it is particularly preferable to contain 40% to 100% by weight.

  Since the piperidyl skeleton has an antioxidant function, it is possible to prevent oxidation of the color filter material by containing even a small amount, and as a result, to prevent a decrease in brightness.

  Specific examples of the ethylenically unsaturated monomer having such a piperidyl skeleton include, for example, a compound represented by the following general formula (6-1), a compound represented by the following general formula (6-2), and the like. be able to.

General formula (6-1)

Formula (6-2)

[In General Formula (6-1) and General Formula (6-2), R ⁵ and R ⁷ each represent a hydrogen atom or a methyl group, and R ⁶ represents a methylene group or a C 2-5 carbon atom. Represents an alkylene group, Q represents a group represented by the general formula (5), Y represents —CONH— *, —SO ₂ —, —SO ₂ NH— * (provided that a bond marked with “*”). Binds to Q.), n represents an integer of 0-9. ]

R ⁶ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. n is preferably an integer of 0 to 8, particularly preferably an integer of 0 to 6.

  Specific examples of the monomer represented by the general formula (6-1) include compounds represented by the following general formulas (7-1) to (7-4).

General formula (7-1)-general formula (7-4)

(In the general formula (7-1 Formula (7-4), ^{R 5} has the same meaning as ^{R 5} in the general formula (6-1).)

  Specific examples of the monomer represented by the general formula (6-2) include compounds represented by the following general formulas (8-1) to (8-3).

General formula (8-1) to general formula (8-3)

(In General Formula (8-1) to General Formula (8-3), R ⁷ has the same meaning as R ⁷ in General Formula (6-2).)

Among these, 1,2,2,6,6-pentamethylpiperidyl methacrylate (a compound in which R ⁵ is a methyl group in the general formula (8-1)) is preferable.

[Other ethylenically unsaturated monomers]
The other ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with an ethylenically unsaturated monomer having a tertiary amino group. For example, description of the dispersant (Xa) The ethylenically unsaturated monomer similar to the ethylenically unsaturated monomer (c) described in (1) can be arbitrarily used.

  Moreover, you may use together the (meth) acrylate which has an alkyloxysilyl group. The (meth) acrylate having an alkyloxysilyl group is 0.01% by weight to the solid content of the ethylenically unsaturated monomer from the viewpoint of adhesion to the substrate and the viscosity and stability of the colorant dispersion. The content is preferably 10% by weight, and particularly preferably 0.05% by weight to 5% by weight.

[Synthesis Method of Vinyl Resin Type Dispersant Having Tertiary Amino Group]
The vinyl resin having a tertiary amino group of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a tertiary amino group and, if necessary, other ethylenically unsaturated monomers. .

  As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. When using this polymerization initiator, 0.01-20 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.

  Moreover, when superposing | polymerizing, a solvent can be used without a solvent depending on the case. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, hexane, toluene, xylene, acetone, methyl ethyl ketone, methoxypropyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl. Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used, but is not particularly limited, and can be arbitrarily selected from applications, costs, and the like. Two or more kinds of polymerization solvents may be mixed and used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

《Other dispersants》
The coloring composition for a color filter of the present invention may be used in combination with other dispersants.
Specific examples of other dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified polymer Acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group to There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

<Solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  A solvent can be used in the quantity of 100-10000 weight part with respect to 100 weight part of coloring agents in a coloring composition, Preferably it is 500-5000 weight part.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 400 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 5 to 400 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
By using polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant.
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Antioxidant>
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. Antioxidants prevent the photopolymerization initiator contained in the color filter coloring composition from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing, and thus increase the transmittance of the coating film. it can. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

Preferable examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfide antioxidants. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with -hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like.

The content of the antioxidant is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the color filter coloring composition.
When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention comprises a kneader, a two-roll mill, a coloring agent, a dispersing agent, a coloring agent carrier such as a resin and / or a solvent, if necessary, and a dispersing aid. It can be produced by finely dispersing using various dispersing means such as a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
One of the dispersant (Xa) and the vinyl resin type dispersant (Xb) having a tertiary amino group may be added later to the colorant dispersion, but preferably both are used during dispersion. Is desirable.
Used when dispersing the colorant, the vinyl resin type dispersant (Xb) having a tertiary amino group is more easily adsorbed on the surface of the colorant, and the interaction with the colorant is enhanced, thereby improving the dispersibility. To do.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, not only the dispersant but also a dispersion aid such as a pigment derivative and a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. Alternatively, the at least one filter segment is formed from the coloring composition of the present invention.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used. A black matrix formed from is preferable. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

  Further, the weight average molecular weight (Mw) of the resin and the dispersant, the acid value of the resin and the dispersant, the average molecular weight of the vinyl resin having a tertiary amino group, the amine value of the vinyl resin having a tertiary amino group, and a pigment The average primary particle diameter and the contrast ratio of the coating film are measured as follows.

(Weight average molecular weight of resin and dispersant (Mw))
The weight average molecular weight (Mw) of the resin and the dispersant was measured using a TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

(Acid value of resin and dispersant (mgKOH / g))
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

(Average molecular weight of vinyl resin having tertiary amino group)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the basic resin type dispersant are HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an N, N-dimethylformamide solution of 10 mM LiBr.

(Amine value of vinyl resin having tertiary amino group)
The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into a solid content.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Contrast ratio of coating film (CR))
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, a dispersing agent, a refinement | purification pigment, a red photosensitive coloring resist material, and a blue photosensitive coloring resist material is demonstrated.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution)
A reactor equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of PGMAc, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2 , 2′-Azobisisobutyronitrile (0.4 parts) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. To prepare an acrylic resin solution.

<Method for producing dispersant>
(Synthesis of dispersant (XC-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was completed after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (XC-1) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of t-butyl methacrylate, and 45.4 parts of PGMAc and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was completed after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (Xa-1) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-2 to 4))
Dispersants (Xa-2 to 4) were synthesized in the same manner as the dispersant (Xa-1) except that the raw materials shown in Table 1 were changed.

The abbreviations in Table 1 are as follows.
<< ethylenically unsaturated monomer (c) >>
MMA: methyl methacrylate n-BA: n-butyl acrylate

[Ethylenically unsaturated monomer having thermally crosslinkable group]
t-BA: tert-butyl acrylate OXMA: “ETERRNACOLL OXMA” manufactured by Ube Industries
(3-Methyl-3-oxetanyl) methyl methacrylate MOI-BM: “Karenz MOI-BM” manufactured by Showa Denko
Methacrylic acid 2-([1′-methylpropylideneamino] carboxyamino) ethyl

AIBN: 2,2′-azobisisobutyronitrile PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
TMA: Trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by Sun Apro Co., Ltd.)

(Synthesis of dispersant (Xa-5))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 part of monobutyltin oxide, PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was performed for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (Xa-5) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-6))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 part of monobutyltin oxide, PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was performed for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. Furthermore, 23.9 parts of MOI (2-methacryloyloxyethyl isocyanate) and 0.04 part of hydroquinone were charged, and the reaction was performed until the disappearance of the peak at 2270 cm −1 based on the isocyanate group was confirmed by IR. After confirming the disappearance of the peak, the reaction solution was cooled and adjusted to 50% non-volatile content with PGMAc to obtain a dispersant (Xa-6) having an unsaturated double bond equivalent 907, an acid value 43, and a weight average molecular weight 9500. .

(Synthesis of dispersant (Xb-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAc and heated to 110 ° C. while purging with nitrogen. In a dropping tank, 120 parts of tetramethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., funcryl FA-712HM), 70 parts of methyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 2,2′-azobis (2 , 4-dimethylvaleronitrile) was added to the reaction vessel, and the mixture was stirred until it was uniform. Thus, a vinyl resin type dispersant (Xb-1) having a tertiary amino group having an amine value per solid content of 145 mg KOH / g and a number average molecular weight of 3,500 (Mn) was obtained.

(Synthesis of dispersant (Xb-2 to 11))
The vinyl resin-type dispersant (Xb-2 to 11) having a piperidyl skeleton was synthesized in the same manner as the dispersant (Xb-1) except that the raw materials and preparation amounts (parts by weight) described in Table 2 were used. Solution was obtained. The respective amine values and number average molecular weights are as shown in Table 2.

2,2,6,6-tetramethylpiperidyl methacrylate: (manufactured by Hitachi Chemical Co., Ltd., funcryl FA-712HM)
1,2,2,6,6-pentamethylpiperidyl methacrylate: (manufactured by Hitachi Chemical Co., Ltd., funcryl FA-711MM)
* Content of ethylenically unsaturated monomer having tertiary amino group (wt%)
= Content of ethylenically unsaturated monomer having tertiary amino group / total content of ethylenically unsaturated monomer

<Method for producing fine pigments>
(Fine refined pigment (PG-1))
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The kneaded product is put into 8 liters of warm water, stirred for 2 hours while being heated to 80 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C., 190 parts The average primary particle diameter of the refined pigment (PG-1) was 29.8 nm.

(Fine refined pigment (PY-1))
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a refined pigment (PY-1) were obtained. The average primary particle diameter of the fine pigment (PY-1) was 37.8 nm.

(Fine refined pigment (PY-2))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a refined pigment (PY-2) was obtained. The average primary particle diameter of the fine pigment (PY-2) was 38.6 nm.

(Fine refined pigment (PY-3))
Isoindoline yellow pigment C.I. I. 500 parts of Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a refined pigment (PY-3) was obtained. The average primary particle diameter of the fine pigment (PY-3) was 40.2 nm.

(Fine refined pigment (PY-4))
Isoindoline yellow pigment C.I. I. 500 parts of CI Pigment Yellow 185 (“Pariogen Yellow D1155” manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a refined pigment (PY-4) was obtained. The average primary particle diameter of the fine pigment (PY-4) was 32.7 nm.

(Refined pigment (PR-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of refined pigment (PR-1) was obtained. The average primary particle diameter of the refined pigment (PR-1) was 37.7 nm.

(Fine refined pigment (PB-1))
Phthalocyanine blue pigment C.I. I. 200 parts of Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of refined pigment (PB-1) were obtained. The average primary particle diameter of the fine pigment (PB-1) was 38.0 nm.

(Fine refined pigment (PB-2))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (9).
Next, 100 parts of aluminum phthalocyanine pigment represented by the formula (9) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. . After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment (PB-2) represented by the following chemical formula (10). The average primary particle diameter of the fine pigment (PB-2) was 31.2 nm.

Chemical formula (9)

Chemical formula (10)

(Fine refined pigment (PB-3))
In a reaction container, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the chemical formula (9) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of an aluminum phthalocyanine pigment (PB-3) represented by the following chemical formula (11). The average primary particle diameter of the fine pigment (PB-3) was 29.5 nm.

Chemical formula (11)

(Fine refined pigment (PB-4))
According to the synthesis method described in JP 2010-79247 A, an aluminum phthalocyanine pigment (PB-4) represented by the following chemical formula (12) was obtained. The average primary particle diameter of the finer pigment (PB-4) was 33.0 nm.

Chemical formula (12)

(Fine refined pigment (PB-5))
To 100 parts of the aluminum phthalocyanine pigment represented by the chemical formula (9), 200 parts of pyridine, 800 parts of xylene and 54.6 parts of phenylphosphonic acid were added, and heating and refluxing were continued for 8 hours. After filtration, washing with methanol and drying, 110 parts of an aluminum phthalocyanine pigment (PB-5) represented by the following chemical formula (13) was obtained. The average primary particle diameter of the fine pigment (PB-5) was 37 nm.

Chemical formula (13)

(Fine refined pigment (PV-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of refined pigment (PV-1) were obtained. The average primary particle size of the fine pigment (PV-1) was 38.4 nm.

<Production of photosensitive red resist material and photosensitive blue resist material>
(Photosensitive red resist material 1)
[Pigment dispersion 1]
First, the following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, A pigment dispersion 1 was prepared by filtration through a 0.0 μm filter.
Refined pigment (PR-1): 11.0 parts acrylic resin solution: 39.0 parts Resin type dispersant (EFKA4300): 2.0 parts Solvent: 48.0 parts Propylene glycol monomethyl ether acetate (PGMAC)

[Pigment dispersion 2]
A pigment dispersion 2 was obtained in the same manner as the pigment dispersion 1 except that the refined pigment (PR-1) was changed to the refined pigment (PY-3).

The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a photosensitive red resist material 1.
Pigment dispersion 1: 42.0 parts C.I. I. Pigment Red 254
Pigment dispersion 2: 8.0 parts C.I. I. Pigment Yellow 139
Acrylic resin solution: 21.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts propylene glycol monomethyl ether acetate (PGMAC)

(Photosensitive blue resist material 1)
[Pigment dispersions 3 and 4]
The pigment dispersion 2 or the pigment dispersion is the same as the pigment dispersion 1 except that the refined pigment (PR-1) is changed to the refined pigment (PB-1) or the refined pigment (PV-1). Body 4 was obtained.

The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a photosensitive blue resist material.

Pigment dispersion 3: 40.0 parts C.I. I. Pigment Blue 15: 6
Pigment dispersion 4: 10.0 parts C.I. I. Pigment Violet 23
Acrylic resin solution: 21.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts propylene glycol monomethyl ether acetate (PGMAC)

[Example 1]
(Pigment dispersion (P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a green pigment dispersion (P-1) was produced.

Fine pigment (PG-1): 11.0 parts acrylic resin solution: 33.0 parts Dispersant (Xa-1): 4.0 parts Dispersant (Xb-1): 4.0 parts Solvent: 48.0 parts Propylene Glycol monomethyl ether acetate (PGMAc)

[Examples 2 to 27, Comparative Examples 1 to 4]
(Pigment dispersion (P-2 to 31))
Hereinafter, the green pigment dispersion (P-2 to P-2) was changed in the same manner as the green pigment dispersion (P-1) except that the finer pigment or the dispersant and the blending amount (parts by weight) thereof shown in Table 3 were changed. 19, P-24-25, P-28-31), a blue pigment dispersion (P-20-23), and a yellow pigment dispersion (P-26-27). In addition, the compounding quantity of a dispersing agent is a total of 8 weight part in all the pigment dispersions.

In addition, the green pigment dispersions of P-24 and 25 are made of fine pigment (PG-1) (PG58) and fine pigment (PY-3) (PY139) or fine pigment (PY-4) (PY185). Used to formulate (PG-1) / (PY-3 or 4) = 77.8 / 22.2.

Disperbyk-111:
Phosphoric ester dispersant “Disperbyk-111” manufactured by Big Chemie
* Dispersant (Xb) / Dispersant (Xa)
= Content of dispersant (Xb) with respect to 100 parts by weight of dispersant (Xa) (parts by weight)

<Evaluation of pigment dispersion>
The obtained pigment dispersion was evaluated for stability over time, brightness, contrast ratio, and heat resistance by the following methods. Table 4 shows the evaluation results. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical level, and x is a level which is not suitable for practical use.

(Evaluation of storage stability)
After the initial viscosity of the obtained pigment dispersion was measured with an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), it was stored in a constant temperature machine at 40 ° C. for 1 week to promote aging. The viscosity of the pigment dispersion was measured by the same method as the above viscosity measurement, and the change rate of the viscosity before and after storage at 40 ° C. for 1 week was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 20% and no sediment is formed.
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is generated even when the viscosity change rate is within ± 20%.

(Lightness evaluation)
The obtained green pigment dispersion, blue pigment dispersion, and yellow pigment dispersion were placed on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that the chromaticity in the C light source would be the following value. And then dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes to produce a substrate. The target chromaticity of each pigment dispersion in the C light source is as follows.

Green pigment dispersion: y = 0.600
Blue pigment dispersion: x = 0.176
Yellow pigment dispersion: x = 0.440

The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Contrast ratio)
Spin the obtained green pigment dispersion, blue pigment dispersion, and yellow pigment dispersion on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness so that the chromaticity in the C light source sandwiches the value shown above. Using a coater, the number of rotations was changed and three coated substrates were produced. Next, after drying at 70 degreeC for 20 minutes, the coating-film board | substrate was produced by heating at 230 degreeC for 60 minutes and standing to cool. The chromaticity and contrast ratio (CR) of each of the obtained coated substrates were measured, and the contrast ratio (CR) at each target chromaticity was determined from the three points of data by the primary correlation method.

(Evaluation of heat resistance of coating film)
The obtained colored composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dried coating film was about 2.5 μm, and then dried at 70 ° C. for 20 minutes. Then, the coated substrate was prepared by heating and cooling at 230 ° C. for 30 minutes.
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔE * ab was determined and evaluated in the following four stages.

ΔE * ab = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

◎: ΔE * ab is less than 3.0 ○: ΔE * ab is 3.0 or more and less than 5.0 Δ: ΔE * ab is 5.0 or more and less than 10.0 ×: ΔE * ab is 10.0 or more

  From the results in Table 4, the pigment dispersions (P-1 to P-1) of Examples 1 to 22 containing the dispersant (Xa) which is the invention of the present application and the vinyl resin type dispersant (Xb) having a tertiary amino group. 19, P-24, 25) were good evaluation results in terms of viscosity stability, heat resistance, and brightness. In particular, the pigments of Examples 2, 4, 5, and 10 using the dispersant (Xb-2, 4, 5, 10) in which the amine value of the dispersant (Xb) is 250 to 400 mg KOH / g, which is the most preferable range. The dispersion (P-2, 4, 5, 10) showed a particularly high contrast ratio.

Further, when the dispersant (Xb) had a piperidyl skeleton, the result was excellent in lightness.
Furthermore, when the content of the dispersant (Xb) was 50 to 250 parts by weight with respect to 100 parts by weight of the dispersant (Xa), the brightness and heat resistance were better.
Further, the blue dispersions (P-20 to 23) of Examples 20 to 23 and the yellow dispersions (P-26 and 27) of Examples 26 and 27 were also excellent in various properties such as stability.

  On the other hand, since the pigment dispersions (P-28, 31) of Comparative Examples 1 and 4 do not contain the dispersant (Xa), the viscosity stability, brightness, and contrast ratio are good, but the coating film heat resistance is improved. There was a problem. In addition, since the pigment dispersions (P-29, 30) of Comparative Examples 2 and 3 do not contain both the dispersant (Xa) and the dispersant (Xb), the pigment dispersion (P-29, 30) has poor stability and low brightness and contrast ratio. there were.

[Example 28]
(Photosensitive green resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing type green resist material (R-1).
Pigment dispersion (P-1): 35.0 parts Pigment dispersion (P-26): 15.0 parts Acrylic resin solution: 21.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Toagosei Co., Ltd. Aronix M-402 ")
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Solvent: 23.2 parts Propylene glycol monomethyl ether acetate (PGMAc)

[Examples 29 to 53, Comparative Examples 5 to 8]
(Photosensitive green resist material (R-2 to 30))
Hereinafter, the alkali-developable green resist material (R-2) was changed in the same manner as the alkali-developable green resist material (R-1) except that the pigment dispersion was changed to the dispersion and blending amount (parts by weight) shown in Table 6. To 30). The content of the pigment dispersion is 50 parts in total.

<Evaluation of photosensitive coloring composition>
Evaluation of the initial viscosity, the temporal stability, the storage stability, the NMP resistance, the heat resistance and the brightness of the obtained colored composition was performed by the following methods. Table 6 shows the evaluation results. In addition, (double-circle) is a very good level, (circle) is a favorable level, and x is a level unsuitable for practical use.

(Evaluation of storage stability)
After the initial viscosity of the obtained photosensitive colored resist material was measured with an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.), it was stored in a thermostat at 40 ° C. for 1 week and accelerated over time. The viscosity of the photosensitive colored resist material after the lapse of time was measured by the same method as the above viscosity measurement, the change rate of the viscosity before and after storage at 40 ° C. for 1 week was calculated, and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 20% and no sediment is formed.
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is generated even when the viscosity change rate is within ± 20%.

(NMP resistance and heat resistance of coating film)
The resulting photosensitive colored resist material was evaluated for NMP resistance and coating film heat resistance by the following methods.
In addition, the film thickness of the coating film was measured using Dektak 3030 (made by Nippon Vacuum Technology Co., Ltd.).

  In the evaluation of NMP resistance and heat resistance, after applying a resist material, UV exposure is performed through a mask having a specific pattern, and then an alkali developer is sprayed to remove the uncured portion to form a specific pattern. doing. This specific pattern is a stripe pattern in which linear patterns are arranged, the pattern width is 200 μm, and the distance between the patterns is also 200 μm.

(Evaluation of coating NMP resistance)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Here, after measuring the chromaticity (L * (1), a * (1), b * (1)) with C light source, it was immersed in NMP (N-methylpyrrolidone) for 30 minutes, and further with C light source. Was measured (L * (2), a * (2), b * (2)).
Using the color difference values before and after NMP immersion, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated in the following three stages.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

◎: ΔE * ab is 1 or less ○: ΔE * ab is greater than 1 and less than 3 ×: ΔE * ab is 3 or more

(Evaluation of heat resistance of coating film)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Thereafter, an ITO (indium tin oxide) film was formed by sputtering so as to have an average film thickness of 1500 angstroms. Using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source Measured. Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 3 hours, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured. Using the measured color difference value, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

◎: ΔE * ab is 1 or less ○: ΔE * ab is greater than 1 and less than 3 ×: ΔE * ab is 3 or more

(Evaluation of brightness)
A resist material was applied on a glass substrate so that the chromaticity of the coating film was y = 0.600 using a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

From the results of Table 6, the coloring composition containing the dispersant (Xa) which is the invention of the present application and the vinyl resin type dispersant (Xb) having a tertiary amino group has a viscosity stability, NMP resistance and heat resistance. In all cases, good evaluation results were obtained.
Further, when the dispersant (Xb) had a piperidyl skeleton, the result was excellent in lightness.
Furthermore, when the content of the dispersant (Xb) was 50 to 250 parts by weight with respect to 100 parts by weight of the dispersant (Xa), the brightness and heat resistance were better.

  On the other hand, since the coloring composition of the comparative example does not contain the dispersant (Xa) or the vinyl-based resin type dispersant (Xb) having a tertiary amino group, there is a problem in terms of stability and resistance. became.

<Manufacture of color filters>
(Production of color filter)
A black matrix is patterned on a glass substrate, and the photosensitive red resist material 1 is applied to the substrate with a spin coater at a C light source (hereinafter also used for green and blue) x = 0.640, y = 0.330 The film was applied to such a thickness that a colored film was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development is performed with an alkali developer composed of a 2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 20 minutes to form a red filter segment. did. In the same manner, the photosensitive green resist material (R-1) is formed to a thickness such that x = 0.300 and y = 0.600, and x = 0.150 using the photosensitive blue resist material 1. Each was applied to a thickness such that y = 0.06 to form a green filter segment and a blue filter segment to obtain a color filter.

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel.

  By using the color filter resist material of the present invention, a color filter having good color characteristics and high heat resistance and solvent resistance could be obtained.

Claims (6)

A color composition for a color filter containing a colorant, a dispersant, a binder resin, and a solvent,
The dispersant contains the dispersant (Xa) and the dispersant (Xb),
Dispersant (Xa) is an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) and a hydroxyl group-containing compound (a). A polyester portion Xa1 ′ having a carboxyl group obtained by reacting with a hydroxyl group;
A vinyl polymer portion Xa2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group;
The thermally crosslinkable functional group is a dispersant that is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group,
A coloring composition for a color filter, wherein the dispersant (Xb) is a vinyl resin type dispersant having a tertiary amino group.   The coloring composition for a color filter according to claim 1, wherein the dispersant (Xb) has a piperidyl skeleton.   The coloring composition for a color filter according to claim 1 or 2, wherein the colorant contains at least one of a zinc halide phthalocyanine pigment and an aluminum phthalocyanine pigment.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the amine value of the dispersant (Xb) is 50 to 500 mgKOH / g.   Furthermore, the coloring composition for color filters of any one of Claims 1-4 containing a photoinitiator and / or a photopolymerizable monomer.   A color filter comprising a filter segment formed on the base material from the colored composition for color filter according to any one of claims 1 to 5.