JP5412867B2 - Red color filter - Google Patents

Description

  The present invention relates to a red coloring composition used for forming a red color filter having high brightness, and a red color filter, thereby improving the visibility of a liquid crystal display device without using a backlight having high luminance. Can be better.

  A color liquid crystal display device is basically sealed between a first transparent substrate on which a first transparent electrode layer is formed, a second transparent substrate on which a second transparent electrode layer is formed, and a gap between them. The color filter is usually formed between the second transparent substrate and the second transparent electrode. First and second polarizing plates are provided outside the first and second transparent substrates, respectively, and a backlight unit including a backlight light source is provided outside the first polarizing plate. .

  In such a liquid crystal display device, the voltage applied between the first and second transparent electrode layers is adjusted for each filter segment, and the degree of polarization of light from the backlight unit that has passed through the first polarizing plate is controlled. The display is performed by controlling the amount of light passing through the second polarizing plate. Therefore, the color characteristics of the color filter and the polarizing plate are important factors that determine the color characteristics of the liquid crystal display device.

  A color filter has a black matrix, which is a light shielding pattern, and red, green, and blue fine band (striped) filter segments arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine filter. It is composed of filter segments arranged in a constant arrangement.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, and power saving due to their thinness, and their applications are rapidly expanding to large televisions and monitors. The demand for higher brightness, higher color reproducibility, and higher contrast is increasing for color filters that determine the color characteristics.

A color filter for a liquid crystal display device is obtained mainly by a pigment dispersion method. However, measures have been taken to increase the transmittance of the color filter by making the particle size of the pigment as small as possible, but the pigment with a small particle size is likely to agglomerate, and stable pigment fine particle dispersion that exhibits sufficient transmission It is very difficult to do. Therefore, in order to improve the visibility of the liquid crystal display device using the color filter obtained by the pigment dispersion method, it is generally used in combination with a backlight having a high luminance, but the backlight having a high luminance is used. Requires a lot of power and does not save energy.
JP-A-63-305173 Japanese Patent Laid-Open No. 57-15620 JP 59-40172 A

The present invention realizes a red color filter having a brightness higher than that of a conventional color filter in order to improve the visibility of a liquid crystal display device without using a backlight having high luminance and requiring large power. An object of the present invention is to provide a red coloring composition.

  The present invention is a red coloring composition containing at least a red dye and a pigment, the red dye has a maximum absorption wavelength (λmax) at 560 nm to 565 nm, and the transmittance of the red dye at 550 nm is 1 %, The wavelength at which the transmittance is 50% is in the range of 595 nm to 600 nm, the transmittance of 400 nm to 550 nm is less than 40%, and the transmittance of 630 nm to 700 nm is 94% or more. It is a red coloring composition.

  Further, the present invention provides the red coloring composition according to the invention, wherein the pigment is C.I. I. Pigment Red 254, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 150, C.I. I. It is a red coloring composition characterized by containing at least one of Pigment Yellow 139.

  Further, the present invention is the red coloring composition according to the above invention, wherein the red dye has an azo skeleton or is an azo-based metal complex.

  In the red coloring composition according to the present invention, the red dye may be C.I. I. Solvent Red 124, or C.I. I. It is a red coloring composition characterized by being Solvent Red 89.

  Moreover, this invention is formed using the red coloring composition of any one of Claims 1-4, It is a red color filter characterized by the above-mentioned.

  The present invention has a maximum absorption wavelength (λmax) at 560 nm to 565 nm as a red dye, and when the transmittance at 550 nm is 1%, the wavelength at which the transmittance is 50% is in the range of 595 nm to 600 nm, In addition, a red dye having a transmittance of 400 nm to 550 nm of less than 40% and a transmittance of 630 nm to 700 nm of 94% or more and a red coloring composition used in combination with a conventional pigment, pigment resist and other dyes It is possible to obtain a red color filter having a lightness higher than that of a resist using.

  The present invention also provides C.I. I. Pigment Red 254, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 150, C.I. I. Since it is a red coloring composition combined with any one of four pigments of Pigment Yellow 139, a red color filter having a higher brightness than a color filter not using a conventional dye can be obtained.

  The present invention also includes C.I. I. Solvent Red 124, or C.I. I. Since it is a red coloring composition using Solvent Red 89, a red color filter having high brightness can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
First, the red coloring composition of the present invention will be described. The red coloring composition of the present invention is a red coloring composition containing at least a red dye and a pigment, and the red dye has a maximum absorption wavelength (λmax) at 560 nm to 565 nm and has a transmittance at 550 nm. When 1%, the wavelength at which the transmittance is 50% is in the range of 595 nm to 600 nm, the transmittance of 400 nm to 550 nm is less than 40%, and the transmittance of 630 nm to 700 nm is 94% or more. It is what. As a result, a red color filter having high brightness can be obtained.

  In addition, when the red dye has an azo skeleton or an azo metal complex, a red coloring composition having high solubility in the organic solvent and good storage stability as a resist can be obtained. Examples of the azo metal complex include C.I. I. Solvent Red 124, C.I. I. Solvent Red 89 and the like can be mentioned, but other dyes in accordance with the gist of the present invention may be used.

  In the red coloring composition, other dyes can be used in combination with the red dye having the spectral characteristics. Usable dyes are azo dye, azo metal complex dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline Examples include dyes, naphthoquinone dyes, and oxazine dyes. Specific examples of dyes that can be used in the red coloring composition are shown by color index (CI) numbers below.

C. I. Solvent Red 2, C.I. I. Solvent Red 24, C.I. I. Solvent Red 27, C.I. I. Solvent Red 52, C.I. I. Solvent Red 57, C.I. I. Solvent Red 111, C.I. I. Solvent Red 114, C.I. I. Solvent Red 119, C.I. I. Solvent Red 135, C.I. I. Solvent Red 136, C.I. I. Solvent Red 137, C.I. I. Solvent Red 138, C.I. I. Solvent Red 139, C.I. I. Solvent Red 143, C.I. I. Solvent Red 144, C.I. I. Solvent Red 145, C.I. I. Solvent Red 146, C.I. I. Solvent Red 147, C.I. I. Solvent Red 148, C.I. I. Solvent Red 149, C.I. I. Solvent Red 150, C.I. I. Solvent Red 151, C.I. I. Solvent Red 152, C.I. I. Solvent Red 155, C.I. I. Solvent Red 156, C.I. I. Solvent Red 162, C.I. I. Solvent Red 168, C.I. I. Solvent Red 169, C.I. I. Solvent Red 170, C.I. I. Solvent Red 171, C.I. I. Solvent Red 172, C.I. I. Solvent Red 177, C.I. I. Solvent Red 178, C.I. I. Solvent Red 179, C.I. I. Solvent Red 181, C.I. I. Solvent Red 190, C.I. I. Solvent Red 191, C.I. I. Solvent Red 194, C.I. I. Solvent Red 199, C.I. I. Solvent Red 200, C.I. I. Solvent Red 201, C.I. I. Solvent Red 299, C.I. I. Direct Red 2, C.I. I. Direct Red 81, C.I. I. Acid Red 1, C.I. I. Acid Red 14, C.I. I. Acid Red 27, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 88, C.I. I. Basic Red 1, C.I. I. Mordant Red 3, C.I. I. Azoic Red 21, C.I. I. Vat Red 1, C.I. I. Vat Red 2, C.I. I. Vat Red 15, C.I. I. Vat Red 23, C.I. I. Vat Red 41, C.I. I. Vat Red 47, C.I. I. Disperse Red 1, C.I. I. Disperse Red 11, C.I. I. Disperse Red 15, C.I. I. Disperse Red 22, C.I. I. Disperse Red 60, C.I. I. Disperse Red 92, C.I. I. Disperse Red 146, C.I. I. Disperse Red 191, C.I. I. Disperse Red 283, C.I. I. Disperse Red 288, C.I. I. Reactive Red 12, C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 7, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 10, C.I. I. Solvent Yellow 11, C.I. I. Solvent Yellow 12, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 16, C.I. I. Solvent Yellow 18, C.I. I. Solvent Yellow 21, C.I. I. Solvent Yellow 25, C.I. I. Solvent Yellow 33, C.I. I. Solvent Yellow 56, C.I. I. Solvent Yellow 58, C.I. I. Solvent Yellow 62, C.I. I. Solvent Yellow 79, C.I. I. Solvent Yellow 83, C.I. I. Solvent Yellow 83: 1, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 89, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 109, C.I. I. Solvent Yellow 117, C.I. I. Solvent Yellow 125, C.I. I. Solvent Yellow 133, C.I. I. Solvent Yellow 146, C.I. I. Solvent Yellow 151, C.I. I. Solvent Yellow 156, C.I. I. Solvent Yellow 157, C.I. I. Solvent Yellow 158, C.I. I. Solvent Yellow 160: 1, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 38, C.I. I. Acid Yellow 49, C.I. I. Acid Yellow 67, C.I. I. Acid Yellow 72, C.I. I. Acid Yellow 99, C.I. I. Acid Yellow 110, C.I. I. Acid Yellow 127, Basic Yellow 21, C.I. I. Vat yellow 1, C.I. I. Vat Yellow 2, C.I. I. Vat yellow 3, C.I. I. Vat yellow 4, C.I. I. Disperse Yellow 9, C.I. I. Disperse Yellow 23, C.I. I. Disperse Yellow 33, C.I. I. Disperse Yellow 42, C.I. I. Disperse Yellow 49, C.I. I. Disperse Yellow 54, C.I. I. Disperse Yellow 58, C.I. I. Disperse Yellow 60, C.I. I. Disperse Yellow 64, C.I. I. Disperse Yellow 66, C.I. I. Disperse Yellow 71, C.I. I. Disperse Yellow 79, C.I. I. Disperse Yellow 86, Disperse Yellow 87, C.I. I. Disperse Yellow 90, C.I. I. Disperse Yellow 93, C.I. I. Disperse Yellow 114, C.I. I. Disperse Yellow 116, C.I. I. Disperse Yellow 119, C.I. I. Disperse Yellow 122, C.I. I. Disperse Yellow 149, Disperse Yellow 160, C.I. I. Disperse Yellow 163, C.I. I. Disperse Yellow 198, C.I. I. Disperse Yellow 211, C.I. I. Disperse Yellow 226, C.I. I. Disperse Yellow 227, C.I. I. Disperse Yellow 231, C.I. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 35, C.I. I. Solvent Orange 43, C.I. I. Solvent Orange 55, C.I. I. Solvent Orange 60, C.I. I. Solvent Orange 64, C.I. I. Solvent Orange 65, C.I. I. Solvent Orange 66, C.I. I. Solvent Orange 68, C.I. I. Solvent Orange 69, C.I. I. Solvent Orange 71, C.I. I. Solvent Orange 77, C.I. I. Solvent Orange 78, C.I. I. Solvent Orange 86, C.I. I. Solvent Orange 87, C.I. I. Solvent Orange 163, C.I. I. Acid Orange 67, C.I. I. Acid Orange 127, C.I. I. Vat orange 1, C.I. I. Vat orange 2, C.I. I. Vat orange 4, C.I. I. Vat orange 7, C.I. I. Vat orange 9, C.I. I. Disperse Orange 25, C.I. I. Disperse Orange 29, C.I. I. Disperse Orange 31, C.I. I. Disperse Orange 32, C.I. I. Disperse Orange 37, C.I. I. Disperse Orange 45, C.I. I. Disperse Orange 56, C.I. I. Disperse Orange 61, C.I. I. Disperse Orange 76, C.I. I. Disperse Orange 96, C.I. I. Disperse Orange 97, C.I. I. Disperse orange 118 and the like can be mentioned, but other dyes may be used. These dyes can be used in combination with required color characteristics.

Moreover, the red coloring composition of this invention can use an organic or inorganic pigment individually or in combination of 2 or more types. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high resistance to thermal decomposition are preferable, and organic pigments are usually used. Dyes generally have a problem that heat resistance and light resistance are weaker than pigments. For this reason, the red coloring composition of this invention contains the said red dye and a pigment, and the red coloring composition with high brightness is obtained, maintaining heat resistance and light resistance.
As the organic pigment contained in the red coloring composition, commercially available ones can be used.

Below, the specific example of the organic pigment which can be used for a red coloring composition is shown by a color index (CI) number.
Examples of red pigments include C.I. I. Pigment Red 7, C.I. I. Pigment Red 9, C.I. I. Pigment Red 14, C.I. I. Pigment Red 41, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 81: 2, C.I. I. Pigment Red 81: 3, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 192, C.I. I. Pigment Red 200, C.I. I. Pigment Red 202, C.I. I. Pigment Red 208, C.I. I. Pigment Red 210, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 240, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272 and other red pigments can be used. I. Pigment Red 177, C.I. I. Pigment Red 254 is preferred. Moreover, a yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 4, C.I. I. Pigment Yellow 5, C.I. I. Pigment Yellow 6, C.I. I. Pigment Yellow 10, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 18, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment Yellow 32, C.I. I. Pigment Yellow 34, C.I. I. Pigment Yellow 35, C.I. I. Pigment Yellow 35: 1, C.I. I. Pigment Yellow 36, C.I. I. Pigment Yellow 36: 1, C.I. I. Pigment Yellow 37, C.I. I. Pigment Yellow 37: 1, C.I. I. Pigment Yellow 40, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 43, C.I. I. Pigment Yellow 53, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 60, C.I. I. Pigment Yellow 61, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 63, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 73, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 77, C.I. I. Pigment Yellow 81, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 98, C.I. I. Pigment Yellow 100, C.I. I. Pigment Yellow 101, C.I. I. Pigment Yellow 104, C.I. I. Pigment Yellow 106, C.I. I. Pigment Yellow 108, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 113, C.I. I. Pigment Yellow 114, C.I. I. Pigment Yellow 115, C.I. I. Pigment Yellow 116, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 118, C.I. I. Pigment Yellow 119, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 123, C.I. I. Pigment Yellow 126, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 152, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 156, C.I. I. Pigment Yellow 161, C.I. I. Pigment Yellow 162, C.I. I. Pigment Yellow 164, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 167, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 169, C.I. I. Pigment Yellow 170, C.I. I. Pigment Yellow 171, C.I. I. Pigment Yellow 172, C.I. I. Pigment Yellow 173, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 177, C.I. I. Pigment Yellow 179, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 182, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 187, C.I. I. Pigment Yellow 188, C.I. I. Pigment Yellow 192, C.I. I. Pigment Yellow 193, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 196, C.I. I. Pigment Yellow 198, C.I. I. Pigment Yellow 199, C.I. I. Pigment Yellow 213, C.I. I. Pigment Yellow 214 can be used, among which C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 is preferred.

  Examples of orange pigments include C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73 and the like.

The red coloring composition can contain an inorganic pigment in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Examples of inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), and cadmium red.
An inorganic pigment is used individually or in combination of 2 or more types. The inorganic pigment can be used in an amount of 0.1 to 10 parts by weight based on the pigment weight of 100 parts by weight.

The pigment contained in the red coloring composition is preferably finely processed and has a large specific surface area in order to realize high brightness and high contrast of the color filter. As a means for controlling the specific surface area of the pigment, a method of controlling the specific surface area by mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a desired specific surface area of the pigment is controlled. There are a method of precipitating a pigment (referred to as a precipitation method), a method of producing a pigment having a desired specific surface area at the time of synthesis (referred to as a synthetic precipitation method), and the like. Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.

Each method will be described below, but any of the above methods may be used as a method for controlling the specific surface area of the pigment contained in the colored composition used in the present invention.
In the grinding method, a pigment is mechanically kneaded with a grinding agent such as a water-soluble inorganic salt such as sodium chloride and a water-soluble organic solvent that does not dissolve the pigment using a ball mill, a sand mill, or a kneader (hereinafter, this step is referred to as a process). This method is called salt milling), and then the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired specific surface area. However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved, but the productivity is lowered because the amount of pigment processed is reduced. In general, 1 to 30 parts by weight, preferably 2 to 20 parts by weight of the inorganic salt is used per 1 part by weight of the pigment. Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified, and depending on the blending ratio of the pigment and the inorganic salt, the amount of the pigment is usually 50 to 300% by weight. Used.
More specifically, the salt milling is performed by adding a small amount of a water-soluble organic solvent as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, kneading with a kneader or the like, and then pouring the mixture into water. Stir with a speed mixer to make a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired specific surface area.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired specific surface area. The specific surface area depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The size of can be controlled. In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited, but examples include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, chlorosulfonic acid, or basic solvents such as liquid ammonia, dimethylformamide solution of sodium methylate, etc. It has been known.

  A typical example of this method is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100% by weight. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes bad. Conversely, if the amount is too large, the treatment efficiency of the pigment is lowered. It is preferable. The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment. As the time increases, the specific surface area tends to decrease.

The specific surface area of the pigment can be controlled while considering the fine particle size of the pigment by selecting a method that combines a precipitation method such as the acid pasting method and a grinding method such as the salt milling method. At this time, it is more preferable because fluidity as a dispersion can be secured.
At the time of salt milling or acid pasting, in order to prevent the aggregation of the pigment accompanying the specific surface area control, the following dispersion aids such as pigment derivatives, resin-type pigment dispersants and surfactants can be used in combination. Further, by controlling the specific surface area in the form of coexisting two or more kinds of pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

  There is a leuco method as a special precipitation method. When a vat dye, such as a flavantron, perinone, perylene, or indanthrone, is reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. A pigment having a large specific surface area that is insoluble in water can be precipitated by adding an appropriate oxidizing agent to the aqueous solution for oxidation.

The synthetic precipitation method is a method in which a pigment having a desired specific surface area is deposited simultaneously with the synthesis of the pigment. However, when the produced fine pigment is taken out of the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments synthesized in water.
Furthermore, as a means of controlling the specific surface area of the pigment, the pigment can be dispersed at the same time as increasing the specific surface area of the pigment by dispersing the pigment for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry pulverized). Is possible.

  The dye carrier contained in the color filter coloring composition of the present invention disperses the dye and is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a 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 transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used.

  The dye carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the dye in the red coloring composition. Moreover, when using the mixture of transparent resin and its precursor as a pigment | dye carrier, transparent resin is 20-400 weight part with respect to 100 weight part of pigment | dye in a red coloring composition, Preferably it is 50-250 weight. It can be used in parts. Moreover, the precursor of transparent resin can be used in the quantity of 10-300 weight part with respect to 100 weight part of pigment | dyes in a red coloring composition, Preferably it is 10-200 weight part.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, various acrylic esters such as epoxy (meth) acrylate and methacrylic acid Examples include esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the red coloring composition.
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-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- Acetophenone photopolymerization initiators such as 1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -F Benzophenone photopolymerization initiators such as nylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone photopolymerization initiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -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 (trichloro Til) -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, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dye in a red coloring composition, Preferably it is 10-150 weight part.
The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

Furthermore, the red coloring composition can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate,
Ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropio Nate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4, Examples include 6-dimercapto-s-triazine. These polyfunctional thiols can be used alone or in combination.
The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by weight, preferably 0.2 to 100 parts by weight, with respect to 100 parts by weight of the dye in the red coloring composition.

Further, in the red coloring composition of the present invention, the dye is sufficiently dispersed in the dye carrier, and is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate formation.
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, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-
ON, 3,3,5-trimethylcyclohexanone, methyl 3-methoxypropionate, 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-butyl alcohol, 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, ethylene glycol monohexyl ether, ethylene glycol Recall 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 glycol monobutyl ether, dipropylene glycol monopropyl Pill 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 ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, and the like. These may be used alone or in combination.
The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, with respect to 100 parts by weight of the pigment in the red coloring composition.

The red coloring composition is composed of one or two or more dyes, if necessary, together with the photopolymerization initiator, in a dye carrier and an organic solvent such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. It can be produced by finely dispersing using a dispersing means. Moreover, the red coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what disperse | distributed each pigment | dye separately in the pigment | dye carrier and the organic solvent separately. When the pigment is dispersed as a pigment in the pigment carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in a dye carrier and an organic solvent using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, 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.

  The pigment derivative is a compound in which a substituent is introduced into an organic dye, and is preferably close to the hue of the pigment to be used. However, if the addition amount is small, those having different hues may be used. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of pigment derivatives include JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5-9469. You can use what is described. In particular, a pigment derivative having a basic group is preferably used because it has a large pigment dispersion effect. These can be used alone or in admixture of two or more.

Specific examples of the basic group possessed by the pigment derivative include substituents represented by the following general formulas (4), (5), (6), and (7). Among these, a pigment derivative having a basic group containing a triazine skeleton represented by the following general formula (7) is preferably used because of a large pigment dispersion effect.

In the general formulas (4) to (7), X represents —SO 2 —, —CO—, —CH 2 NHCOCH 2 —, —CH 2 — or a direct bond. n represents an integer of 1 to 10, preferably an integer of 1 to 3.
R1 and R2 each independently represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Or R1 and R2 combine to form an optionally substituted heterocycle containing additional nitrogen, oxygen or sulfur atoms. R1 and R2 are preferably unsubstituted or substituted alkyl groups having 1 to 5 carbon atoms.
R 3 represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. R3 is preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.
R4, R5, R6 and R7 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms or a substituted group. Represents a good phenyl group. R4, R5, R6 and R7 are preferably unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms.
Y represents -NR8-Z-NR9- or a direct bond.
R8 and R9 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents. R8 and R9 are preferably each a hydrogen atom.
Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted. Z is preferably an unsubstituted or substituted phenylene group.

P represents a substituent represented by the following general formula (8) or a substituent represented by the general formula (9). In the general formulas (8) and (9), R1 to R7 and n are as defined above.
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8) or a substituent represented by the general formula (9). Q is preferably a substituent represented by the general formula (8).

  Examples of the organic dye constituting the pigment derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, and anants. Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complexes Systematic dyes. Moreover, the organic pigment illustrated previously may be sufficient.

A pigment derivative having a basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (10) to (13) into an organic dye, it reacts with the substituent to form a substituent represented by the general formulas (4) to (7). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

When the organic dye is an azo dye, the basic group is introduced by introducing the substituent represented by the general formulas (4) to (7) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by the general formulas (4) to (7) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

Examples of the amine component used for forming the substituents represented by the general formulas (4) to (7) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine. N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, di Butylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N , N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylamino The Pyramine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like. The pigment derivatives can be used alone or in admixture of two or more.
The pigment derivative can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment. If the amount is less than 0.1 parts by weight, the effect of dispersing the pigment cannot be obtained, which is not preferable. If the amount is more than 40 parts by weight, the hue may change, which is not preferable.

The red coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.
Examples of the storage stabilizer include hydroquinone such as hydroquinone, methyl hydroquinone, 2,5 di-tert-butyl hydroquinone, tert-butyl hydroquinone, tert-butyl-β benzoquinone, tert-butyl hydroquinone 2,5 diphenyl-p-benzoquinone. Compounds, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc. Phosphine compounds, trioctyl phosphine oxide, phosphine oxide compounds such as triphenylphosphine oxide, triphenyl phosphite, trisnoni Examples thereof include phosphite compounds such as ruphenyl phosphite and t-butylpyrocatechol. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, 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 pigment in the coloring composition.

The red coloring composition of the present invention can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type color resist. The colored resist is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent.
The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the red coloring composition (100% by weight). More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by a pigment carrier.
The red coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust.

The red color filter of the present invention is formed on the transparent substrate using the above-described colored composition of the present invention by a printing method or a photolithography method.
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. Further, 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 for driving the liquid crystal after the liquid crystal panel is formed.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. 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 each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it apply | coats so that a dry film thickness may be set to 0.2-10 micrometers. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.
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, 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. 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 the UV exposure sensitivity, a film that prevents polymerization inhibition by oxygen by coating and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin after coating and drying the colored composition of the present invention. After forming, UV exposure can also 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. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate. Further, the ink jet method is a method of manufacturing a color filter by forming each color filter segment by an ink jet method using an ink jet ink.

Next, a liquid crystal display device provided with the color filter of the present invention will be described.
FIG. 8 is a schematic cross-sectional view of a liquid crystal display device provided with the color filter of the present invention. A device 10 shown in FIG. 8 is a typical example of a TFT drive type liquid crystal display device for a notebook personal computer, and includes a pair of transparent substrates 11 and 21 which are arranged to be spaced apart from each other, and between them, a liquid crystal (LC) is enclosed. Liquid crystals (LC) are TN (Twisted Nematic) and STN (Super Twiste).
d Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (
Oriented according to the driving mode such as Optically Compensated Birefringence.
A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown). A transparent protective film (not shown) is formed so as to cover the color filter 22 and further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and the alignment layer 24 covers the transparent electrode layer 23. Is provided. A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 including a three-wavelength lamp 31 is provided below the polarizing plate 15.
Further, as the backlight included in the liquid crystal display device including the color filter of the present invention, an LED backlight can be used in addition to the cold cathode fluorescent lamp (CCFL) backlight.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” means “parts by weight”.
[Preparation of pigment]
The dyes and pigments used in Examples and Comparative Examples are those shown in Table 1 and red pigments 2 and 4 and yellow pigments 2 and 4 prepared as follows. Table 2 shows the spectral characteristics of the dyes used in the examples and comparative examples. In addition, Table 3 shows the dispersants used in Examples and Comparative Examples.

[Red Pigment 2 (R-5)]
136 parts of red pigment 1 (R-4) shown in Table 1, 24 parts of Dispersant A-1 shown in Table 3, 1600 parts of sodium chloride, and 190 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) And kneaded at 60 ° C. for 8 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 156 parts of salt milling process pigments (red pigment 2, R-5).

[Red Pigment 4 (R-7)]
160 parts of red pigment 3 (R-6) shown in Table 1, 1600 parts of sodium chloride and 190 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60 ° C. for 12 hours. Kneaded. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 156 parts of salt milling process pigments (red pigment 4, R-7).

[Yellow Pigment 2 (Y-2)]
280 parts of yellow pigment 1 (Y-1) shown in Table 1, 21 parts of dispersant A-2 shown in Table 3, 1400 parts of sodium chloride, and 280 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) And kneaded at 80 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, After drying at 80 ° C. for 24 hours, 298 parts of salt milled pigment (yellow pigment 2, Y-2) was obtained.

[Yellow Pigment 4 (Y-4)]
200 parts of yellow pigment 3 (Y-3) shown in Table 1, 10 parts of Dispersant A-2 shown in Table 3, 1500 parts of sodium chloride, and 200 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) And kneaded at 60 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It was dried at 80 ° C. for 24 hours to obtain 207 parts of a salt milled pigment (yellow pigment 4).

[Preparation of acrylic resin solution]
Next, preparation of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts
Methyl methacrylate 10.0 parts
n-Butyl methacrylate 35.0 parts
2-hydroxyethyl methacrylate 15.0 parts
2,2'-azobisisobutyronitrile 4.0 parts
20.0 parts of paracylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.)
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. 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 cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

[Preparation of pigment dispersion]
A mixture having the composition (weight ratio) shown in Table 4 was uniformly stirred and mixed, then dispersed with an Eiger mill for 2 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 5 μm filter to prepare a pigment dispersion. .

[Preparation of red coloring composition (resist)]
Next, a mixture having a composition (weight ratio) shown in Table 5 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain each resist.

Multifunctional thiol: TPMB
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd. “NK ester ATMPT”)
Photopolymerization initiator: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
Sensitizer: 4,4′-bis (diethylamino) benzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)
Organic solvent: cyclohexanone

[Examples 1-4, Comparative Examples 1-4]
The spectral characteristics of the red dyes (R-1, R-2) used in Examples 1 to 4 and the red dye (R-3) used in Comparative Examples 2 and 4 are as shown in FIG. .

[Production of color filter]
The red coloring composition of the present invention was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form striped filter segments on the substrate. The film thicknesses of the filter segments were all 2.0 μm.
The following evaluation was performed about the red color filter which consists of a red filter segment obtained by the Example and the comparative example.

[Evaluation of spectral characteristics of red color filter]
About the red color filter obtained by the Example and the comparative example, spectroscopic measurement was implemented using Olympus OSP-200. CIE chromaticity, x, y, and Y were obtained by simulation with the chromaticity x and y being constant (ie, the hue being constant) with an F10 light source. The respective calculation results are shown in Table 6. Moreover, the spectral transmittance spectrum at that time is shown in FIG. 2, FIG. 3, FIG. 4, and FIG. Examples 1 and 2 and Comparative Examples 1 and 2 are red color filters having the same hue, and Examples 3 and 4 and Comparative Examples 3 and 4 are red color filters having the same hue.

  As shown in Table 6, in the case of the same hue, the color filter obtained using the red coloring composition of the present invention had a very high brightness as compared with the comparative example.

[Measurement of contrast ratio of color filter]
First, as shown in FIG. 6A, the polarizing plates 13 and 15 are overlapped on both sides of the obtained red color filter 14, and the polarization axes of the polarizing plates 13 and 15 are parallel to each other. Using a color luminance meter BM-5A (manufactured by Topcon Corporation) 12, the luminance LP (luminance of parallel transmitted light) of the light 18 that has passed through the other polarizing plate 13 by applying the backlight 17 from the plate 15 side, Measurement was performed under the condition of 2 ° visual field (CIE1931 color system).
Next, as shown in FIG. 6B, with the polarization axes of the polarizing plates 13 and 15 orthogonal to each other, the backlight 17 was applied from one polarizing plate 15 side and transmitted through the other polarizing plate 13. The luminance LC (luminance of orthogonal transmitted light) of the light 19 was measured with the color luminance meter 12.
Further, the luminance LP of the parallel transmitted light and the luminance LC of the orthogonal transmitted light in the polarizing plate alone (state excluding the color filter) are the same in the state where the red color filter 14 is removed from FIGS. 6 (a) and 6 (b). Measured.

Note that the backlight has an emission spectrum as shown in FIG. 7, luminance = 1937 cd / m 2, and chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram are (0.316, 0.301). The one having the characteristics of color temperature = 6525K and chromaticity deviation duv = −0.0136 was used. The polarizing plate used was NPF-SEG1224DU (manufactured by Nitto Denko Corporation).
The contrast ratio was calculated by LP / LC using the obtained measured value. The results are also shown in Table 6. As shown in Table 6, since the pigment component can be reduced in the red coloring composition of the present invention, a high contrast was obtained.
As described above, the red coloring composition of the present invention has high brightness and high contrast.

Spectral transmittance spectra of dyes used in Examples and Comparative Examples 2 and 4 Spectral transmittance spectrum of red color filter of Example 1 and Comparative Example 1 Spectral transmittance spectrum of red color filter of Example 2 and Comparative Example 2 Spectral transmittance spectrum of red color filter of Example 3 and Comparative Example 3 Spectral transmittance spectrum of red color filter of Example 4 and Comparative Example 4 Explanatory drawing of the contrast ratio measuring method of the present invention Backlight emission spectrum It is a schematic sectional drawing of the liquid crystal display device provided with the color filter of this invention.

DESCRIPTION OF SYMBOLS 10 ... Backlight unit 11 ... Three wavelength lamp 12 ... Color luminance meter 13, 15 ... Polarizing plate 14 ... Color filter 16 ... Backlight 17 ... Backlight unit 18 ... Parallel transmitted light 19 ... Orthogonal transmitted light (leakage light)

Claims (3)

A red coloring composition in which at least a red dye and a pigment are dispersed in a pigment carrier composed of a mixture of a transparent resin and a precursor thereof, and the red dye has a maximum absorption wavelength (λmax) at 560 nm to 565 nm. When the transmittance of the red dye at 550 nm is 1%, the wavelength at which the transmittance is 50% is in the range of 595 nm to 600 nm, and the transmittance of 400 nm to 550 nm is less than 40%, 630 nm to 700 nm. der transmittance 94% or more is, and the pigment is, C. I. Pigment Red 254, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 150, C.I. I. A red color filter formed using a red coloring composition containing at least one of Pigment Yellow 139 . The red color filter according to claim 1 , wherein the red dye has an azo skeleton or is an azo metal complex. The red dye is C.I. I. Solvent Red 124, or C.I. I. The red color filter according to claim 2 , wherein the red color filter is Solvent Red 89.

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