JP2011170011A - Method for manufacturing color filter for liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color composition free from the occurrence of wrinkles even when the composition is cured in a manufacturing process, and to provide a method for manufacturing a color filter with high lightness and high contrast with excellent reliability. <P>SOLUTION: In the method for manufacturing the color filter for a liquid crystal display device, the color filter having color pixels on a transparent substrate and having a transparent conductive film on the color pixels, is characterized in that: the color pixel in at least one color comprises a color composition containing at least one dye and at least one thermosetting compound; the color composition used is characterized by including the thermosetting compound by 5 mass% or more and 50 mass% or less in terms of a solid content in the color composition; the baking temperature T1 in a baking process for forming the color pixel is 150°C or higher and 220°C or lower; and the baking temperature T2 of the transparent conductive film is in the range satisfying (T1-20)≤T2≤(T1+20). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a color filter for a liquid crystal display device using a coloring composition containing a dye.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, and power saving due to their thinness. In particular, the spread to display applications such as television receivers is rapidly advancing, and it is desired to improve display performance such as brightness, contrast, and visibility in all directions, and further increase the brightness of the color filters used therefor. High contrast is desired.

  As a method for producing a color filter, a printing method, an electrodeposition method, a pigment dispersion method, and the like are known. Among these, the pigment dispersion method is based on a colored composition in which pigments are dispersed in various photosensitive compositions, This is a method for producing a color filter by a photolithography method. Since the pigment dispersion method uses a pigment, it is excellent in heat resistance and light resistance, is suitable as a color filter for liquid crystal display devices, and has been widely used.

  However, color filters manufactured using the pigment dispersion method are known to diffuse light in the liquid crystal display device due to the effect of pigment fine particles, leading to a decrease in display contrast. As discussed, as long as pigments are used, this diffusion is not completely eliminated.

  In order to solve this problem, it is conceivable to use a dye that develops color when dissolved in a colored composition. Conventionally, color filters using dyes have been studied and proposed in Japanese Patent Application Laid-Open No. 6-75275 and the like, but coloring compositions containing dyes have new problems. That is, (1) A general dye has low solubility in an organic solvent used in a general color filter coloring composition. (2) Since the dye acts as a so-called “radical eater” that deactivates the generated radical polymerization terminal in radical polymerization generally used in the photolithography method, the exposure sensitivity is lowered and the coating film cannot be cured sufficiently. (3) Dyes are generally inferior in heat resistance and light resistance compared to pigments. (4) Elution occurs when the dye in the coating film is immersed in an organic solvent.

  Among these problems, regarding the heat resistance of (3), it is necessary to consider the temperature of the baking process (the baking process after the exposure and development processes) in the manufacturing process of the color filter by the photolithography method. That is, although it is generally fired at a temperature of about 220 ° C. to 250 ° C., it is necessary to fire at a lower temperature because the dye may be decomposed and oxidized at such a high temperature. However, as shown in (2), in the coloring composition containing a dye, the exposure sensitivity is lowered, so that the coating film is not sufficiently cured. In addition to insufficient curing by exposure, the film is not sufficiently cured when baked at a low baking temperature.

  Insufficient film hardening may cause problems such as poor heat resistance and chemical resistance, but in the manufacturing process of color filters, a transparent conductive film is formed on the color filters. The film of the color filter contracts due to heat applied for firing the transparent conductive film, and stress may be generated between the transparent conductive film and wrinkles may occur.

From the viewpoint of reliability such as heat resistance, a photosensitive composition is disclosed in which the coating film strength after curing is improved by using a blocked isocyanate compound having an isocyanurate ring (for example, Patent Document 1 to Patent Reference 3). In addition to the above, there is a technique that describes a technique for improving heat resistance, chemical resistance, electrical insulation and the like by using a blocked isocyanate compound. However, for the purpose of solder resist, it is composed using epoxy or epoxy acrylate in the composition, so that the blocked isocyanate reacts randomly with OH groups derived from epoxy or epoxy acrylate when the block is removed and is strong However, it does not take into account the improvement of wrinkles. (For example, refer to Patent Documents 4 to 6). There are other technologies that use blocked isocyanates in the color filter coloring composition to reduce the dielectric constant, but they are not intended to improve the appearance and are not devised. Therefore, the effect of suppressing the generation of wrinkles cannot be expected (see Patent Document 7).

JP 2001-305726 A JP 2003-64236 A JP 2009-93164 A JP-A-6-295060 JP-A-8-234432 JP 2003-64236 A JP 2006-119441 A

  The present invention has been made in view of the above circumstances, and provides a colored composition that does not generate wrinkles even when cured and baked in the production process, and a method for producing a highly reliable, high-brightness, high-contrast color filter. The purpose is to provide.

  A first aspect of the present invention for achieving the above object is a method for producing a color filter for a liquid crystal display device having a colored pixel on a transparent substrate and a transparent conductive film on the colored pixel, wherein at least 1 The colored pixel is composed of a coloring composition containing at least one dye and at least one thermosetting compound, and the thermosetting compound is 5% by mass to 50% by mass as a solid content in the coloring composition. And a baking temperature T1 in the baking step when forming the colored pixel is 150 ° C. or higher and 220 ° C. or lower, and the transparent conductive film is fired. It is a method for producing a color filter for a liquid crystal display device, characterized by firing at a temperature T2 in a range of (T1-20) ≦ T2 ≦ (T1 + 20).

As a second aspect of the present invention, the thermosetting compound is a melamine compound, an epoxy monomer, an isocyanate monomer, or a blocked isocyanate monomer in which an isocyanate group of the isocyanate monomer is blocked with a protective group. A third aspect of the present invention is the production of a color filter for a liquid crystal display device according to 1, wherein the thermosetting compound is an epoxy group, an isocyanate group or a block in which the isocyanate group is blocked with a protective group as a functional group It is a binder resin which has an isocyanate group, The manufacturing method of the color filter for liquid crystal display devices of Claim 1 characterized by the above-mentioned.

  When the coloring composition according to the present invention is used, a color filter having high brightness and high contrast without wrinkles can be produced. Therefore, a liquid crystal display device including a high quality color filter can be manufactured.

It is sectional drawing which shows the structure of the color filter which concerns on embodiment of this invention.

In a color filter for a liquid crystal display device having a colored pixel on a transparent substrate and a transparent conductive film on the colored pixel, the present inventors comprise a dye, a binder resin, and a thermosetting compound as coloring materials, It has been found that a wrinkle-free color filter can be obtained by using a coloring composition in which the content of the curable compound is 5% to 50% in the solid content of the coloring composition.
Further, the temperature T1 applied in the baking process in the patterning process of the color filter coloring composition in the color filter manufacturing process is 150 ° C. or higher and 220 ° C. or lower, and the relationship with the temperature T2 applied in the ITO film forming process is (T1 It has been found that a more preferable color filter for a liquid crystal display device can be obtained by manufacturing in a process that satisfies −20) ≦ T2 ≦ (T1 + 20).

Hereinafter, various embodiments of the present invention will be described.
1st embodiment which concerns on this invention is a coloring composition for color filters containing at least 1 sort (s) of dye and at least 1 type of thermosetting compound as a coloring material, This coloring composition of this thermosetting compound Is contained in a solid content of 5% by mass to 50% by mass. In addition, solid content in a coloring composition is a solid component which remains after removing the organic solvent contained in a coloring composition.

The coloring composition contains at least one dye that is soluble in an organic solvent. The dye is not particularly limited, and a dye that is soluble in a known organic solvent can be used.
Examples of the known dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Patent No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828.

  Examples of these dyes include acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, and direct dyes. For example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorans Dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes. Specific examples of color index numbers include the following. C. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190, 191, C.I. I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113, C.I. I. SolventRed 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 23 , 238,239,240,241,242,243,244,245,247,248, C. I. SolventViolet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60, 61, C.I. I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139, 143, C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62, 63, C.I. I. Solvent Black 3, 5, 5: 2, 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49, 50, C.I. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. AcidGreen 25, 27, C.I. I. Acid Blue 22, 25, 40, 78, 92, 113, 129, 167, 230, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. BasicGreen 3, 4, C.I. I. BasicBlue 3, 7, 9, 17, 41, 66, C.I. I. BasicViolet 1, 3, 18, 39, 66, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. DirectRed 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. DirectGreen 26, 28, C.I. I. DirectBlue 71, 78, 98, 106, 108, 192, 201, C.I. I. DirectViolet 51, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Direct Orange 26, 29, 34, 37, 72, C.I. I. SulfurRed 5, 6, 7, C.I. I. SulfurGreen 2, 3, 6, C.I. I. SulfurBlue 2, 3, 7, 9, 13, 15, C.I. I. Sulfur Violet 2, 3, 4, C.I. I. Sulfur Yellow 4, C.I. I. VatRed 13, 21, 23, 28, 29, 48, C.I. I. VatGreen 3, 5, 8, C.I. I. VatBlue 6, 14, 26, 30, C.I. I. VatViolet 1, 3, 9, 13, 15, 16, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Vat Orange 2, 5, 11, 15, 18, 20, C.I. I. Azoic Coupling Component 2, 3, 4, 5, 7, 8, 9, 10, 11, 13, 32, 37, 41, 48, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Reactive Blue 1, 2, 7, 19, C.I. I. Reactive Violet 2, 4, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, C.I. I. DisperseBlue 3, 24, 79, 82, 87, 106, 125, 165, 183, C.I. I. DisperseViolet 1, 6, 12, 26, 27, 28, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64, C.I. I. Disperse Orange 13, 29, 30. These dyes can be used alone or in combination of two or more in order to develop a desired spectral spectrum.

  The mass concentration of the dye in the coloring composition is preferably 0.1% to 20%, more preferably 0.5% to 18%, and still more preferably 0.5% to 15%. If the dye concentration is less than 0.1%, the dye concentration is low, and in order to form a colored pixel having a sufficient color as a color filter, the thickness of the colored pixel must be very large. Since it is difficult to form and productivity is deteriorated, there is a practical difficulty. On the other hand, if the concentration exceeds 20%, the concentration is too high, so that the dye may not be sufficiently dissolved and crystals may be deposited. Further, a colored composition is applied on the substrate to form a colored pixel, and an organic solvent is used. There is also a risk that the dye may be precipitated when drying.

  The coloring composition for a color filter according to the present invention can contain a pigment in addition to the dye. The mass concentration of the pigment in the coloring composition is preferably 0.1% to 50%, more preferably 0.5% to 40%, and still more preferably 0.5% to 30%. If it is less than 0.1%, the pigment concentration is low, and in order to form colored pixels of sufficient color as a color filter, it is difficult to form the pixels because the thickness of the colored pixels must be very large. Yes, there is a practical difficulty because productivity deteriorates, and if it exceeds 50%, the amount of resin for dispersing the pigment decreases, becomes unstable, and causes viscosity increase and contrast decrease due to pigment aggregation. It becomes.

The pigment is not particularly limited, but a known pigment can be used without particular limitation.
For example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123 as a red pigment. 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240 242, 246, 254, 255, 264, 272, 279 and the like. I. Pigment Red 177, 242, and 254 are preferably used.

  Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 1 2, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc., and CI Pigment Yellow 138, 139150 is particularly preferred. Used.

  Examples of the orange pigment include C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73, and C.I. Pigment Orange 36 is preferably used. As the green pigment, green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58 can be used, and C.I. Pigment Green 7, 36, 58 is particularly preferably used.

  Examples of the blue pigment include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, and the like. : 3, CI Pigment Blue 15: 6 can be used. Further, C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like are used as the purple pigment, and C.I. Pigment Violet 23 is particularly preferably used.

  Inorganic pigments include yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders Etc. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

The pigment contained in the coloring composition is preferably subjected to a finer treatment and preferably has a small primary particle diameter in order to achieve high brightness and high contrast of the color filter. The primary particle diameter of the pigment was calculated by taking the pigment with a transmission electron microscope and analyzing the image of the photograph. The primary particle diameter referred to here represents a particle diameter (equivalent circle diameter) corresponding to 50% of the total amount in the cumulative curve of the number particle size distribution. The primary particle diameter of the pigment is preferably 40 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less. Moreover, it is preferable that a primary particle diameter is 5 nm or more.
When the primary particle diameter of the pigment is larger than the upper limit value, the visibility of the liquid crystal display device during black display is poor. Moreover, when smaller than a lower limit, pigment dispersion | distribution becomes difficult, it becomes difficult to maintain stability as a coloring composition and to ensure fluidity | liquidity. As a result, the luminance and color characteristics of the color filter are deteriorated.

  As a means for controlling the primary particle diameter of the pigment, a method of controlling the primary particle diameter 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 the desired primary particle diameter is controlled. There are a method for precipitating a pigment having a particle size (referred to as a precipitation method) and a method for producing a pigment having a desired primary particle size at the time of synthesis (referred to as a synthetic precipitation method). 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 primary particle size of the pigment contained in the colored composition used in the present invention.

In the grinding method, the pigment is mechanically kneaded using a ball mill, sand mill or kneader together with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it. This is a method of obtaining a pigment having a desired primary particle size by washing and removing the inorganic salt and the organic solvent, followed by drying. 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. The water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified. Although depending on the blending ratio of the pigment and the inorganic salt, the water-soluble organic solvent is usually added in an amount of 0.1% by weight with respect to 1 part by weight of the pigment. Used in an amount of 5 to 30 parts by weight. More specifically, with respect to the above grinding method, a small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured 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 primary particle size.

  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 primary particle size. The particle size 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 primary particle size tends to increase.

  The primary particle size 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 the fluidity as a dispersion can be secured. At the time of salt milling or acid pasting, in order to prevent aggregation of the pigment accompanying the control of the primary particle size, the following dispersion aids such as a dye derivative, a resin-type pigment dispersant, and a surfactant can be used in combination. Further, by controlling the primary particle size in the form of coexistence of 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 small primary particle size 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 of synthesizing a pigment and simultaneously depositing a pigment having a desired primary particle size. 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 for controlling the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously 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). It is also possible.

  The binder resin as a pigment carrier contained in the coloring composition for a color filter of the present invention disperses the pigment, 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 binder resin 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 pigment in the coloring composition. When a mixture of a transparent resin and its precursor is used as a pigment carrier, the transparent resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment in the coloring composition. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.
The binder resin is a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that cure upon irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.

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

  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. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, 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. Among these, acrylic resins are preferably used from the viewpoint of transparency.

  Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or 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 in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer can be converted to (meth) acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that produce the binder resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (meth) acrylate, diethylene 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, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) a Relate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Acrylic esters and methacrylic esters such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

Examples of the thermosetting compound according to the present invention include epoxy, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine compound, melamine resin, urea resin, phenol resin, and isocyanate compound. Among them, epoxy compounds, melamine, melamine compounds obtained by condensing melamine, isocyanate compounds, and blocked isocyanate compounds in which isocyanate groups are protected with a blocking agent are suitable. In any case, a polyfunctional compound having two or more heat-reactive functional groups per molecule is preferred, and a tetrafunctional or more functional compound is more preferred.

  The epoxy compound can be used without particular limitation, and can be selected from known ones. The number of epoxy groups is not particularly limited, but those having two or more functional groups are preferred, and more preferably tetrafunctional or more. Examples thereof include Celoxide 2021P, Celoxide 3000, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), AK601, EPPN series (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Melamine can be used without particular limitation, and can be selected from known melamines. For example, melamine compounds are exemplified below.

  In the formula, R1, R2, and R3 are a hydrogen atom, a methylol group, an alkoxymethyl group, an alkoxy n-butyl group, and R4, R5, and R6 are a methylol group, an alkoxymethyl group, and an alkoxy n-butyl group, respectively. To R6 are more preferably an alkoxymethyl group or an alkoxy n-butyl group. A copolymer combining two or more kinds of repeating units may be used. Two or more homopolymers or copolymers may be used in combination. In addition to the above, compounds having a 1,3,5-triazine ring, for example, those described in JP-A No. 2001-166144 can be used.

  Further, a compound represented by the following general formula (2) is also preferably used.

  R7 to R14 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and particularly preferably a hydrogen atom.

  Furthermore, it is a melamine compound obtained by reacting a melamine resin, a compound containing an isocyanate group, and / or an acid anhydride, and the melamine compound has a mass average molecular weight of 2500 or more and a solid content acid value of 60 mgKOH / It is more preferable that it is g or less. When a large amount of conventional melamine resin is blended, there is a problem that the sensitivity of the photosensitive resin composition decreases, the exposure time necessary for sufficient curing becomes long, and the productivity is deteriorated. Furthermore, the alkali developability of the photosensitive resin composition deteriorates, the development speed cannot be adjusted appropriately, the development time becomes longer, and conversely, the development speed is too high and the coating film is easily peeled off from the substrate. As a result, there is a limit to the amount of melamine resin added, making it difficult to exhibit the effect of a sufficient thermosetting resin.

  Isocyanate compounds can be used without particular limitation, and can be selected from known ones. The number of isocyanate groups is not particularly limited, and examples thereof include aliphatic, aromatic or alicyclic mono- or diisocyanate and triisocyanate compounds.

Since isocyanate has high reactivity, in view of pod life, a blocked isocyanate in which an isocyanate group is protected with a blocking agent is suitable. Examples of the blocked isocyanate include compounds in which an isocyanate group is blocked using a blocking agent having a phenol group, an imidazole group, a pyrazole group, an oxime group, a lactam group, an alcohol group, or the like with respect to the isocyanate group. The blocking agent may be any as long as the water-soluble vinyl resin is stable in an aqueous solution and the isocyanate group is unblocked at about 100 ° C. to 200 ° C. Methyl salicylate and imidazole containing a phenol group Examples include imidazole containing a group, 3,5-dimethylpyrazole containing a pyrazole group, methyl ethyl ketone oxime containing an oxime group, ε-caprolactam containing a lactam group, and ethylhexanol containing an alcohol group. is not. Examples include BURNOCK DB-980K (manufactured by DIC Corporation), Duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Corporation), KA-1000 (manufactured by Sanyo Chemical Industries), and the like.

  The above thermosetting compounds may be integrated with the binder resin. For example, an epoxy group or an isocyanate group is incorporated as a unit structure in the binder resin. Although it may be incorporated in any form, an example in which it is incorporated in an acrylic resin will be shown as an example.

  As an example of introducing an epoxy group into an acrylic resin, as an acrylic monomer having an epoxy group, glycidyl acrylate, glycidyl (meth) acrylate, or vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (Celoxide 2000 Z Daicel Chemical) And a method using an industrial company). Examples of introducing isocyanate groups or blocked isocyanate groups include 2-isocyanatoethyl (meth) acrylate (produced by Karenz MOI Showa Denko) and Karenz MOI-EG (produced by Showa Denko) as acrylic monomers having these functional groups. And a method using 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, Showa Denko KK) containing a blocked isocyanate group. These thermosetting compounds and binder resin-integrated compounds can be used in combination with the aforementioned thermosetting compounds.

  The content of these thermosetting compounds is preferably 5% by mass to 50% by mass in the solid content of the colored composition. More preferably, it is 5% to 40%, and further preferably 10% to 40% by mass. If the thermosetting compound is less than 5% by mass, the amount of the thermosetting compound is too small, and the colored pixels are not sufficiently cured in the post-baking process in the color filter manufacturing process. When heating in the process (heating during sputtering or heating for subsequent annealing), the colored pixels shrink due to heat, and stress is generated between the transparent conductive film, causing wrinkles and cracks. Become. On the other hand, when the content of the thermosetting compound exceeds 50% by mass, the thermosetting compound undergoes a thermal reaction due to heating in the film forming step of the transparent conductive film, and the transmittance decreases due to yellowing associated therewith. Furthermore, many thermosetting compounds are not designed with a molecular design that takes into account the developability in the photolithographic process (specifically, they do not have an acidic group for imparting alkali solubility, etc.). When used as a product, the developability is inferior, causing a residue and the like.

  In the coloring composition for a color filter of the present invention, one or two or more kinds of organic solvents can be used for coating so that the dry film thickness is 0.2 to 5 μm. The organic solvent is selected in consideration of viscosity, surface tension, boiling point, solubility parameter, and the like from the viewpoints of applicability, drying property, film thickness uniformity, wettability and the like when applying the colored composition. For example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethyl lactate, methyl lactate, ethylbenzene, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, isoamyl acetate, methanol, ethanol, isopropyl alcohol But, but not limited to, butanol, isobutyl ketone, petroleum solvent and the like. The organic 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 total color materials in the coloring composition.

  The coloring composition for a color filter according to the present invention may be a photosensitive composition. For example, a dye-containing colored photosensitive composition for a color filter using at least one photopolymerization initiator and at least one photopolymerizable compound in addition to the color filter coloring composition described above.

  As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfite Benzophenone compounds such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2 Thioxanthone compounds such as 2,4-diethylthioxanthone, 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 (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bi (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazines such as triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone Quinone compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. These photopolymerization initiators can be used alone or in combination. A photoinitiator can be used in the amount of 5-200 weight part with respect to a total of 100 weight part of the pigment in a coloring composition, Preferably it is 10-150 weight part.

The photopolymerization initiators may be used alone or in combination of two or more, or as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4 ′ Amine compounds such as -bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  Furthermore, a polyfunctional thiol that functions as a chain transfer agent can be contained. 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 tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-to Azine, 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine. These polyfunctional thiols can be used alone or in combination. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the total pigment in the coloring composition.

  The photopolymerizable compound is a compound that can be polymerized by an active radical or an acid generated from a photopolymerization initiator by light irradiation. Examples of the photopolymerizable compound include compounds having a polymerizable carbon-carbon unsaturated bond.

  As the photopolymerizable compound, a known photopolymerizable compound can be used without particular limitation. As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. It is more preferable that it is a (meth) acryl compound. From the viewpoint of sensitivity and high curing, the photopolymerizable compound is more preferably a polyfunctional (meth) acrylic compound.

  Examples of photopolymerizable compounds include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Hexanediol di (meth) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloilo) Shiechiru) isocyanurate, such as those (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylol ethane.

  The color filter coloring composition according to the present embodiment may contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and in order to improve adhesion to the transparent substrate, silane coupling. An adhesion improving agent such as an agent can also be contained. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, 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) methyltri Epoxysilanes such as ethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Methoxysilane, N-phenyl-γ-aminopropyltrieth Examples thereof include aminosilanes such as xysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The color filter according to the present invention includes a red pixel, a green pixel, and a blue pixel as necessary, and further includes other color pixels such as a yellow pixel, a cyan pixel, a magenta pixel, and a transparent pixel as necessary. May be included. Other than the colored pixels according to the present invention, a known coloring composition containing a color pigment, a color dye, or both a color pigment and a color dye may be used.

  In the color filter according to this embodiment, the colored pixels preferably have a thickness of 0.1 μm to 5.0 μm, more preferably 0.5 μm to 4.0 μm, and still more preferably 1.0 μm to 3.5 μm. That is, when the blue pixel according to the present invention is formed by photolithography, it is difficult to form the pixel if the film thickness is less than 0.1 μm, and if the film thickness is more than 5 μm, the composition is applied to the coating film. This is because it becomes difficult to form and apply.

The color filter which concerns on this embodiment comprises the colored pixel which consists of a colored coating film formed using the coloring composition for color filters mentioned above on the transparent substrate.
That is, as shown in FIG. 1, the color filter includes a black matrix 2 that is a light shielding film and a colored pixel 3 on a transparent substrate 1 such as glass. The colored pixel 3 includes a blue pixel 3B, a red pixel 3R, and a green pixel 3G formed using the above-described blue coloring composition.
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, when the color filter according to the present invention is incorporated in a liquid crystal display device, a transparent electrode made of indium oxide, tin oxide, or the like is formed on the surface of a glass plate or a resin plate for driving a liquid crystal after forming the liquid crystal panel. It may be.

  The present invention is a method for producing a color filter, wherein the colored composition is cured on a transparent substrate to form colored pixels.

  The formation of the colored pixels can be performed by, for example, a printing method, an ink jet method, a photolithography method, or the like.

  The formation of each color coloring pixel by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above-mentioned 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.

  As a method for manufacturing a color filter using an inkjet method, a method is proposed in which a black matrix is formed on a glass substrate, and ink is applied to the openings of the black matrix using an inkjet printing apparatus to form a colored portion. . Further, in this method, the material constituting the black matrix is made of a repellent material such as a fluorine compound or a silicon compound so that the ink is accurately filled into the predetermined opening and the mixed color in which the ink is mixed between the adjacent colored portions does not occur. Water material may be included.

  As an apparatus used for inkjet, there are a piezo conversion method and a heat conversion method depending on a difference in an ink discharge method. In addition, the ink particleization frequency in the ink jet apparatus is about 5 to 100 KHz. The nozzle diameter in the ink jet apparatus is desirably about 5 to 80 μm. In addition, the ink jet apparatus may be one in which a plurality of heads are arranged and about 60 to 500 nozzles are incorporated in one head.

  After the colored portion pattern is formed by the ink jet method, a colored layer pattern is formed by heat treatment using a convection oven, an IR oven, a hot plate, or the like. According to the ink jet method, since a plurality of colors of ink can be applied simultaneously, it is possible to manufacture a color filter at a low cost by a simple process.

  When each color pixel 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 by spray coating, spin coating, slit coating, roll coating or the like. 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 pattern exposure photomask 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. In developing the colored composition, 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 sensitivity of the film during UV exposure, the colored resist is applied and dried, and then water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After the film to be formed is formed, ultraviolet exposure can be performed.

  The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and electrodepositing colored pixels on the transparent conductive film by electrophoresis of colloidal particles.

  The transfer method is a method in which colored pixels are formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and the colored pixels are transferred to a desired transparent substrate.

If a black matrix is formed in advance before forming each color-colored pixel on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light shielding agent is dispersed may be used.

  Regardless of which method is used, it is necessary to perform a baking process after the formation of the colored pixels in order to promote the curing of the colored pixels (after the developing process in the photolithography method). The baking temperature T1 in the baking process is preferably 150 ° C. or higher and 220 ° C. or lower, more preferably 180 ° C. or higher and 210 ° C. or lower, and still more preferably 180 ° C. or higher and 200 ° C. or lower. When the firing temperature is less than 150 ° C., the firing of the colored pixels does not proceed sufficiently, and wrinkles are induced by the film stress generated between the colored pixels and the transparent conductive film in the firing process of the transparent conductive film described later. To do. On the other hand, when the baking process is performed at a temperature exceeding 220 ° C., many dyes are discolored or faded due to thermal decomposition or oxidation reaction. Furthermore, since the thermosetting compound turns yellow when baked at a temperature exceeding 220 ° C., the transmittance is reduced. The firing time is preferably from 5 minutes to 60 minutes, more preferably from 10 minutes to 40 minutes, and even more preferably from 15 minutes to 30 minutes. In the case of the photolithography method, this baking time is the baking time in the baking process for each color. For example, in the case of a three-color filter, the first colored pixel is subjected to baking in the baking step of the subsequent colored pixels, so that three firings are performed, and the second color is subjected to two firings. . In this case, it is not always necessary that the baking process conditions for each color are the same, and the temperature and time are not necessarily in the above-described range. For example, when the first color and the second color use a pigment-dispersed colored composition (resist not related to the present invention) and the third color uses the colored composition according to the present invention, the first color and the second color are within the above-mentioned range. It may be fired at other temperatures and times, and when the colored composition according to the present invention for the third color is used, it may be fired at a temperature and time in the above-mentioned range.

  A known material can be used for the transparent conductive film without any particular limitation. Of these, ITO is particularly preferably used. Most of the transparent conductive films are formed on the color filter by sputtering or the like, but many of them are formed while being heated, or an annealing process is required after the film formation. The heating temperature T2 in the present invention is preferably (T2-20) ≦ T1 ≦ (T2 + 20), more preferably (T2-20), where T1 is the firing temperature of the colored composition according to the present invention. ) ≦ T1 ≦ (T2 + 10), and more preferably (T2-10) ≦ T1 ≦ (T2 + 10). When T2 is a temperature lower than this range, the transparent conductive film is not sufficiently baked, the transmittance is low, and the resistance value is increased, so that sufficient performance as a transparent conductive film cannot be obtained. On the other hand, if the baking is performed at a temperature exceeding this range, the thermal contraction of the colored pixel due to heat is large, the difference in the contraction amount between the transparent conductive film and the colored pixel is large, and stress is generated to cause wrinkles of the colored pixel and the transparent conductive film. Cracks occur. As described above, the heating when forming the transparent conductive film includes the method of simultaneously heating during sputtering (heating sputtering) and the method of post-heating after sputtering (annealing), but there is also a method using both of them. That is, it is a method in which a transparent conductive film is formed by heat sputtering and then annealing is further performed. In this case, the firing temperature T2 is a higher temperature.

When the color filter according to the present invention is incorporated in a liquid crystal display device, a thin film transistor (TFT) is formed in advance on the transparent substrate or the reflective substrate, and then a colored pixel can be formed. By forming colored pixels on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
On the color filter according to the present embodiment, an overcoat film, a columnar spacer, a liquid crystal alignment film, or the like may be formed as necessary.

EXAMPLES Examples and comparative examples of the present invention will be shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. The pigment symbol indicates the color index number. For example, “PR254” is “CI Pigment Red 2”.
54 ”and“ PB15: 6 ”represent“ CI Pigment Blue 15: 6 ”.

  Production examples of dyes and pigments are shown below.

a) Coloring composition The following were used as the coloring agents for coloring the coloring composition used for producing the color filter.

Red pigment: C.I. I. Pigment Red 254 (“Ilgar Forred B-CF” manufactured by Ciba Specialty Chemicals), and C.I. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
Blue pigment: C.I. I. Pigment Blue 15: 6 (Toyo Ink Manufacturing Co., Ltd. “Lionol Blue ES”)

[Production Example 1]
100 parts of diketopyrrolopyrrole red pigment PR254 ("Irgafoa Red B-CF" manufactured by Ciba Specialty Chemicals), 10 parts of pigment derivative (D-1), 1000 parts of crushed salt, and 120 parts of diethylene glycol 1 made of stainless steel It was charged in a gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained the refined pigment (R-1). The average particle diameter of the obtained pigment was 25 nm.

[Production Example 2]
Stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) 100 parts of anthraquinone red pigment PR177 (“chromophthaled red A2B” manufactured by Ciba Specialty Chemicals Co., Ltd.), 8 parts of pigment derivative (D-2), 700 parts of ground salt and 180 parts of diethylene glycol And kneaded at 70 ° C. for 4 hours. The mixture was put into 4000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and the refined pigment (R-2) was obtained. The average particle diameter of the obtained pigment was 30 nm.

[Production Example 3]
200 parts of blue pigment (CIPigment Blue 15: 6, “LIONOLBLUEES” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of sodium chloride, and 100 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. Next, this mixture is poured into about 5 liters of warm water, stirred in a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol. And dried at 80 ° C. for 24 hours to obtain 198 parts of a salt milled pigment (blue pigment B-1).

[Production Example 4]
C. Tokyo Chemical Industry Co., Ltd. I. 5.14 parts by weight of Basic Blue 7 (CI-42595) was dissolved in 500 parts by weight of water, and 4.60 parts by weight of sodium 1-naphthalenesulfonate was added with stirring, followed by stirring at room temperature for 1 hour. The mixture was cooled on ice, and the precipitate was collected by filtration and washed with water. The cake was air-dried and then dried under reduced pressure to obtain 1.11 parts by weight of a dye DB represented by the following structural formula.

[Manufacture of acrylic resin solution]
[Production Example 5]
Below, preparation of the acrylic resin solution used by the Example and the comparative example is demonstrated. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
Put 370 parts of cyclohexanone in a reaction vessel and heat to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 20.0 parts of methacrylic acid (MAA), 10.0 parts of methyl methacrylate (MMA), benzyl methacrylate ( (BzMA) 55.0 parts, 2-hydroxyethyl methacrylate (HEMA) 15.0 parts, and 2,2′-azobisisobutyronitrile 4.0 parts were added dropwise over 1 hour to conduct a polymerization reaction. It was.

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. 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. Then, an acrylic resin solution (P-1) was prepared.
Acrylic resin solutions P-2 to P-4 were obtained in the same manner as in Production Example 5 except that the acrylic monomers listed in Table 4 were used.

GMA (Glycidyl methacrylate, Blemmer GH-LC NOF Corporation)
MOI-BP (manufactured by Showa Denko methacrylic acid 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl.

[Preparation of pigment dispersion]
[Production Example 6]
The mixture having the composition shown in Table 2 was uniformly stirred and mixed, and then dispersed with an Eiger mill for 2 hours using zirconia beads having a diameter of 0.1 mm, and then filtered with a 5 μm filter to prepare a pigment dispersion. The structures of pigment derivatives D-1 to D-3 are shown in Table 3.

Dispersant: Acrylic dispersant (BYK-2001 manufactured by Big Chemie)
Organic solvent: cyclohexanone

[Preparation of thermosetting compound solution]
[Production Example 7]
As a thermosetting compound, 20 masses of melamine compounds (Mw30: manufactured by Sanwa Chemical Co., Ltd.), epoxy monomers (EHPE-3150: manufactured by Daicel Chemical Industries, Ltd.), and blocked isocyanate monomers (KA-1000: manufactured by Sanyo Chemical Co., Ltd.), respectively. Diluted with cyclohexanone to give a% solution. Respective solutions are designated as ME-1, EP-1, and BI-1.

[Preparation of coloring composition]
[Production Example 8]
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a colored composition B-1.
Dye DB-1: 0.9 parts acrylic resin solution (P-1): 20.0 parts epoxy monomer solution (EP-1) 20.0 parts by mass trimethylolpropane triacrylate 8.0 parts by mass (Osaka Organic Chemical Industry) (Biscoat PET-S)
Photopolymerization initiator (Int-1) 3.6 parts by mass (“Irgacure-907” manufactured by Ciba Geigy)
Photosensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts by mass Organic solvent (cyclohexanone) 47.1 parts by mass

[Examples and comparative examples]
A colored composition was obtained in the same manner as in Example 1 except that the dyes, pigment dispersions, resins, thermosetting compound solutions, and photopolymerization initiators described in Table 4 below were used. In Table 4, the coloring composition according to Example 1 is also shown.

DY-1: C.I. I. Basic Yellow 87
Photopolymerization initiator (Int-2): “Irg. OXE02” manufactured by Ciba Geigy.

  B-1 and B-2 are examples in which blue dye DB-1 is contained as a dye, B-1 is an epoxy monomer, and B-2 is a blocked isocyanate monomer as a thermosetting compound. B-3 and B-4 are examples including DB-1 as a coloring material and a blue pigment as coloring materials, B-3 is an epoxy monomer, and B-4 is a blocked isocyanate monomer as a thermosetting compound. B-5 and B-6 contain DB-1 as a coloring material and a blue pigment as coloring materials, B-5 contains a binder resin containing an epoxy group in a cryl resin as a thermosetting compound, and B-6 is a block It is an example containing binder resin containing an isocyanate group. B-7 is an example which contains a blue dye and a blue pigment as coloring materials but does not contain a thermosetting compound. Although B-8 contains a blue dye and a thermosetting compound, the content of the thermosetting compound is more than the scope of the present invention, and B-9 contains a blue dye and a thermosetting compound. This is an example in which the content of the thermosetting compound is less than the range of the present invention.

  R-1 to R-3 include a red pigment and a yellow dye DY-1 as coloring materials, R-1 is a melamine compound as a thermosetting resin, R-2 is a blocked isocyanate compound, and R-3 is a block. This is an example including an isocyanate compound and a binder resin having a blocked isocyanate group, and R-4 includes a red pigment and a yellow dye DY-1 as coloring materials, but does not include a thermosetting compound.

b) [various evaluation methods]
[Method for creating evaluation board]
The coloring compositions B-1 to B-7 and R-1 to R-4 were applied to a glass substrate by spin coating so that the film thickness after curing was 2 μm, dried, and then a 130 μm stripe pattern was formed. It exposed with the ultraviolet-ray using the ultrahigh pressure mercury lamp through the photomask which has a negative image. Thereafter, spray development was performed using a sodium carbonate aqueous solution at 23 ° C., followed by washing with ion-exchanged water and air drying. Then, post-baking was performed for 30 minutes at a temperature T1 shown in Table 5 in a clean oven to obtain a glass substrate having a colored film pattern of each color.
Thereafter, ITO (indium-tin oxide) was deposited by sputtering as a transparent conductive film. The ITO film thickness was 1400 mm. Thereafter, the ITO film was annealed at a temperature T2 shown in Table 5 for 1 hour to obtain an ITO-attached color film pattern substrate.

  In Table 5, as the temperature condition 1, the case where the post-baking temperature T1 is 150 ° C. or higher and 220 ° C. or lower is indicated as ◯, and the case where it is out of the range is indicated as ×. Further, as the temperature condition 2, the case where the annealing temperature T2 satisfies (T1-20) ≦ T2 ≦ (T1 + 20) is indicated as “◯”, and the case outside the range is indicated as “X”.

[Chromaticity and transmittance]
Before and after annealing the above-mentioned ITO adhesion color film pattern substrate, the spectral transmittance was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.), and the chromaticity ( Y, x, y) were calculated. In addition, by measuring the reference at the portion of the glass-ITO film between the colored film patterns at the time of measurement, the chromaticity of the colored film pattern can be measured so that the spectral transmittance of ITO of the above chromaticity is not reflected. It was done like that.

[Heat resistance evaluation]
The color difference ΔEab (C) was calculated using the chromaticity (Y, x, y) before and after the annealing. If the color difference was less than 5.0, it was evaluated as ◯, if it was 5.0 or more and less than 8.0, Δ, and if it was 8.0 or more, ×.
The results are shown in Table 5 below.

[Appearance evaluation]
The annealed ITO adhered color film pattern substrate was observed with an optical microscope at a magnification of 200 times that of an eyepiece 10 times and an objective lens 20 times. The case where wrinkles or cracks occurred in the colored film pattern was evaluated as x, and the case where there was no abnormality was evaluated as ◯. The results are shown in Table 5.

  Examples 1 and 2 are examples in which a coloring composition containing only the blue dye DB-1 as a coloring material and containing a thermosetting compound is used, and both the temperature condition 1 and the temperature condition 2 are satisfied. In any case, the appearance is good with no change, and the color difference is an allowable range of less than 8. It is thought that the color difference exceeded 5 because the coloring material was only a dye. Examples 3 to 6 are examples in which a coloring composition containing a blue dye and a blue pigment as a coloring material and containing a thermosetting compound is used, and both the temperature condition 1 and the temperature condition 2 are satisfied. . In all examples, the color difference and the appearance evaluation were both good and good results. Examples 7 to 10 are examples in which a red pigment and a yellow dye are included as coloring materials and a thermosetting compound is included, and both the temperature condition 1 and the temperature condition 2 are satisfied. In any case, the appearance evaluation is good. The color difference was Δ only in Example 8. Although the annealing temperature is as high as 220 ° C., it is in a range where there is no practical problem.

  Comparative Examples 1 to 3 use a blue colored composition containing a thermosetting compound, but Comparative Examples 1 to 2 do not satisfy the temperature condition 2. As a result, wrinkles were generated due to the stress caused by thermal shrinkage before and after annealing. In Comparative Example 4, the temperature condition 2 is satisfied, but the temperature condition 1 is not satisfied. As a result, since the post-baking temperature was too high, the color difference became x due to the fading of the dye by heat. In Comparative Example 7, since the content of the thermosetting resin was larger than the range of the present invention, the color difference was increased due to the yellowing of the thermosetting compound. On the other hand, Comparative Example 8 with less thermosetting resin had no effect and wrinkles were observed in appearance evaluation. Although the comparative example 9 uses the red coloring composition containing a thermosetting compound, since the temperature condition 2 was not satisfy | filled, generation | occurrence | production of wrinkles occurred. In Comparative Example 10, since the temperature condition 1 was not satisfied, the color difference was x. Comparative Example 11 and Comparative Example 12 are examples in which both the temperature condition 1 and the temperature condition 2 are satisfied but do not contain a thermosetting compound, and wrinkles were generated.

1, 5, 6, 21 ... transparent substrate,
2 ... Black matrix,
3 ... Colored pixels, 3B ... Blue pixels, 3R ... Red pixels, 3G ... Green pixels

Claims (3)

A method for producing a color filter for a liquid crystal display device having a colored pixel on a transparent substrate and a transparent conductive film on the colored pixel,
At least one colored pixel is composed of a colored composition comprising at least one dye and at least one thermosetting compound;
Using the coloring composition characterized in that the thermosetting compound is contained in the range of 5% by mass to 50% by mass as a solid content in the coloring composition,
The baking temperature T1 in the baking step when forming the colored pixels is 150 ° C. or higher and 220 ° C. or lower, and the baking temperature T2 of the transparent conductive film is baking in the range of (T1-20) ≦ T2 ≦ (T1 + 20). A method for producing a color filter for a liquid crystal display device.   The color for a liquid crystal display device according to claim 1, wherein the thermosetting compound is a melamine compound, an epoxy monomer, an isocyanate monomer, or a blocked isocyanate monomer in which an isocyanate group of the isocyanate monomer is blocked with a protective group. A method for manufacturing a filter.   2. The liquid crystal display device according to claim 1, wherein the thermosetting compound is a binder resin having an epoxy group, an isocyanate group or a blocked isocyanate group in which the isocyanate group is blocked with a protective group as a functional group. A method for producing a color filter.

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