JP2014085585A - Color filter for liquid crystal display device and liquid crystal display device - Google Patents

Abstract

A color filter having an overcoat layer, which has excellent adhesion to glass as a substrate and does not cause peeling or cracking of a transparent electrode.
A color filter for a liquid crystal display device in which a colored pixel, an overcoat layer, and a transparent electrode are laminated on a transparent substrate,
Apply a photosensitive resin composition for forming an overcoat layer of the color filter,
Furthermore, the stress value of the coating film obtained by drying and firing is measured at least 3 points between 40 ° C. and 200 ° C.,
A photosensitive resin composition having physical properties such that the absolute value of the slope when the measured stress is plotted on the vertical axis and the temperature is plotted on the horizontal axis is 0.15 Mpa / ° C. or less is used.
[Selection] Figure 3

Description

  The present invention relates to a color filter for a liquid crystal display device that has excellent adhesion and does not cause peeling or cracking of a transparent electrode, and a liquid crystal display device using the same.

  In recent years, liquid crystal display devices using TFTs (thin film transistors) have become the mainstream as display devices. Since the liquid crystal display device is thin and light, it is widely used from a large size like a television receiver to a small size like a mobile phone display. Liquid crystal display devices used for mobile phones have been required to have higher resolutions as mobile phones become more sophisticated. The color filter is also required to have high resolution in accordance with the demand.

  Generally, for colorization of a liquid crystal display device, a black matrix (BM) is provided on the glass substrate facing the glass substrate on which the TFT is formed or on the TFT, and red, blue, Colored pixels of the three primary colors of green are formed. A transparent resin layer may be provided on the formed colored pixel as a planarizing layer (overcoat, hereinafter referred to as overcoat). Further, a transparent electrode is laminated as a liquid crystal driving electrode. ITO (tin-doped indium oxide) is generally used for the transparent electrode from the viewpoints of transparency, low resistivity, and the like.

  The overcoat often causes problems such as peeling of the transparent electrode and generation of cracks, adhesion to the colored layer, and adhesion to glass. It is pointed out that the cause is the adhesiveness of the overcoat and the residual stress of the transparent electrode.

  For example, in Patent Document 1, attention is paid to the residual stress of the transparent electrode at room temperature, and sputtering is performed so that the compressive stress of the transparent electrode is 30 to 300 MPa, so that cracks do not occur due to heat in the subsequent process. It is an attempt.

  In Patent Document 2, the range of the product of the tensile stress and the thickness of the transparent electrode layer is set to 35 to 60 N / m so that the force acting in the surface direction of the overcoat layer, that is, the product of the tensile stress and the thickness of the overcoat layer is increased. This is an attempt to suppress the occurrence of unevenness and cracks in the transparent electrode layer.

  Patent Document 3 is an example of trying to improve the thermal shock resistance by paying attention to the thermal expansion coefficients of the overcoat layer and the transparent electrode.

  Both are inventions that focus on the residual stress of the transparent electrode at room temperature, but the cracks and wrinkles of the transparent electrode on the overcoat are an annealing process after forming the transparent electrode and a process for producing a photospacer formed on the transparent electrode. It is generated by the thermal process in That is, it is insufficient to focus only on the residual stress at room temperature as in these inventions.

  In Patent Document 4, the ratio of the binder polymer and the photopolymerizable compound of the transparent resin material is 0.6 to 1.0, and the Vickers hardness of the film is 50 to 65, thereby suppressing wrinkles in the transparent electrode layer and the colored layer. Attempting to achieve both cohesion. However, attention is paid only to the adhesion with the colored layer, and attention is not paid to the adhesion with the glass outside the frame of the black matrix.

Japanese Patent No. 3965716 JP 2009-192575 A Japanese Patent Application Laid-Open No. 6-067015 JP 2010-11748 A

  The present invention has been made in view of the above circumstances, and provides a color filter having an overcoat layer, which has excellent adhesion to glass as a substrate and does not cause peeling or cracking of a transparent electrode.

  As a result of intensive studies to solve the above problems, the present inventors measured at least three stress values of the transparent resin material used for the overcoat layer between 40 ° C. and 200 ° C., and the temperature is plotted on the horizontal axis. The absolute value of the slope value when the stress value is plotted on the vertical axis is 0.15 or less, and the ratio of the binder polymer to the photopolymerizable compound used in the overcoat layer (photopolymerizable compound / binder polymer) is We found that it can be solved by setting it to 0.6-0.9.

As a means for solving the above problems, the invention according to claim 1 is a color filter for a liquid crystal display device in which a colored pixel, an overcoat layer, and a transparent electrode are laminated on a transparent substrate,
A photosensitive resin composition for forming an overcoat layer of the color filter is applied onto a silicon wafer,
Measure the stress of the coating film of the photosensitive resin composition obtained by drying and baking at least 3 points between 40 ° C. and 200 ° C.,
A photosensitive resin composition having physical properties in which the stress value obtained by the measurement is plotted on the vertical axis and the temperature at that time is plotted on the horizontal axis, and the absolute value of the slope of the straight line is 0.15 Mpa / ° C. or less. A color filter for a liquid crystal display device characterized by being used.

In the invention according to claim 2, the photosensitive resin composition contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a surfactant, and a solvent.
2. The color filter for a liquid crystal display device according to claim 1, wherein the ratio of the binder polymer to the photopolymerizable compound (photopolymerizable compound / binder polymer) is in the range of 0.6 to 0.9. is there.

  The invention according to claim 3 is the color filter for a liquid crystal display device according to claim 1 or 2, wherein the transparent electrode is ITO (tin-doped indium oxide).

  According to a fourth aspect of the present invention, there is provided a liquid crystal display device comprising the color filter for a liquid crystal display device according to any one of the first to third aspects.

  According to the present invention, in the liquid crystal display device, it is possible to obtain a strong liquid crystal display device having good adhesion between the overcoat layer of the frame portion and the glass and free from peeling or cracking of the transparent electrode.

It is the conceptual diagram which showed the stress measuring apparatus by the optical lever method. It is a conceptual sectional view showing an example of the structure of a color filter. It is a temperature-stress relationship figure of the coating film obtained by apply | coating, drying, and baking the photosensitive resin composition described in the Example and the comparative example.

  Hereinafter, modes for carrying out the present invention will be described. The first embodiment according to the present invention is a color filter for a liquid crystal display device having colored pixels, and has at least red, green, and blue colored pixels. If necessary, it has pixels of other colors (for example, cyan, magenta, and yellow which are complementary colors).

  The coloring material used for these pixels is not particularly limited, and known pigments or dyes can be used. The coloring material in the color filter has a pigment or dye mass concentration of preferably 0.1% to 50%, more preferably 1% to 45%, and still more preferably 10% to 40%.

  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. There is a practical difficulty because productivity deteriorates, and if it exceeds 50%, the amount of resin for dispersing pigments and dyes becomes less and becomes unstable, and viscosity increases due to aggregation of pigments and dyes. It causes a decrease in contrast (light scattering by coarse particles).

  Known pigments include, for example, red pigments, C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 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 orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like. I. Pigment Orange 36 is preferably used.

  Examples of yellow pigments include C.I. I. 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, 172, 1 3,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 and the like, but, in particular C. I. Pigment Yellow 138, 139, 150 is preferably used.

  Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like can be used. I. Pigment Green 7, 36, and 58 are preferably used.

Examples of blue pigments include C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, and the like. I. Pigment Blue 1, 15: 4, 15: 6 can be used.

  Further, as a purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. are used. I. Pigment Violet 23 is preferably used.

  Inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, etc., metal oxide powder, metal sulfide powder, metal powder, etc. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness.

  The pigments described so far are preferably finely processed in order to realize high transmittance of the color filter, and preferably have a small primary particle diameter. 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 150 nm or less, more preferably 100 nm or less, and still more preferably 40 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 transmittance decreases due to light scattering by the pigment. 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 primary method depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. 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 dye is not particularly limited, and a dye soluble in a known organic solvent can be used.
Examples of the known dyes include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 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. Specifically, in addition to the dyes exemplified so far, the following are listed as color index numbers.

  C. 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. 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 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. 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. 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. 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 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. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, 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. 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 colored composition used for forming the colored pixel of the color filter of the present invention contains a binder polymer and a resin precursor (hereinafter, monomer) as a pigment carrier.

  The binder polymer 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 polymer 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. Moreover, when using the mixture of transparent resin and its precursor as a binder polymer, transparent resin is 20-400 weight part with respect to 100 weight part of pigments in a coloring composition, Preferably it is 50-250 weight part. 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.

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 transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyl 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) acrylate , 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.

  As the photopolymerizable compound, known ones and commercially available ones can be used without particular limitation. In particular, tri- or higher functional acrylic or methacrylic monomers are preferably used. For example, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and urethane acrylate obtained by polyfunctionalization using trimethylolpropane triacrylate are preferably used.

  A thermosetting compound can also be used for the colored composition for forming the colored pixel according to the present invention. By using a thermosetting compound, chemical resistance and environmental resistance can be imparted. Examples of the thermosetting compound include epoxy, rosin-modified maleic 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.

［式中、Ｒ₁、Ｒ_２、Ｒ_３はそれぞれ水素原子、メチロール基、アルコキシメチル基、アルコキシｎ−ブチル基、Ｒ_４、Ｒ_５、Ｒ_６はそれぞれメチロール基、アルコキシメチル基、アルコキシｎ−ブチル基であるが、Ｒ_１からＲ_６はアルコキシメチル基、アルコキシｎ−ブチル基であることがより好ましい。］
二種類以上の繰り返し単位を組み合わせたコポリマーを用いてもよい。二種類以上のホモポリマーまたはコポリマーを併用してもよい。また、上記以外に１，３，５‐トリアジン環を有する化合物で例えば特開２００１‐１６６１４４公報に記載のものを使用することができる。また以下示す化合物も好んで用いられる。

[Wherein, R ₁ , R ₂ and R ₃ are a hydrogen atom, a methylol group, an alkoxymethyl group, an alkoxy n-butyl group, R ₄ , R ₅ and R ₆ are a methylol group, an alkoxymethyl group and an alkoxy n- Although it is a butyl group, R ₁ to R ₆ 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-2001-166144 can be used. The following compounds are also preferably used.

［Ｒ_７からＲ_１４はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基または複素環基であり、水素原子であることが特に好ましい。］
さらには、メラミン樹脂とイソシアネート基を含有する化合物、または酸無水物とを反応させてなるメラミン化合物であり、該メラミン化合物の質量平均分子量が２５００以上かつ固形分酸価が６０ｍｇＫＯＨ／ｇ以下であるとより好適である。

[R ₇ to R ₁₄ each independently represents 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 with an isocyanate group-containing compound 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 / g or less. And more preferred.

  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, ethylhexanol containing an alcohol group, etc. is not. Examples thereof include BURNOCK DB-980K (manufactured by DIC Corporation), Duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Corporation), and KA-1000 (manufactured by Sanyo Chemical Industries).

The above thermosetting compounds may be integrated with the binder polymer. For example, an epoxy group or an isocyanate group is incorporated as a unit structure in the binder polymer. 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) containing a blocked isocyanate group. These thermosetting compounds and pigment-dispersed resin integrated compounds can also 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 still more preferably 10% to 40% by weight. 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 molecularly designed in consideration of developability in the photolithographic process (specifically, they do not have an acidic group for imparting alkali solubility, etc.), as a photosensitive coloring composition When used, the developability is inferior, causing a residue and the like.

  In order to apply the colored composition used for forming the colored pixels of the color filter according to the present invention so that the dry film thickness is 0.2 to 5 μm, one or more organic solvents are used. Can do. 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 used for forming the colored pixel of the color filter according to the present invention may be a photosensitive composition. For example, a colored photosensitive composition for a color filter using at least one photopolymerization initiator and at least one photopolymerizable compound in addition to the above-described colored composition for a color filter.

  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- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone and 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 (trichloro) (Romethyl) -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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ Oxime ester compounds such as -methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4, -Phosphine compounds such as trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, etc. It is done.

  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 above photopolymerization initiators may be used alone or in combination of two or more. 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-trimerca DOO -s- triazine, 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 colored composition used for forming the colored pixel of the color filter according to the present invention may contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and also adheres to the transparent substrate. In order to improve the property, an adhesion improving agent such as a silane coupling agent may 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 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- Epoxy cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and other epoxy silanes, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Examples thereof include aminosilanes such as silane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The color filter according to the present invention has a transparent overcoat layer 24 on the colored pixels 23. The resin composition used for the overcoat layer 24 is the same as a binder polymer and a precursor of a resin (hereinafter referred to as a monomer) as a pigment carrier of the colored composition used to form the colored pixel 23 described above.

  The binder polymer 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 the precursor thereof includes a monomer or an oligomer as a photopolymerizable compound that is cured by radiation irradiation to form a transparent resin. These can be used alone or in admixture of two or more.

  For the resin composition used for the overcoat layer 24, the stress value is measured at least 3 points between 40 ° C. and 200 ° C., and the absolute value of the slope value when the temperature is plotted on the horizontal axis and the stress is plotted on the vertical axis is 0.15 or less. However, the unit of temperature is Celsius, and the unit of stress is MPa.

  The absolute value of this slope is proportional to the thermal expansion coefficient of the coating film obtained from the resin composition. The smaller the thermal expansion coefficient, the smaller the expansion due to the thermal process when manufacturing color filters and liquid crystal display devices. The stress applied to the transparent electrode formed on the overcoat layer is small.

  When the temperature is plotted on the horizontal axis and the stress is plotted on the vertical axis, the absolute value of the slope value, that is, the thermal expansion coefficient, can be reduced by increasing the crosslinking density of the coating film. In order to obtain such a coating film, it is desirable to include a thermosetting compound in the resin composition. The content is preferably 10% or more, more preferably 20% or more by weight ratio in the solid content.

  As a thermosetting compound, it is the same as that which can be used for the above-mentioned coloring pixel. Particularly preferred are melamine compounds and epoxy compounds.

  The resin composition forming the overcoat layer may have photocurability by containing the above-described active energy ray-curable resin. The organic solvent for imparting coating properties is the same as that of the colored composition.

  The measurement of the temperature-stress relationship of the resin composition is as follows. Brenner and S.M. Senderoff: J.M. Res. Natl. Bur. Stand. 42, 105 (1949) and Japanese Patent Laid-Open No. 10-253821 and Japanese Patent Laid-Open No. 2000-329921, the stress is obtained with reference to the method of measuring the change in the radius of curvature of the silicon substrate.

The method of measuring the radius of curvature includes a method using a stylus type measuring instrument and an optical lever method using a laser light source 14, but any method may be used. In the present invention, since it is necessary to measure the temperature dependence of stress, the silicon wafer 12 is placed on the heating stage 11 and measured. FIG. 1 shows a conceptual diagram of an apparatus when the optical lever method is used.

  The stress of the resin composition is calculated by forming the coating film 13 of the resin composition on the silicon wafer 12 and using the following formula from the radius of curvature before and after the coating film formation.

^{σ = Eh 2/6 (1} -ν) rt Formula 1
σ: Stress E: Young's modulus of silicon substrate h: Thickness of silicon substrate ν: Poisson's ratio of silicon substrate r: Effective radius of curvature of silicon substrate (calculated by the following equation 2)
t: film thickness of the coating film of the resin composition r = r ₁ r ₂ / (r ₁ -r ₂ ) Formula 2
r ₁ : radius of curvature of silicon wafer before film formation using resin composition r ₂ : radius of curvature of silicon wafer after film formation using resin composition Size and thickness of silicon wafer 12 used for measurement The crystal form is not particularly limited. After measuring the radius of curvature of the silicon wafer 12, a coating film 13 of a colored composition is formed on the silicon wafer. The film thickness of the coating film is desirably matched to the film thickness when a color filter is prepared using the resin composition. After the resin composition is applied on the silicon wafer 12, pre-baking, exposure, and post-baking are performed under the conditions assuming that the resin composition is used in a production line. The curvature radius of the substrate that has been subjected to this post-baking is measured. Further, the radius of curvature of the silicon wafer 12 is measured while being heated by the heating stage 11. The stress value is calculated from the measured curvature radius using the above formula.

The slope of the temperature-stress plot calculated by the above method corresponds to the value of thermal stress as shown in Equation 3, and is proportional to the thermal expansion coefficient. (Reference: Hideya Yamadera, Toyota Central R & D Review Vol. 34, No. 1, P19-24 (1999)
σ = σ ₀ + σ _T T Equation 3
σ ₀ : Internal stress at 0 ° C. σ _T : Thermal stress T: Measurement temperature σ _T = (E _f / 1−ν _f ) (α _f −α _s ) Equation 4
E _f : Young's modulus of coating film ν _f : Poisson's ratio of coating film α _f : Thermal expansion coefficient of coating film α _s : Thermal expansion coefficient of silicon wafer The Young's modulus and Poisson's ratio of the resin composition depend on the composition of the resin composition. It can be said that the thermal expansion coefficient of the silicon wafer can be considered as a constant, and it can be considered that the thermal stress is proportional to the thermal expansion coefficient of the coating film.

If the coefficient of thermal expansion of the resin pixel is large, the amount of thermal expansion of the overcoat layer at the time of sputtering or baking of ITO or heating in the subsequent process increases. Compared with the thermal expansion coefficient of the overcoat layer, the thermal expansion coefficient of ITO is an order of magnitude smaller. Therefore, it is assumed that ITO cannot follow the expansion of the overcoat layer, and that ITO is broken or wrinkled. . The thermal expansion coefficient of the resin composition is about 3 × 10 ⁻⁵ to 4 × 10 ⁻⁵ , and the thermal expansion coefficient of ITO is 7.2 × 10 ⁻⁶ (Japanese Patent Laid-Open No. 6-0667015).

The temperature-stress gradient, that is, the thermal expansion property of the resin composition is affected by the crosslinkability in the coating film. That is, it can be controlled by the content of the crosslinkable monomer in the resin composition and the double bond equivalent amount of the crosslinkable monomer. In order to increase the temperature-stress gradient (increase the thermal expansion property), the content of the crosslinkable monomer may be increased and the double bond equivalent of the crosslinkable monomer used may be decreased. Examples of the monomer having a small double bond equivalent include dipentaerythritol hexaacrylate (DPHA) and pentaerythritol tetraacrylate.

  On the other hand, in order to reduce the slope (low thermal expansion), it is preferable to reduce the content of the crosslinkable monomer and increase the double bond equivalent of the monomer used. Monomers having a large double bond equivalent include caprolactone-modified DPHA (for example, DPCA30, DPCA60, DPCA120 manufactured by Nippon Kayaku Co., Ltd.) and urethane acrylate monomers (for example, U-6HA, U-6LPA, UA-110HA manufactured by Shin-Nakamura Chemical Co., Ltd.) ).

  In the color filter according to the present embodiment, the colored pixels 23 preferably have a film 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 23B according to the present invention is formed by photolithography, it is difficult to form a pixel when the film thickness is less than 0.1 μm, and when the film thickness is greater than 5 μm, the colored composition is formed. This is because it is difficult to form the coating film 13 by coating.

The color filter which concerns on this embodiment comprises the colored pixel 23 which consists of a colored coating film formed using the coloring composition for color filters mentioned above on the transparent base material. Further, an overcoat layer 24 is provided on the colored pixel 23, and a transparent electrode is formed thereon.
That is, as shown in FIG. 2, the color filter includes a black matrix 22 that is a light shielding film and a colored pixel 23 on a transparent substrate 21 such as glass. The colored pixel 23 includes a blue pixel 23B, a red pixel 23R, and a green pixel 23G formed using the above-described blue coloring composition. An overcoat layer 24 is formed thereon, and a transparent electrode 25 is formed thereon.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate 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.

  Each colored pixel 23 can be formed by, for example, a printing method, an inkjet method, a photolithography method, or the like.

  The formation of each color coloring pixel 23 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. Are better. 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 producing a color filter using an ink jet method, a black matrix 22 is formed on a glass substrate which is a transparent substrate 21, and an ink is applied to an opening of the black matrix 22 using an ink jet printing apparatus to form a colored portion. A method of forming has been proposed. Further, in this method, the material constituting the black matrix 22 is made of a fluorine compound, a silicon compound, or the like 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. A water repellent 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 forming each color colored pixel 23 by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on the transparent substrate 21 by spray coating, spin coating, slit coating, roll coating or the like. The coating method is applied so that the dry film thickness is 0.2 to 10 μm. 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 of manufacturing a color filter by using a transparent conductive film formed on a transparent substrate 21 and electrodepositing each color-colored pixel 23 on a transparent electrode 25 by electrophoresis of colloidal particles. is there.

  The transfer method is a method in which colored pixels 23 are formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and the colored pixels 23 are transferred to a desired transparent substrate 21.

  If the black matrix 22 is formed in advance before forming the colored pixels 23 on the transparent substrate 21 or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix 22, 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.

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. 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.

  When the color filter according to the present invention is incorporated in a display device, an electrode (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 electrode substrate, the aperture ratio can be increased and the luminance can be improved.

  A columnar spacer or the like may be formed in the color filter according to the present invention 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 symbol of the pigment indicates a color index number. For example, “PR254” is “CI PigmentRed254”, “PB15: 6” is “CI PigmentBlue15: 6”, and dyes and pigments are described below. The example of manufacture of is shown.

<Coloring composition>
The following were used for the coloring agent for coloring the coloring composition used for color filter preparation.

  Red pigment: C.I. I. Pigment Red 254 (“Ilgar Forred B-CF” manufactured by Ciba Specialty Chemicals), C.I. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals).

  Green pigment: C.I. I. Pigment Green 58 (manufactured by DIC Corporation, “Phthalocyanine Green A110”; G-1).

  Blue pigment: C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.).

  Yellow pigment: C.I. I. Pigment Yellow 150 ("YELLOW PIGMENT E4GN" manufactured by LANXESS; Y-1).

The red pigment (R-1) could be reacted with the following composition.
100 parts of diketopyrrolopyrrole red pigment PR254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals)
Pigment derivative (D-1) 10 parts ground salt 1000 parts diethylene glycol 120 parts were charged in a stainless steel 1 gallon kneader (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.

  The structural formula of the dye derivative (D-1) is shown in Chemical Formula 3.

赤色顔料（Ｒ‐２）は下記組成を反応させ得た。
アントラキノン系赤色顔料ＰＲ１７７ １００部（チバスペシャリティケミカルズ社製「クロモフタールレッドＡ２Ｂ」）
色素誘導体（Ｄ‐２） ８部粉砕した食塩 ７００部エチレングリコール １８０部をステンレス製１ガロンニーダー（井上製作所製）に仕込み、７０℃で４時間混練した。

The red pigment (R-2) could be reacted with the following composition.
100 parts of anthraquinone red pigment PR177 (“Chromoval Red A2B” manufactured by Ciba Specialty Chemicals)
Pigment derivative (D-2) 8 parts of pulverized salt 700 parts Ethylene glycol 180 parts were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) 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 obtained the refined pigment (R-2). The average particle diameter of the obtained pigment was 30 nm.

  The structural formula of the dye derivative (D-2) is shown in Chemical Formula 4.

青色顔料（Ｂ‐１）は下記組成を反応させ得た。
青色顔料 ２００部（Ｃ．Ｉ．ＰｉｇｍｅｎｔＢｌｕｅ１５：６、東洋インキ製造社製「ＬＩＯＮＯＬＢＬＵＥＥＳ」）
塩化ナトリウム １６００部ジエチレングリコール（東京化成社製） １００部をステンレス製１ガロンニーダー（井上製作所社製）に仕込み、７０℃で１２時間混練した。次に、この混合物を約５リットルの温水に投入し、約７０℃に加熱しながらハイスピードミキサーで約１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウム及びジエチレングリコールを除き、８０℃で２４時間乾燥し、１９８部のソルトミリング処理顔料（青色顔料Ｂ‐１）を得た。

The blue pigment (B-1) could be reacted with the following composition.
200 parts of blue pigment (CI Pigment Blue 15: 6, “LIONOLBLUEES” manufactured by Toyo Ink Co., Ltd.)
Sodium chloride 1600 parts diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. 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).

The acrylic resin solution (P-1) could be reacted with the following composition.
Preparation of the binder polymer solution used in the 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 is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and methacrylic acid (MAA) 20.0 parts methyl methacrylate (MMA) 10.0 parts benzyl methacrylate (BzMA) at the same temperature 55.0 parts 2-hydroxyethyl methacrylate (HEMA) A mixture of 15.0 parts 2,2′-azobisisobutyronitrile (4.0 parts) was added dropwise over 1 hour to conduct a polymerization reaction.

After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours,
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 to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 20,000.

  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.

  The pigment dispersion is prepared by uniformly stirring and mixing a mixture having the composition shown in Table 1, and then dispersing the mixture for 2 hours with an Eiger mill using zirconia beads having a diameter of 0.1 mm, followed by filtering with a 5 μm filter to prepare a pigment dispersion. did.

表１に示す材料の詳細を下記に示す。
分散剤 ： アクリル系分散剤（ビックケミー社製ＢＹＫ‐２００１）有機溶剤 ： シクロヘキサノンである。

Details of the materials shown in Table 1 are shown below.
Dispersant: Acrylic dispersant (BYK-2001 manufactured by Big Chemie) Organic solvent: Cyclohexanone.

  The structural formula of the dye derivative (D-3) is shown in Chemical Formula 5.

色素誘導体（Ｄ‐４）の構造式を化６に示す。

The structural formula of the dye derivative (D-4) is shown in Chemical Formula 6.

着色組成物は、下記組成の混合物を均一になるように攪拌混合した後、
顔料分散体 ＰＲ‐１： ２２．５質量部顔料分散体 ＰＲ‐２： ２２．５質量部アクリル樹脂溶液（Ｐ‐１）： １．５質量部モノマー（Ｍ−１）： ５．１質量部（ジペンタエリスリトールヘキサアクリレート、東亞合成社製アロニックスＭ４０２）
光重合開始剤： １．０質量部（チバガイギー社製「イルガキュア‐３７９」）
光増感剤： ０．２質量部（日本化薬社製「ＫＡＹＡＣＵＲＥ ＤＥＴ‐Ｘ」）
有機溶剤：（プロピレングリコールモノメチルエーテルアセテート） ４７．２質量部５μｍのフィルタで濾過して赤色着色組成物（ＰＲ‐１）を得た。

The coloring composition is stirred and mixed so that a mixture of the following composition is uniform,
Pigment dispersion PR-1: 22.5 parts by mass Pigment dispersion PR-2: 22.5 parts by mass Acrylic resin solution (P-1): 1.5 parts by mass Monomer (M-1): 5.1 parts by mass (Dipentaerythritol hexaacrylate, Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.0 part by mass (“Irgacure-379” manufactured by Ciba Geigy)
Photosensitizer: 0.2 parts by mass (“KAYACURE DET-X” manufactured by Nippon Kayaku Co., Ltd.)
Organic solvent: (propylene glycol monomethyl ether acetate) A red colored composition (PR-1) was obtained by filtration through a filter of 47.2 parts by mass of 5 μm.

  The green colored composition RG-1 and the blue colored composition RB-1 were prepared in the same manner as in Comparative Example 3, except that the pigment dispersion, photopolymerization initiator, and photosensitizer described in Table 3 below were used. Obtained. In Table 3, the colored composition according to Comparative Example 3 is also shown.

The overcoat resin composition was obtained by the following reaction. 37 g of cyclohexanone and 52 g of diethylene glycol dimethyl ether were placed in a sample bottle. While stirring, epoxy resin; ESF-300 (manufactured by Nippon Steel Chemical Co., Ltd .: bisphenolfluorene type epoxy resin, epoxy equivalent of 231 g / eq) 6 g, epoxy resin; EHPE3150 (manufactured by Daicel Chemical Industries, Ltd .: alicyclic type) Solid epoxy resin, 9 g of epoxy groups in molecule, epoxy equivalent 170 g / eq) 2 g, epoxy resin; EOCN-1020 (Nippon Kayaku Co., Ltd. Orthocresol novolak type epoxy resin, epoxy equivalent 200 g / eq) 14 g In addition, it was completely dissolved to prepare an epoxy compound (EP).

  After adding 20 g of trimellitic anhydride as a curing agent and sufficiently stirring and dissolving, 0.10 g of dimethylcyclohexylamine was added as a curing accelerator. Further, 3.0 g of a silane coupling agent (S-510 manufactured by Chisso Corporation) and 0.12 g of a surfactant (manufactured by Sumitomo 3M; Fluorad FC-430) were added and sufficiently stirred and dissolved. Thus, a resin composition for forming an overcoat layer was obtained.

  Resin compositions of Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were the same as Example 1 except that the acrylic resin, monomer, and photopolymerization initiator were used as described in Table 3. I got a thing. Table 3 also shows the resin composition of Example 1.

表３に示す材料の詳細は、
アクリル樹脂：Ｐ‐１
モノマー：Ｍ‐１
（ジペンタエリスリトールヘキサアクリレート、東亞合成社製アロニックスＭ４０２）光重合開始剤：（チバガイギー社製「イルガキュア−３７９」）
界面活性剤：１％ポリエーテル変性シリコンオイルＳＨ８４００
（商品名：トーレシリコーン社製）
有機溶剤：シクロヘキサノン
である。

For details of the materials shown in Table 3,
Acrylic resin: P-1
Monomer: M-1
(Dipentaerythritol hexaacrylate, Aronix M402 manufactured by Toagosei Co., Ltd.) Photopolymerization initiator: ("Irgacure-379" manufactured by Ciba Geigy)
Surfactant: 1% polyether-modified silicone oil SH8400
(Product name: manufactured by Torre Silicone)
Organic solvent: cyclohexanone.

<Measurement of stress>
It describes about the measuring method of the stress of a resin composition. A thin film stress measuring device (FLX2328 manufactured by Tencor Instruments) was used as a measuring device. The silicon wafer used for the measurement was a wafer having a diameter of 4 inches, a thickness of 525 μm, and a Miller index [111].

  First, the curvature radius of only the silicon wafer was measured. Next, the coloring composition was applied by a spin coater so that the film thickness after firing was 2.0 μm. Thereafter, it was dried and baked in an oven at 230 ° C. for 30 minutes. Next, the heating stage of the thin film stress measuring apparatus is set to 40 ° C., silicon is set, and after 5 minutes, the temperature rises at a rate of 15 ° C./minute, and the measurement interval is 1 minute. The stress value was measured. The measurement results of the resin compositions described in Example 1, Example 2 and Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are shown in FIG. 3 as a temperature-stress relationship.

  Table 4 shows the slope of each temperature-stress plot. In addition, when the stress value became zero at a temperature lower than 230 ° C., the value of the slope before reaching zero was adopted.

＜ガラス上密着性評価＞
上記の実施例1〜３、比較例１〜３のオーバーコート材料を用いて、ガラス上に仕上がり２．５μｍとなるようにスピンコート法により塗膜し、９０℃で２分間乾燥した。

<Evaluation of adhesion on glass>
Using the overcoat materials of Examples 1 to 3 and Comparative Examples 1 to 3, the film was coated on glass by a spin coat method so as to have a finish of 2.5 μm, and dried at 90 ° C. for 2 minutes.

Light from a high-pressure mercury lamp was irradiated through a photomask for forming an overcoat layer at 100 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers. Then, it developed using the developing solution similar to preparation of the above-mentioned colored layer. After washing with water, baking was performed at 230 ° C. for 30 minutes to form an overcoat layer on the glass substrate.

<Evaluation of adhesion>
Adhesiveness was evaluated about the overcoat layer on the glass obtained by using said Examples 1-3 and Comparative Examples 1-3. Classification was made from 0 to 5 according to JIS-K-5600-5-6. The transparent electrode layer for the color filter is preferably classified as 0 or 1, more preferably classified as 0. The evaluation results are shown in Table 5.

＜カラーフィルタの作成方法＞
赤色着色組成物ＲＲ‐１、緑色着色組成物ＲＧ‐１、青色着色組成物ＲＢ‐１を用いてカラーフィルタを作製した。まず、赤色着色組成物ＲＲ‐１を、硬化後の膜厚が２．５μｍとなるように、スピンコート法によりブラックマトリクスを形成してあるガラス基板に塗布し、乾燥した後、ネガ像を有するフォトマスクを介して超高圧水銀ランプを用いて紫外線で露光した。その後、２３℃の炭酸ナトリウム水溶液を用いてスプレー現像した後、イオン交換水で洗浄し、風乾した。その後、クリーンオーブン中で、２３０℃で３０分のポストベークを行い、赤色着色パターンを有するガラス基板を得た。その後、緑色着色組成物ＲＧ‐１を用いて同様に緑色着色パターンを得る。さらに青色着色組成物ＲＢ‐１を用いて青色着色パターンを得た。

<How to create a color filter>
Color filters were prepared using the red coloring composition RR-1, the green coloring composition RG-1, and the blue coloring composition RB-1. First, the red coloring composition RR-1 is applied to a glass substrate on which a black matrix has been formed by spin coating so that the film thickness after curing is 2.5 μm, dried, and then has a negative image. It exposed with the ultraviolet-ray using the ultrahigh pressure mercury lamp through the photomask. Thereafter, spray development was performed using a sodium carbonate aqueous solution at 23 ° C., followed by washing with ion-exchanged water and air drying. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to obtain a glass substrate having a red coloring pattern. Then, a green coloring pattern is similarly obtained using the green coloring composition RG-1. Furthermore, a blue coloring pattern was obtained using the blue coloring composition RB-1.

  As the overcoat layer, the resin composition described in Example 1 was applied to the color filter obtained by the procedure shown in the color filter preparation method by a spin coat method so as to have a film thickness of 2.0 μm. It dried for 2 minutes with a 100 degreeC hotplate, and implemented post-baking for 30 minutes in 230 degreeC oven.

Next, the color filter was made of ITO using an ITO sputtering apparatus. In a sputtering apparatus, Ar: 400 SCCM, O2: 0.2 SCCM were introduced at room temperature using an ITO target, and after adjusting the gas pressure to 0.67 Pa, the ITO film was applied with an output of 3.5 W / cm ^2. A film was formed. The film thickness was 150 nm. Thereafter, heat treatment was performed in an oven at 230 ° C. to obtain an ITO film having desired characteristics. The color filter obtained by the above procedure is referred to as Example 4.

  Overcoat layers were formed on the color filters obtained by the same procedure using the resin compositions described in Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively, and ITO was formed. did. The ITO filter was evaluated for the color filter on which the overcoat layer obtained by the above procedure and ITO were formed.

<Evaluation of ITO tear>
The color filters of Examples 1 to 3 and Comparative Examples 1 to 3 were observed with a scanning electron microscope. An evaluation was performed based on whether tearing was observed in ITO. The case where ITO tearing was observed was judged as x, and the case where it was not observed was judged as ◯, and is shown in Table 6.

＜ＩＴＯシワの評価＞
上記実施例および比較例で得られたカラーフィルタについて透明電極層のシワ、ムラおよび密着性を評価した。シワ、ムラについては、Ｎａランプ下で目視により、シワおよびムラがある場合を×、ない場合を○とした。

<Evaluation of ITO wrinkles>
The color filters obtained in the examples and comparative examples were evaluated for wrinkles, unevenness and adhesion of the transparent electrode layer. For wrinkles and unevenness, the case where there were wrinkles and unevenness was visually evaluated under a Na lamp, and the case where there was no wrinkle was indicated as ◯.

<Color filter adhesion evaluation>
Adhesiveness was evaluated about the overcoat layer on the glass obtained by using said Examples 1-3 and Comparative Examples 1-3. Classification was made from 0 to 5 according to JIS-K-5600-5-6. The transparent electrode layer for the color filter is preferably classified as 0 or 1, more preferably classified as 0.

  In Examples 1 to 3 in which the monomer / resin ratio is 0.6 to 0.9 and the stress is 0.15 or less, the color filter has no glass adhesion, color filter adhesion, ITO tearing, and ITO wrinkle generation A substrate can be obtained.

  On the other hand, Comparative Example 1 and Comparative Example 2 in which the monomer ratio is 1.0 or more have poor glass adhesion and color filter adhesion, and ITO cracks are also generated. On the other hand, Comparative Example 3 having a low ratio has good glass adhesion and color filter adhesion, but the occurrence of ITO wrinkles was confirmed.

DESCRIPTION OF SYMBOLS 11 ... Heating stage 12 ... Silicon wafer 13 ... Coating film 14 of coloring composition ... Laser light source 15 ... Mirror 16 ... Detector 17 ... Measurement laser beam 18 ... Enclosure 21 for maintaining temperature ... Transparent substrate 22 ... Black matrix 23 ... Colored pixel 23R ... Red pixel 23G ... Green pixel 23B ... Blue pixel 24 ... Overcoat layer 25 ... Transparent electrode 26 ... Sealing material

Claims (4)

A color filter for a liquid crystal display device in which a colored pixel, an overcoat layer, and a transparent electrode are laminated on a transparent substrate,
A photosensitive resin composition for forming an overcoat layer of the color filter is applied onto a silicon wafer,
Measure the stress of the coating film of the photosensitive resin composition obtained by drying and baking at least 3 points between 40 ° C. and 200 ° C.,
A photosensitive resin composition having physical properties in which the stress value obtained by the measurement is plotted on the vertical axis and the temperature at that time is plotted on the horizontal axis, and the absolute value of the slope of the straight line is 0.15 Mpa / ° C. or less. A color filter for a liquid crystal display device characterized by being used. The photosensitive resin composition contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a surfactant, and a solvent,
2. The color filter for a liquid crystal display device according to claim 1, wherein a ratio of the binder polymer to the photopolymerizable compound (photopolymerizable compound / binder polymer) is in a range of 0.6 to 0.9.   The color filter for a liquid crystal display device according to claim 1, wherein the transparent electrode is ITO (tin-doped indium oxide).   A liquid crystal display device comprising the color filter for a liquid crystal display device according to claim 1.

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