JP2006343399A - Color filter and colored composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a satisfactory color filter having no foreign matter inferiority and no image defect by reducing charge gathering on a glass substrate where a coating layer of a colored composition is applied and preventing sticking of dirt and destruction of an exposure mask pattern. <P>SOLUTION: In the colored composition for the color filter produced by dispersing a dyestuff in a transparent resin, the transparent resin contains a heteroatom-containing dielectric polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter used for a color liquid crystal display device and the like, and a coloring composition used therefor.

  For example, a color filter used in a color liquid crystal display device, etc., regularly arranges three colored patterns of red (R), green (G), and blue (B) on a transparent substrate, for example, in the form of dots or stripes. Thus, between each colored layer, a lattice-shaped or stripe-shaped light shielding layer so-called black matrix serving as a partition for optically separating each colored layer is provided. As a manufacturing method of such a color filter, for example, a method of manufacturing by a pigment dispersion method, a printing method, a transfer method, a dyeing method, or the like is known.

  In the pigment dispersion method, three-color coloring compositions each containing a photosensitive resin and red, green, and blue organic pigments are prepared. On a transparent substrate provided with a black matrix, for example, first, red coloring is performed. Using the composition, a red coloring composition is applied to form a coating layer, followed by drying, pattern exposure, development, and baking to form a red filter layer, and then a green coloring composition and a blue color Using the colored composition in order, the same steps are repeated, and each layer of a black matrix and a three-colored colored pattern is formed using a photolithography method for forming a green filter layer and a blue filter layer (for example, Patent Documents) 1).

  Such a colored composition becomes an insulator because it contains the organic pigment and the resin as described above, and is easily charged with static electricity. For this reason, while this coating composition is repeatedly used for coating, drying, pattern exposure, development, and baking, charges accumulate on the glass substrate on which the coating layer is formed, and dust adheres to the foreign matter. There is a problem in that the electrostatic mask is generated and electrostatic charges are induced to the exposure mask used at the time of pattern exposure due to the accumulated charges, and the exposure mask is destroyed.

Therefore, as a conventionally proposed method, a method of depositing a polyvinyl alcohol resin layer on a surface of a photomask on which a mask pattern is formed (see, for example, Patent Document 1), a transparent conductive film on a transparent substrate for photomask. And a transparent insulating film are sequentially laminated, and a light-shielding metal film is laminated above the transparent insulating film (see, for example, Patent Document 2), or light is transparent over the entire glass surface including the photomask pattern surface. There are methods for coating a conductive thin film (see, for example, Patent Document 3). By these methods, generation of static electricity can be suppressed, and dust adhesion and electrostatic breakdown can be prevented. However, both of these methods add a processing step to the photomask substrate, and adding such a step increases the possibility of causing defects during the manufacture of an expensive photomask, and makes it difficult to correct the mask pattern. It was to make.
Japanese Patent Laid-Open No. 60-4944 Japanese Patent Publication No.62-35663 JP-A-2-248950

  The present invention reduces the charge accumulated on the glass substrate coated with the coating layer of the colored composition during the production of the color filter without additional processing on the photomask as described above, An object of the present invention is to provide a good color filter that prevents the exposure mask pattern from being destroyed and has no foreign matter defects or image defects.

  In addition, the present invention reduces the charge accumulated on the glass substrate coated with the coating layer of the colored composition during the production of the color filter, prevents adhesion of dust and destruction of the exposure mask pattern, It is an object of the present invention to provide a colorant composition capable of forming a good color filter without defects.

  The colored composition for a color filter of the present invention is a colored composition for a color filter in which a pigment is dispersed in a transparent resin, wherein the transparent resin contains a heteroatom-containing dielectric polymer.

  In a preferred color composition for a color filter of the present invention, the heteroatom-containing dielectric polymer is polyethylene dioxythiophene.

  In a preferred color composition for a color filter of the present invention, the heteroatom-containing dielectric polymer is contained in an amount of 2 to 60% by weight based on 100% by weight of the total solid content of the color composition.

  In a preferred color filter coloring composition of the present invention, the heteroatom-containing dielectric polymer has a volume resistivity of 5 Ω · cm or less.

  The preferable coloring composition for color filters of the present invention further contains a photosensitive resin.

  The color filter of the present invention has a color filter layer of a plurality of colors formed by the above color filter coloring composition and arranged in a pattern.

  According to the present invention, sufficient conductivity can be imparted by adding a heteroatom-containing dielectric polymer to the colored composition for a color filter, so that a glass coated with a coating layer of the colored composition is applied. By reducing the charge accumulated on the substrate and preventing the adhesion of dust and the destruction of the exposure mask pattern, it is possible to form a good color filter free from foreign matter defects and image defects.

  The coloring composition for a color filter of the present invention contains a transparent resin and a pigment dispersed in the transparent resin, and the transparent resin contains a heteroatom-containing dielectric polymer.

  Here, the transparent resin containing the heteroatom-containing dielectric polymer is assumed to be a heteroatom-containing dielectric polymer, or a part of the transparent resin is a heteroatom-containing dielectric polymer.

  The colored composition for a color filter according to the present invention is imparted with conductivity by a heteroatom-containing dielectric polymer added as a conductive polymer. Thereby, the electric charge which accumulates on the glass substrate with which the coating layer of the coloring composition was apply | coated can be reduced, and adhesion of refuse and the destruction of an exposure mask pattern can be prevented. For this reason, by using the coloring composition for a color filter according to the present invention, it is possible to form a good color filter free from foreign matter defects and image defects.

  The heteroatom-containing dielectric polymer used in the present invention is preferably contained in an amount of 2 to 60% by weight based on 100% by weight of the total solid content of the coloring composition.

  If the content of the heteroatom-containing dielectric polymer is less than 2% by weight, sufficient conductivity may not be obtained. If the content exceeds 60% by weight, a color change occurs in the colored layer itself, resulting in reliability. There is a tendency that the color characteristics of the color filter including the color filter cannot be maintained.

  In addition, as the heteroatom-containing dielectric polymer, those having a volume resistivity of 5 Ω · cm or less can be preferably used.

  If it exceeds 5 Ω · cm, the content of heteroatoms is too large, causing a color change in the colored filter layer, which tends to affect the color characteristics of the color filter.

  The volume resistivity of the heteroatom-containing dielectric polymer is more preferably 0.01 to 5 Ω · cm. Furthermore, it is preferably 0.1 to 3 Ω · cm.

  As the heteroatom-containing dielectric polymer, for example, polyethylene dioxythiophene (PEDOT) can be used.

  The polyethylene dioxythiophene preferably used in the present invention is represented by poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonate).

Poly (3,4-ethylenedioxythiophene) is represented by the following chemical formula (1).

-Poly (styrene sulfonate) is represented by following Chemical formula (2), and can be used as a dopant of a conductive polymer.

  Colorants such as pigments and dyes can be used as the pigment.

  Preferred examples of the colorant include C.I. I. Pigment red 254, C.I. I. A red colorant such as a mixture of CI Pigment Red 177, C.I. I. Pigment green 36, C.I. I. Pigment yellow 150 or C.I. I. Green colorants such as mixtures with CI Pigment Yellow 138, and C.I. I. Pigment blue 15, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, and C.I. I. And blue colorants such as CI Pigment Blue 64.

  The coloring composition for a color filter of the present invention may further contain a photosensitive resin.

  As a photosensitive resin, for example, a substituent such as an isocyanate group, an aldehyde group, and an epoxy group is intervened in a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group. ) A resin into which a photocrosslinkable group such as an acrylic compound or cinnamic acid is introduced is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified polymer can also be used.

  The color filter of this invention is formed using the said coloring composition for color filters.

  The color filter includes, for example, a substrate and a plurality of color filters formed using the above-described coloring composition and arranged in, for example, a stripe shape or a dot shape.

  Preferably, a black matrix can be provided between the colored filters.

  In order to apply the above colorant, heteroatom-containing dielectric polymer, and photosensitive resin color composition to the substrate, these materials described above are composed of a two-roll mill, a three-roll mill, a sand mill, and It can be prepared by kneading using a disperser such as a paint conditioner.

  As the substrate, a transparent substrate having a certain degree of strength and not affected by the coloring composition can be used. Examples of such a substrate include a glass plate, a polycarbonate plate, a polymethyl methacrylate plate, and a polyester film.

  FIG. 1 is a cross-sectional view illustrating a configuration of an example of the color filter of the present invention.

  The color filter 10 of the present invention includes a substrate 1 and a plurality of colored filter layers 2 arranged in a predetermined pattern on the substrate 1, for example, a red colored filter layer 2R, a green colored filter layer 2G, and a blue colored filter layer 2B. A plurality of color pixel portions and a black matrix 3 that shields light between adjacent colored filter layers 2, and at least a part of the colored filter layer 2 uses the colored composition for a color filter of the present invention. Is formed.

  On these pixel portions and the black matrix, an overcoat layer 4 can be optionally formed to protect them.

  The black matrix can be formed on the substrate by, for example, printing or photolithography using the coloring composition for a color filter of the present invention, or other photosensitive resin composition, or a metal such as chromium.

  Hereinafter, an example of a method for producing a color filter of the present invention using photolithography will be described with reference to FIGS.

  First, as shown in FIG. 2, a transparent substrate 5 such as glass on which the black matrix 3 is formed is prepared.

  Next, for example, according to the color filter layer of red, green, and blue, for example, as shown in FIG. 3, for example, as shown in FIG. After the green filter coloring composition is applied by spin coating, heating is performed, for example, at 100 ° C. for 3 minutes to dry volatile components such as a solvent (prebaking), and the green filter coloring composition layer The coating layer 6 is formed. In the present invention, since the coating layer 6 has sufficient conductivity, dust is difficult to adhere and the occurrence of foreign matter defects can be prevented.

  As a coating method of the color filter coloring composition, known methods such as a spray coating method, a spin coating method, a roll coating method, and a curtain coating method can be used.

  Next, after cooling, as shown in FIG. 4, this coating layer 6 is exposed to active energy rays through a photomask 9 having a predetermined pattern, for example, using an ultrahigh pressure mercury lamp as a light source. At this time, the photomask 9 is placed in close proximity to the coating layer 6 and separated after the exposure. However, the coating layer 6 using the color filter coloring composition has sufficient conductivity, so that the photomask 9 is separated at the time of separation. The mask is charged and dust does not adhere to the photomask or cause electrostatic breakdown.

  Thereafter, the unexposed portion is developed with an alkaline developer such as a 2.5% aqueous sodium carbonate solution, washed thoroughly with water, and further washed with water and dried. In this way, as shown in FIG. 5, the patterned green filter layer 11G is obtained on the transparent substrate 5 on which the black matrix 3 is formed. An antifoaming agent or a surfactant can be added to the developer as necessary. After the development, for example, heat treatment is performed at 230 ° C. for 60 minutes to perform main curing (post-bake). By repeating this until the pixel portion having the desired number of colors is formed, the colored filter layer is patterned, for example, the blue filter layer patterned using the blue filter coloring composition is colored for the red filter. A red filter layer patterned with the composition is obtained. In this way, the color filter of the present invention can be obtained.

  As an alkali component of the alkali developer, for example, sodium hydroxide, sodium carbonate, or the like can be used.

  FIG. 6 is a cross-sectional view illustrating the configuration of the color filter obtained.

  As shown in the figure, the color filter 20 includes a transparent substrate 5 and a colored filter layer 2 arranged in a predetermined pattern, for example, a red color filter layer 11R, a green color filter layer 11G, and a blue color filter layer 11B. And a black matrix 3 that shields light between the adjacent colored filter layers 11R, 11G, and 11B.

  This method can be applied not only when the pixel portion is formed but also when a black matrix is provided.

  Moreover, the coloring composition for color filters of this invention is once apply | coated on transcription | transfer support members, such as a transcription | transfer cylinder (what is called blanket) and a transcription | transfer film, the said pattern process can be performed, and it can transcribe | transfer to a board | substrate after that.

  As an active light source used for exposure, light having a wavelength of 300 to 450 nm such as an ultraviolet electron beam can be used. For example, light irradiated from ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, or the like is used. be able to.

  The color filter using the coloring composition for a color filter of the present invention has different components depending on the application, and there is no limitation on the configuration, but in general, it is patterned on a transparent substrate and this transparent plate. And a pixel portion based on a plurality of colored filter layers arranged in color, and white light incident on the pixel portion is colored in the color of the pixel portion.

  Examples of the black colorant used in the black matrix include carbon black, graphite, iron black, aniline black, cyanine black, and titanium black. Carbon black is preferred from the standpoints of light-shielding properties and image characteristics.

  The color filter of the present invention can be used for, for example, a liquid crystal display, a plasma display, an electroluminescence panel, etc., and uses light from a light source built in the display as incident light or sunlight incident on a display screen. Color screens can be displayed with colored light that has passed through the color filter, and can also be used for color video cameras, digital cameras, etc., and provided as a component of a solid-state image sensor to split light incident from the subject. Can play a role.

  In a liquid crystal display device applicable to the present invention, liquid crystal is sealed between a pair of transparent substrates, and a pixel electrode or the like is provided between one transparent substrate and the liquid crystal, for example, between the other transparent substrate and the liquid crystal. May have a configuration in which a color filter, a counter pixel electrode, and the like are provided in order from the transparent substrate side.

  FIG. 7 is a cross-sectional view illustrating a configuration of an example of a liquid crystal display device to which the color filter of the present invention is applied.

  As shown in the figure, the liquid crystal display device 30 includes a pair of transparent substrates 11 and 21 provided to face each other, and a liquid crystal 29 sealed therebetween. One transparent substrate 11 includes a pixel electrode 12 provided on the main surface on the transparent substrate 21 side, an alignment film 13 provided on the pixel electrode 12 and subjected to an alignment treatment such as rubbing, and other main substrates. And a polarizing plate 14 provided on the surface. Further, the other transparent substrate 21 is a pixel portion of a plurality of colors composed of, for example, a red filter layer 22R, a green filter layer 22G, and a blue filter layer 22B arranged in a predetermined pattern on the main surface on the transparent substrate 11 side. And a color filter 28 including a black matrix 23 that shields light between the adjacent colored filter layers 22R, 22G, and 22B, a counter electrode 24 provided on the color filter 28, and an orientation provided on the counter electrode 24. The alignment film 25 is subjected to the alignment treatment in the same manner as the film 13. The liquid crystal 29 is sealed between the alignment film 13 and the alignment film 25. As the liquid crystal 29, a twisted nematic liquid crystal (TN) or a super twisted nematic liquid crystal (STN) can be preferably used, and these liquid crystal molecules are twisted and aligned in a range of 90 to 270 ° in each driving mode. A backlight unit (not shown) is provided below the polarizing plate 14.

  Hereinafter, the present invention will be specifically described with reference to examples.

  In Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”.

  The molecular weight of the resin is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

  First, a photosensitive resin and a non-photosensitive resin used for the color filter coloring composition were synthesized as follows.

(Synthesis Example 1)
560 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate, As the monomer (a), 22.0 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.), 47.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 4 0.0 part of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 120.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows.

  The obtained photosensitive transparent resin had a weight average molecular weight of 21,000 and a double bond equivalent of 470.

(Synthesis Example 2)
570 parts of cyclohexanone is placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 35.0 parts of benzyl methacrylate, single amount As the body (a), 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 48.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 3.0 Part of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 336 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows.

  The obtained photosensitive transparent resin had a weight average molecular weight of 32,000 and a double bond equivalent of 460.

(Synthesis Example 3)
520 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 63.0 parts of 2-hydroxyethyl methacrylate at the same temperature. Then, a mixture of 66.0 parts of glycerol monomethacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 70 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, with respect to 220 parts of the obtained transparent resin solution, a mixture of 26.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 220.0 parts of cyclohexanone was added at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows.

  The obtained photosensitive transparent resin had a weight average molecular weight of 20,000 and a double bond equivalent of 270.

(Synthesis Example 4)
480 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate, 29.0 parts of benzyl methacrylate, 19.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) as monomer (a), 15.0 parts of glycerol monomethacrylate, 2,2′- A mixture of 4.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 80 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, with respect to 445 parts of the obtained transparent resin solution, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 55.0 parts of cyclohexanone was added at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows.

  The obtained photosensitive transparent resin had a weight average molecular weight of 21,000 and a double bond equivalent of 1,000.

(Synthesis Example 5)
560 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 22.0 parts of methacrylic acid, 22.0 parts of n-butyl methacrylate, 2-hydroxyethyl methacrylate 104. A polymerization reaction was carried out by dropping a mixture of 0 part and 4.0 part of 2,2′-azobisisobutyronitrile over 1 hour. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows.

  The obtained photosensitive transparent resin had a weight average molecular weight of about 20,000 and a double bond equivalent of 470.

(Synthesis Example 6)
570 parts of cyclohexanone was placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 7.0 parts of methacrylic acid, 11.0 parts of methyl methacrylate, 32.0 parts of benzyl methacrylate, 2- A mixture of a monomer comprising 101.0 parts of hydroxyethyl methacrylate and 3.0 parts of 2,2′-azobisisobutyronitrile and a thermal polymerization initiator was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.

  Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 337 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling this solution to room temperature, about 2 g of the photosensitive transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and the previously synthesized photosensitive transparent resin solution had a nonvolatile content of 20 wt. % Cyclohexanone was added.

  The obtained photosensitive transparent resin had a weight average molecular weight of about 30,000 and a double bond equivalent of 460.

(Synthesis Example 7)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained. After cooling this solution to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content. Cyclohexanone was added so that it might become 20 weight%.

  The obtained non-photosensitive transparent resin had a weight average molecular weight of 40,000.

(Synthesis Example 8)
70 parts of cyclohexanone is put into a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 5. 3 parts, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.) as monomer (a), 0.4 part of 2,2'-azobisisobutyronitrile Was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that

  The weight average molecular weight of the obtained non-photosensitive transparent resin was 27000.

(Synthesis Example 9)
70 parts of cyclohexanone is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 14.4 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 3. 2 parts, a mixture of 7.4 parts paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.) as monomer (a), 0.4 parts 2,2'-azobisisobutyronitrile Was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained. After cooling this solution to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content. Cyclohexanone was added so that it might become 20 weight%.

  The obtained non-photosensitive transparent resin had a weight average molecular weight of 25,000.

Table 1 below shows the weight average molecular weight, double bond equivalent, and acid value of the photosensitive transparent resin and the non-photosensitive transparent resin obtained in Synthesis Examples 1 to 9. The acid value was measured and calculated according to JIS-K-0070.

Example 1
(Method for producing blue pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.

ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF) 11.0 parts 1.0 part of a phthalocyanine pigment represented by the following structural formula (3)

In the formula, Cu-pc is a photosensitive transparent resin solution obtained in copper phthalocyanine residue synthesis example 9.8 parts Non-photosensitive transparent resin solution obtained in synthesis example 7 30.1 parts cyclohexanone 48.1 parts (Production method of blue coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue colored composition.

Blue pigment dispersion 45.0 parts Photosensitive transparent resin solution obtained in Synthesis Example 1 15.9 parts Dipentaerythritol hexaacrylate 5.4 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy) 2.0 Part sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part ethyl cellosolve 11.5 parts cyclohexanone 20.0 parts (method for producing colored composition for conductive blue filter)
Subsequently, the blue coloring composition and Vitron P (manufactured by Bayer, solid content: 1.3%) were mixed in the following composition to obtain a coloring composition for a conductive blue filter. The ratio of the solid content of Vitron P to the total solid content in the colored composition for the conductive blue filter is 5%.

Blue coloring composition 55.5 parts Vitron P 44.5 parts Comparative Example 1
In Example 1, the blue coloring composition before mixing Vitron P was designated as Comparative Example 1.

Example 2 and Example 3
In Example 1, a blue colored composition was prepared by replacing the photosensitive transparent resin solution, the non-photosensitive transparent resin solution, and the monomer as shown in Table 3 below, and the ratio of Vitron P shown in Table 3 (total solid content) A colored composition for a conductive blue filter was obtained in the same manner as in Example 1 except that the blending was carried out so that the solid content ratio was in the middle).

Comparative Example 2 and Comparative Example 3
In Example 2 and Example 3, the blue coloring composition before mixing Vitron P was set as Comparative Example 2 and Comparative Example 3.

Example 4
(Method for producing green pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.

Green pigment: C.I. I. Pigment Green 36 7.1 parts ("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Yellow pigment: C.I. I. Pigment Yellow 150 3.9 parts ("E4GN-GT" manufactured by Bayer)
1.0 part of a triazine pigment derivative represented by the following structural formula (4)

Photosensitive transparent resin solution obtained in Synthesis Example 1 10.0 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 7 30.0 parts Cyclohexanone 50.0 parts (Method for producing green coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition.

Green pigment dispersion 67.0 parts Photosensitive transparent resin solution obtained in Synthesis Example 1 2.0 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 7 3.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 1.4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts ethyl cellosolve 7.4 parts cyclohexanone 15.0 parts ( Method for producing colored composition for conductive green filter)
Next, the green coloring composition and Vitron P (manufactured by Bayer, solid content 1.3%) were mixed in the following composition to obtain a conductive green coloring composition. The ratio of the solid content of Vitron P to the total solid content in the conductive green coloring composition is 5%.

Green coloring composition 55.5 parts Vitron P 44.5 parts Comparative Example 4
In Example 4, the green coloring composition before mixing Vitron P was designated as Comparative Example 4.

Example 5
In Example 4, the photosensitive transparent resin solution, the non-photosensitive transparent resin solution, and the monomer were replaced as shown in Table 3 to prepare a green colored composition, and the ratio of Vitron P shown in Table 3 (in the total solid content) A colored composition for a conductive green filter was obtained in the same manner as in Example 4 except that it was blended so that the solid content ratio of

Comparative Example 5
In Example 5, the green coloring composition before mixing Vitron P was designated as Comparative Example 5.

Example 6
(Method for producing red pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion was prepared.

Red pigment: diketopyrrolopyrrole pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals) 11.0 parts 1.0 part of diketopyrrolopyrrole pigment derivative represented by the following structural formula (5)

Photosensitive transparent resin solution obtained in Synthesis Example 1 10.0 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 7 30.0 parts Cyclohexanone 50.0 parts (Manufacturing method of red coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a red colored composition.

Pigment dispersion 37.5 parts Photosensitive transparent resin solution obtained in Synthesis Example 1 11.8 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 7 12.2 parts Pentaerythritol triacrylate hexamethylene diisocyanate 4.1 Part photopolymerization initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 1.5 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 parts ethyl cellosolve 11.0 parts cyclohexanone 21.8 parts (Method for producing colored composition for conductive red filter)
Subsequently, the red coloring composition and Vitron P (manufactured by Bayer, solid content 1.3%) were mixed in the following composition to obtain a conductive red coloring composition. The ratio of the solid content of Vitron P to the total solid content in the conductive red coloring composition is 5%.

Red colored composition 57.8 parts Vitron P 42.2 parts Comparative Example 6
In Example 6, the red coloring composition before mixing Vitron P was designated as Comparative Example 6.

Example 7 and Example 8
In Example 6, the photosensitive transparent resin solution, the non-photosensitive transparent resin solution, and the monomer were replaced as shown in Table 3 to prepare a red colored composition, and the ratio of Vitron P shown in Table 3 (in the total solid content) The conductive red coloring composition was obtained in the same manner as in Example 6 except that the blending was performed so that the solid content ratio of

Comparative Example 7 and Comparative Example 8
In Example 7 and Example 8, the red coloring composition before mixing Vitron P was designated as Comparative Examples 7 and 8.

  The list of polyfunctional monomers used in the above Examples and Comparative Examples is shown in Table 2 below.

  About the coloring composition for electroconductive color filters obtained by the Example and the comparative example, electroconductivity was evaluated with the following method.

(Evaluation of conductivity of colored filter layer)
The colored composition for a color filter was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after pre-baking at 70 ° C. for 20 minutes, heat treatment was performed at 230 ° C. for 60 minutes to form a test colored filter layer.

  The surface resistance value of the colored filter layer was measured by a four probe method using Loresta AP manufactured by Dia Instruments. The four-probe method is a method in which the terminals of the energization circuit and the pickup circuit are separated and measurement is performed using four probes. The outer electrode pair is energized from a low current source, and the inner electrode pair is energized. Is a method of measuring the voltage between the two with an operational amplifier.

The obtained surface resistance values are shown in Table 3 below.

As apparent from Table 3 above, the filter layer using the colored composition for conductive color filter obtained in Examples 1 to 8 has a surface resistance value of at least 8.2 × 10 ⁷ Ω / □ or less. The filter layer using the colored compositions of Comparative Examples 1 to 8 exhibited a surface resistance value of at least 2.7 × 10 ¹⁴ Ω / □ and was sufficient. Conductivity was not obtained.

(Pattern defect test)
The colored filter layer was patterned by the following steps.

  First, a transparent substrate made of alkali-free glass on which a black matrix is formed is prepared, and the colored composition for conductive color filter obtained in Examples 1, 4, and 6 is used on the transparent substrate using a spin coater. The coating layer was formed by heating and drying at 70 ° C. for 1 minute.

  Next, a photomask having a stripe pattern formed of a Cr film was brought into close contact with the coating layer, and ultraviolet rays were exposed using an ultrahigh pressure mercury lamp as a light source.

  Thereafter, the unexposed portion was developed with a developer comprising an aqueous sodium carbonate solution, washed thoroughly with water, and further washed with water and dried. In this way, a patterned color filter layer was obtained on the transparent substrate.

  After the development, heat treatment was performed at 230 ° C. for 60 minutes and post-baked.

  This process is repeated until a pixel portion having a desired number of colors is formed, and the color filters of each color are patterned, and a plurality of color filter layers arranged in a pattern on a transparent substrate on which a black matrix is formed. Formed.

  The patterning process of the colored filter layer was performed 57 lots in 8 days, but no pattern defect occurred. One lot refers to a management unit of several hundreds of the same product type. In this case, one lot was 200 sheets.

  On the other hand, when 57 lots of pattern processing steps were performed in 8 days using the colored compositions obtained in Comparative Examples 1, 4, and 6, pattern defects occurred 9 times. In addition, cleaning must be performed to remove dust attached to the photomask.

  The color filter of the present invention can be used for, for example, a liquid crystal display, a plasma display, an electroluminescence panel, a color video camera, a digital camera, and the like.

Sectional drawing showing the structure of an example of the color filter of this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention Sectional drawing showing the structure of an example of the liquid crystal display device to which the color filter of this invention is applied

Explanation of symbols

    DESCRIPTION OF SYMBOLS 1,5 ... Board | substrate, 2, 2R, 2G, 2B, 11R, 11G, 11B ... Colored filter layer, 3 ... Black matrix, 4 ... Protective layer, 6 ... Colored photosensitive resin layer, 9 ... Photomask 10, 20 …Color filter

Claims (6)

  A coloring composition for a color filter in which a pigment is dispersed in a transparent resin, wherein the transparent resin contains a heteroatom-containing dielectric polymer.   The colored composition for a color filter according to claim 1, wherein the heteroatom-containing dielectric polymer is polyethylene dioxythiophene.   The colored composition for a color filter according to claim 1 or 2, wherein the heteroatom-containing dielectric polymer is contained in an amount of 2 to 60% by weight based on 100% by weight of the total solid content of the colored composition.   The colored composition for a color filter according to any one of claims 1 to 3, wherein the heteroatom-containing dielectric polymer has a volume resistivity value of 5 Ω · cm or less.   Furthermore, photosensitive resin is contained, The coloring composition for color filters of any one of Claim 1 thru | or 4 characterized by the above-mentioned.   A color filter comprising a plurality of colored filter layers formed by using the color filter coloring composition according to claim 1 and arranged in a pattern.

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