JP5028819B2 - Manufacturing method of color filter - Google Patents

Description

  The present invention relates to a method for producing a color filter for use in a liquid crystal display device and the like. More specifically, in a color filter in which each colored layer is printed by an ink jet method, each pixel having no mixed color or white spot defect is provided. The present invention relates to a method for producing a color filter having a flat and uniform colored layer.

A color filter used in a color liquid crystal display device or the like is an indispensable member for a color liquid crystal display device or the like, and has a role of improving the image quality of the liquid crystal display device or giving each pixel a color of each primary color. Yes. Various studies have been made on the manufacturing method of this color filter, and a photolithography method, an ink jet method, and the like are known as typical methods.
In the photolithography method, a coating film of a photosensitive resin layer of each color is formed on the entire substrate, and unnecessary portions of the coating film are removed later, and the remaining pattern is used as each color pixel. In this method, many of the coating films are unnecessary, and a large amount of materials such as pigments are wasted when manufacturing the color filter. In addition, since the exposure and development processes are performed for each color pixel, the number of processes increases.

  For this reason, the production of color filters by the photolithography method has problems in both cost and environment. In this respect, the ink jet method has recently attracted attention. In the production of a color filter by the ink jet method, each of the colors can be printed at the same time using three colored resin compositions of R, G, and B as inks. For this reason, there is little waste of material and the pixel formation process is shortened, so that it is possible to expect a reduction in environmental load and a significant cost reduction.

As a method for producing a color filter substrate using an ink jet method, methods described in Patent Documents 1 to 4 have been proposed. In Patent Document 1, in order to prevent the ink from spreading outside the desired colored layer region on the glass substrate, a pattern is formed by adding a hydrofluoric acid-based water / oil repellent to a black partition partitioning each pixel in advance. By doing so, it is described that the ink is fixed only in the pixel.
Patent Document 2 and Patent Document 3 describe that a black resin layer containing a fluorine-containing compound and / or a silicon-containing compound is used as a partition wall for bleeding in ink and preventing color mixing in a colored layer forming step. Has been.

  Further, Patent Document 4 discloses a substrate treatment in which a black matrix or pixel having a water / oil repellency on the surface is formed, and a pixel or a black matrix is formed by filling the space between the surfaces, and then the water / oil repellency is eliminated. The manufacturing method including the process is described. These methods do not require the step of imparting ink repellency to the partition wall surface after forming the partition walls, or imparting ink repellency to the pixels surrounded by the partition walls, and the number of processes is small. This can be said to be a very preferable method that can reduce the load and the manufacturing cost.

  However, in the above conventional method, when the baking temperature at the time of forming the partition wall is 170 ° C. or higher, the ink repellent agent is thermally decomposed and scattered, or the ink repellent agent bleeds out of the partition wall, Ink repellency is reduced, the substrate surface in the pixel surrounded by the partition wall is contaminated with an ink repellant, and a colored resin composition (hereinafter referred to as a colored layer) printed by an ink jet is whitened, The problem was that the shape of the pixel was not flat.

On the other hand, when the baking temperature at the time of forming the partition wall was 160 ° C. or lower, the partition wall had insufficient solvent resistance, and when an organic solvent-based ink was used, dissolution of the partition wall and color mixing occurred. Therefore, when using an organic solvent-based ink, the partition wall pattern is usually baked at 200 to 250 ° C., and the partition wall surface is surrounded by the ink repellency and the partition wall depending on the type and amount of the ink repellent agent contained in the partition wall. However, it was necessary to control the balance of the ink affinity (wetting property) of the substrate surface of the opening, but the margin was extremely narrow and adjustment was difficult.
JP-A-6-347637 JP-A-7-35915 JP 7-35917 A JP-A-7-248413 Japanese Patent Application No. 2005-209886

The present invention has been made in order to solve the above-mentioned problems.
Provided is a method for stably producing a color filter having a flat and uniform colored layer on each pixel, which is free from mixed colors and white defects, in a color filter on which each colored layer is printed by an ink jet method. It is.

Further, the present invention relates to a method for producing a color filter in which a colored layer is formed by ejecting ink into a pixel partitioned by a partition by an ink jet method, and 1) a material imparting ink repellency and a photosensitive resin. And a step of coating a photosensitive resin composition containing a thermosetting resin on a substrate to form a coating film, and 2) a step of pattern exposure and development on the coating film to form a partition wall pattern; 3) a) The partition wall pattern is subjected to light irradiation or radiation irradiation treatment to be photocured or radiation cured, and b) The partition wall pattern irradiated with light or radiation is subjected to heat treatment at a temperature of 140 ° C. or more and less than 160 ° C. forming a partition wall is thermally cured, 4) separated by the pixel partition wall, less the step of forming a colored layer by ejecting a pigment-dispersed ink organic solvent free from water by ink-jet method A method of manufacturing a color filter, characterized in that it also has.

Further, the present invention provides a method of manufacturing a color filter according to the invention, a method of manufacturing a color filter according to claim 1, characterized in that part or all of the partition wall is black.

  According to the present invention, the ink repellent agent in the partition wall can prevent scattering due to thermal decomposition and bleed out to the partition wall while having sufficient solvent resistance that does not dissolve in organic solvent-based inks. Even when an amount of the ink repellent agent is added, the substrate surface of the opening surrounded by the partition wall is not contaminated with the ink repellent agent, and white spots and color unevenness of the colored layer do not occur. For this reason, a highly reliable high-definition color filter that has sufficient margin to cope with material lot differences and process condition fluctuations and does not cause color mixing, white spots, or color unevenness can be stabilized. Could be manufactured.

Hereinafter, embodiments of the present invention will be described in detail.
According to the inventor's study, a photosensitive resin composition containing a material imparting ink repellency (ink repellent) is applied to a substrate, subjected to pattern exposure and development, and then irradiated with light or radiation. By photocuring or radiation curing the partition walls, thermal decomposition and bleeding out of the ink repellent agent are suppressed, and the ink repellency of the partition wall surface is maintained, and the substrate surface of the opening (inside the pixel) surrounded by the partition walls is maintained. A partition wall having solvent resistance that was not contaminated with an ink repellent and was not dissolved in an organic solvent ink was obtained.

  Furthermore, in this manufacturing method, even when a sufficient amount of ink repellent agent that does not mix colors is added, the ink affinity of the opening (inside the pixel) is maintained, so that the color layer is not mixed and white color is not lost. Wide range. Therefore, it has a sufficient margin to cope with material lot differences and process condition fluctuations, and there is no color mixing of pixels or white spots, it has a flat colored layer, and has good characteristics without color unevenness. A good color filter could be obtained.

  The present invention has been made based on such knowledge. FIG. 1 is a cross-sectional view of an example of a color filter manufactured by the method for manufacturing a color filter according to the present invention. 2 (a) to 2 (g) are explanatory views of a method for manufacturing a color filter according to the present invention. As shown in FIG. 2, the color filter manufacturing method according to the present invention first comprises partition walls 2 on a transparent substrate 1 in order to prevent color mixing of red (R), green (G), and blue (B) colored inks. Is provided. Furthermore, in order to improve the contrast of the color filter, it is desirable to provide light shielding properties to a part or all of the partition walls 2. In general, as a means for imparting light-shielding properties, a black material is used for a part or all of the partition walls to make it black. In the following description, part or all of the partition walls are referred to as a “black matrix” for convenience, but the black matrix does not necessarily have a black color.

Next, red (R), green (G), and blue (B) colored layers 3 are formed on the transparent substrate.
In the case of using this for liquid crystal, a transparent conductive layer and an alignment film layer are sequentially stacked, and for example, a counter substrate on which an electrode such as a thin film transistor is formed is disposed so as to face a liquid crystal display device. Hereinafter, the configuration of the transparent substrate, the black matrix, the red, green, and blue colored layers is referred to as a color filter. If necessary, a protective layer 4 can be provided on the color filter.

As described above, the colored layer 3 is provided in the opening between the black matrices, and usually the colored layer 3 composed of the three primary colors of the red colored layer (R), the green colored layer (G), and the blue colored layer (B). It is arranged in a desired shape. Examples of the general forming method include a pigment dispersion method, a dye method, an electrodeposition method, a printing method, a transfer method, and an ink jet method. In the present invention, the colored resin composition is patterned by an ink jet apparatus, and the colored layer 3 is formed through a heating process.

  For the transparent substrate 1 of the color filter, a known transparent substrate material such as a glass substrate, a quartz substrate, or a plastic substrate can be used. Among them, the glass substrate is excellent in transparency, strength, heat resistance, and weather resistance.

  The colored resin composition used for the colored layer 3 of the color filter can use a known material such as a colorant, a thermosetting resin, or a solvent, and is prepared by adding an additive such as a dispersant as necessary. be able to. As the colorant, a dye or a pigment can be used, but a pigment dispersion type is particularly preferable in terms of reliability such as heat resistance and weather resistance. Moreover, water-based and organic solvent-based solvents can be used as the solvent. However, the organic solvent is highly soluble in a wide range of resin compositions and can discharge an ink jet even at a high solid content concentration. It is particularly preferable to use

  Hereinafter, the formation of the black matrix will be described in detail. In the present invention, the black matrix is formed by a photolithography method. More specifically, a step of applying a photosensitive resin composition containing a material imparting ink repellency to a substrate, a step of pattern exposure and development to form a partition pattern, and light irradiation or radiation to the partition pattern. It is characterized by having at least a step of applying an irradiation treatment to light curing or radiation curing.

  In the step of coating the substrate with the photosensitive resin composition containing the material imparting ink repellency, the negative substrate, which will be described later, containing an ink repellant, which will be described later, is applied to the transparent substrate 1 that has been appropriately washed. The photosensitive resin composition is uniformly coated using a known coating apparatus such as a slit die coater or a spin coater. Then, in order to remove a solvent component, a reduced pressure drying process and a prebaking process can be performed as needed. In this case, when a fluorine-based ink repellent agent is used, the ink repellent agent dispersed in the coating film has a property of gradually segregating on the surface of the coating film. The segregation state of the ink repellent agent changes depending on the time until completion and the conditions. Therefore, in order to obtain the partition wall 2 with uniform performance, it is desirable to keep the time interval from coating to vacuum drying or pre-baking and the conditions thereof uniform in this step.

  In the step of forming the barrier rib pattern by pattern exposure and development, the barrier rib pattern can be formed by a conventionally known exposure and development method.

  In the step of performing light irradiation or radiation irradiation treatment on the partition pattern to perform photocuring or radiation curing, the partition pattern is cured by irradiating ultraviolet rays or electron beams from the upper surface of the transparent substrate 1. The light or radiation to be irradiated is not particularly limited as long as it has an absorption wavelength at which the photosensitive resin composition is cured, but ultraviolet rays or electron beams are particularly preferable. However, those containing a wavelength that promotes the decomposition of the ink repellent agent are not preferable because the decomposed ink repellent agent contaminates the substrate surface of the opening.

  It is desirable to cut unnecessary wavelengths through an appropriate filter. Ultraviolet irradiation treatment with an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp or the like is particularly preferable. In the present invention, in this step, the thermal decomposition and bleed-out of the ink repellent agent are suppressed as much as possible, and the partition wall 2 is cured until solvent resistance that does not dissolve in organic solvent ink is obtained. Thus, it is possible to prevent color mixing, white spots, and color unevenness when the colored layer is formed.

Further, when the black matrix formed of the photosensitive resin composition containing the ink repellent agent is a light shielding layer having a light shielding property, the surface of the partition wall 2 is cured in the light irradiation treatment, but is shielded from light. It may not harden to the inside. In that case, a step of performing heat treatment at a temperature of 160 ° C. or lower to be thermally cured can be provided. As a heating method, a hot air circulation type oven, a hot plate, heating by infrared rays, or the like can be used, and is not particularly limited.
However, when heated at a temperature of 160 ° C. or higher, even if the surface of the partition wall 2 is light-cured or radiation-cured in the previous step, scattering of the ink repellent agent and bleed-out are observed on the substrate surface of the opening. When the colored layer 3 is formed, white spots and flatness are deteriorated, which is not preferable. The heating temperature for thermosetting is preferably suppressed to 160 ° C. or lower.

  Here, the partition walls 2 are preferably formed with a height of 1.0 μm or more. Furthermore, it is more preferable to form with a height of 1.5 μm to 5 μm. When the height of the partition wall 2 is 1.0 μm or less, color mixing of colored inks occurs. On the other hand, when the height of the partition wall 2 is too high, it is not preferable because it is difficult to form a fine black matrix and a step with the colored layer 3 becomes large.

  The partition wall 2 may have a single-layer structure or a multilayer structure including two or more layers. In general, the height of the black matrix that can be formed in a single process is limited, so that when the partition wall 2 having a large layer thickness is formed, a black matrix having the same pattern can be stacked to form a multilayer structure. . When the black matrix has a multilayer structure, it is preferable that at least one of the layers is provided with a light shielding property to form a light shielding layer. At least the uppermost layer in the case of a multilayer structure is preferably formed as described above using a photosensitive resin composition containing an ink repellent agent.

On the transparent substrate 1 on which the partition walls 2 are formed as described above, three colored inks are printed by a known ink jet method to form a colored layer 3 and baked to obtain a color filter. Here, the firing conditions are preferably heating at 100 ° C. to 250 ° C. for 10 minutes to 60 minutes, and particularly preferably heating at 150 ° C. to 230 ° C. In this baking, the black matrix is completely cured together with the colored ink, and sufficient resistance as a color filter is obtained.
In addition, since the ink repellent agent for the partition walls 2 is thermally decomposed during the firing, the ink repellency is already lowered when the protective layer 4 and the like are formed in the next step. Further, in order to completely remove the ink repellent agent of the partition wall 2, it is possible to provide a process such as cleaning with a solvent or detergent, UV irradiation with a low-pressure mercury lamp or excimer UV irradiation, polishing and the like.

Hereinafter, components and materials contained in the photosensitive resin composition used for forming the black matrix will be described in detail.
The photosensitive resin composition in the present invention is a negative photosensitive resin composition, the main components of which are composed of a binder resin, a radically polymerizable compound, a photopolymerization initiator, a solvent, an ink repellent, and a light-shielding member. Further, a melamine derivative and a photoacid generator can be added.
First, as the binder resin, an alkane-soluble thermosetting resin is preferable, and specific examples include a cresol-novolak resin, a polyvinylphenol resin, an acrylic resin, and a methacrylic resin. These binder resins may be used alone or in combination of two or more. Moreover, in order to accelerate | stimulate sclerosis | hardenability at low temperature, in addition to these resins, a melamine derivative and a photo-acid generator can also be contained. The melamine derivative may be a compound having a methylol group or a methoxymethyl group, but is particularly preferably a compound having high solubility in a solvent.

As the compound having radical polymerizability in the present invention, for example, a monomer or oligomer having a vinyl group or an allyl group, or a polymer having a vinyl group or an allyl group at the terminal or side chain can be used. Specifically, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, Mention may be made of N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof. Examples of suitable compounds include relatively low molecular weight polyfunctional acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and hexaacrylate. Can be, but this is not the case. These radically polymerizable compounds may be used alone or in combination of two or more. The amount of the compound having radical polymerizability can be in the range of 1 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder resin.

  In the present invention, the photopolymerization initiator generates radicals upon exposure and crosslinks the binder resin through a compound having radical polymerizability. Specific examples of the photopolymerization initiator include benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylacetophenone, 2,2 Acetophenone derivatives such as 2-dimethoxy-2-phenylacetophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, thioxanthone, 2,4-diethylthioxanthone, 2-isopropyl Thioxanthone derivatives such as thioxanthone, 2-chlorothioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as chloroanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether derivatives such as phenyl ether, acylphosphine derivatives such as phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, 2- (o-chlorophenyl) -4,5-bis (4′-methyl) Lophine isomers such as phenyl) imidazolyl dimer, N-aryl glycines such as N-phenylglycine, organic azides such as 4,4′-diazidochalcone, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarboxy) benzophenone, quinonediazide group-containing compounds, and the like. These photopolymerization initiators may be used alone or in combination of two or more. The quantity of a photoinitiator can take the range of 0.1-50 weight part with respect to 100 weight part of binder resin, Preferably it is 1-20 weight part.

A melamine derivative and a photoacid generator can be added to the photosensitive resin composition. When a melamine resin and a photoacid generator are added, the binder resin undergoes a crosslinking reaction with the melamine derivative, so that it is sufficiently cured even when heated at a low temperature. Therefore, the effect of suppressing the elution and bleeding of the ink repellent agent is exhibited. Moreover, since it heats at low temperature, there exists an effect which the cross-sectional shape of a partition pattern does not heat-sag. The melamine derivative may be a compound having a methylol group or a methoxymethyl group, but is particularly preferably a compound having high solubility in a solvent.
Examples of melamine derivatives include Gee, Tri, Tetra, Penter, Hexamethylol Melamine, Gee, Tree, Tetra, Penter, Hexamethylol Melamine, or Melamine Compounds such as Gee, Tree, Tetra, Penter, Hexamethylol Melamine, Or the melamine derivative obtained by making these compounds react with formaldehyde etc. can be mentioned. These melamine derivatives may be used alone or in combination of two or more.
The amount of the melamine derivative can be in the range of 1 to 50 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is less than 5 parts by weight, there is a problem that the resin of the partition wall dissolves in the colored ink of the ink jet. When the amount exceeds 30 parts by weight, the development cannot be performed.

A photo-acid generator accelerates | stimulates the dehydration reaction and crosslinking reaction of a melamine derivative and binder resin by the effect | action of the acid generate | occur | produced when exposing. Among the photoacid generators, those having particularly high solubility in a solvent are preferred.
As an example, specifically, diphenyliodonium, ditolyliodonium, phenyl (4-anisyl) iodonium, bis (3-nitrophenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (4-chlorophenyl) iodonium Diaryl iodonium such as bis (4-n-dodecylphenyl) iodonium, 4-isobutylphenyl (4-tolyl) iodonium, 4-isopyrphenyl (4-tolyl) iodonium, or triarylsulfonium such as triphenylsulfonium Triarylsulfonium chloride, bromide, or borofluoride, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate Salts, sulfonium organic boron complex salts such as diphenylphenacylsulfonium (n-butyl) triphenylborate, 2-methyl-4,6-bistrichloromethyltriazine, 2- (4-methoxyphenyl) -4, Triazine compounds such as 6-bistrichloromethyltriazine, 2- {2- (5-methylfuran-2-yl) ethenyl} -4,6-bis (trichloromethyl) -s-triazine, or 1,2-naphthoquinonediazide, 1 , 2-Naphthoquinonediazido-4-sulfonsan sodium, 1,2-naphthoquinonediazido5-sulfonic acid sodium, 1,2-naphthoquinonediazido-4-sulfonic acid ester derivative, 1,2-naphthoquinonediazido5-sulfonic acid Diazonaphthoquinone compounds such as ester derivatives And the like can be given.
The addition amount of the photoacid generator can be in the range of 1 to 50 parts by weight, preferably 3 to 30 parts by weight with respect to 100 parts by weight of the binder resin.

  Specific examples of solvents include dichloromethane, dichloroethane, chloroform, acetone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxyacetate, 2-butoxyethyl acetate. 2-methoxyethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2′ethoxyethoxy) ethyl acetate, 2- (2-butoxy) Ethoxy) ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran and the like can be used. The amount of the solvent used is preferably a coating that is homogeneous when applied onto the substrate and can form a coating film without pinholes and uneven coating. The amount of solvent is 50 with respect to the total weight of the photosensitive resin composition. It is preferable to prepare so that it may become -97weight%.

  The light shielding member imparts light shielding properties to the black matrix and improves the contrast of the color filter. As the light shielding member, black pigment, black dye, carbon black, aniline black, graphite, iron black, titanium oxide, inorganic pigment, and organic pigment can be used. These light shielding members may be used alone or in combination of two or more.

  Furthermore, the ink repellent used in the present invention imparts ink repellency to the colored ink on the black matrix. The ink repellent agent can be added in advance to the photosensitive resin composition used for forming the black matrix. As the ink repellent agent, a fluorine-containing compound or a silicon-containing compound can be used, and it is more preferable to use a mixture thereof. Specific examples of the fluorine-containing compound include vinylidene fluoride, vinyl fluoride, ethylene trifluoride and the like, and fluororesins such as copolymers thereof.

  In particular, the fluorine-containing copolymer having a mass average molecular weight of 10,000 to 100,000 is particularly preferable in the present invention in order to achieve both the ink repellency on the black matrix surface and the ink affinity on the surface of the opening base material. Specifically, the fluorine-containing copolymer described in Japanese Patent Application No. 2005-209886 is exemplified. These fluorine-containing compounds can be used alone or in combination of two or more.

Examples of the silicon-containing compound include organic silicon in a main chain or a side chain, and examples thereof include a silicon resin containing a siloxane component and silicone rubber. These silicon-containing compounds can be used alone or in combination of two or more. Further, the fluorine-containing compound and the silicon-containing compound, or other ink repellent components may be used in combination. The amount of the fluorine-containing compound or silicon-containing compound contained in the photosensitive resin composition in the present invention is preferably 0.1% by weight to 10% by weight with respect to the total part by weight.
In addition, the photosensitive resin composition used for forming the black matrix has compatible additives as necessary, for example, a leveling agent, a chain transfer agent, a stabilizer, a sensitizing dye, a surfactant, a coupling agent, and the like. Can be added.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to this form.

<Comparative Examples 1-5>
(Create black matrix)
As the photosensitive resin composition containing a material imparting ink repellency, a photosensitive resin composition blended at the following composition ratio and sufficiently kneaded with three rollers was used. As the transparent substrate, non-alkali glass (“# 1737” manufactured by Corning) was used, and this photosensitive resin composition was applied thereon and pre-baked at 90 ° C. for 2 minutes to form a film having a thickness of 2.0 μm. .
[Photosensitive resin composition A]
・ Cresol-novolak resin “EP4050G” (Asahi Organic Materials Co., Ltd.)
20 parts by weight, 80 parts by weight of cyclohexanone, 23 parts by weight of carbon pigment “MA-8” (manufactured by Mitsubishi Materials), and “Solsperse # 5000” (manufactured by Zeneca) 1.4 parts by weight of compound having radical polymerizability “Trimethylolpropane triacrylate” (manufactured by Osaka Organic Chemical Co., Ltd.)
5 parts by weight of photopolymerization initiator “Irgacure 369” (manufactured by Ciba Specialty Chemicals)
2 parts by weight / fluorine-containing compound “Modiper F-200” (manufactured by NOF Corporation, mass average molecular weight 35000) 0.5 parts by weight Next, using a photomask having a lattice pattern, 100 mJ / A cm ² exposure was performed and a development process was performed. Subsequently, heat treatment was performed in an oven for 20 minutes under the temperature conditions shown in Table 1.

Subsequently, when the OD value (optical density) of the black matrix was measured, it was 6, and it was confirmed that any of them could be used as a black matrix because it had sufficient light shielding properties. The definition of the OD value is shown below. When the visible light is transmitted through a 1 μm sample, the incident light intensity is I ₀ , and the transmitted light intensity is I.
OD value = -log (I / I ₀ )
In addition, when colored ink was printed on the transparent substrate having the black matrix by using an ink jet apparatus, in Comparative Examples 1 to 5, either a white spot or a mixed color defect occurred. Further, in Comparative Examples 1 to 3 where the heating temperature was low, the black solvent swelled or dissolved or the black matrix surface unevenness occurred due to the ink solvent.

<Examples 1-3 and Comparative Examples 6-8>
In the preparation of the above black matrix, Comparative Example 1 except that after the development treatment, after the ultraviolet irradiation treatment of 1000 mJ / cm ² with a high-pressure mercury lamp, the heat treatment was carried out in an oven for 20 minutes under the temperature conditions shown in Table 2. In the same manner as in No. 5, a black matrix was formed.
When the OD value (optical density) of the black matrix was measured, it was 6. Since it had sufficient light-shielding properties, it was confirmed that any of them could be used as a black matrix.

  Subsequently, the amount of fluorine on the surface of the black matrix and the glass surface of the opening printed by the ink jet was analyzed by TOF-SIMS and shown in Table 2. The amount of fluorine is shown as a percentage (%) of the elemental fluorine with respect to the total amount of element detected. It can be seen that the amount of fluorine on the surface of the opening glass increases as the heating temperature increases.

  Moreover, when colored ink was printed on the transparent substrate having the black matrix by using an ink jet apparatus, white spots occurred in Comparative Examples 6 to 8. On the other hand, in Examples 1 to 3, neither white spots nor mixed colors occurred, and no unevenness occurred on the surface of the black matrix, and a good color filter was obtained.

<Examples 4 to 6 and Comparative Examples 9 to 11>
(Create black matrix)
As the photosensitive resin composition containing a material imparting ink repellency, a photosensitive resin composition blended at the following composition ratio and sufficiently kneaded with three rollers was used. As the transparent substrate, non-alkali glass (“# 1737” manufactured by Corning) was used, and this photosensitive resin composition was applied thereon and pre-baked at 90 ° C. for 2 minutes to form a film having a thickness of 2.0 μm. .
[Photosensitive resin composition B]
・ Poly (4-vinylphenol) "Marlinker MS-1" (manufactured by Maruzen Petrochemical Co., Ltd.)
20 parts by weight, 80 parts by weight of cyclohexanone, 23 parts by weight of carbon pigment “MA-8” (manufactured by Mitsubishi Materials), and “Solsperse # 5000” (manufactured by Zeneca) 1.4 parts by weight of compound having radical polymerizability "Trimethylolpropane triacrylate" (manufactured by Osaka Organic Chemicals Co., Ltd.) 5 parts by weight, photopolymerization initiator "Irgacure 369" (manufactured by Ciba Specialty Chemicals)
2 parts by weight and fluorine-containing compound “F179” (Dainippon Ink Chemical Co., Ltd., mass average molecular weight 10,000)
0.5 parts by weight Next, using a photomask having a lattice pattern, 100 mJ / cm ² exposure was performed with an ultrahigh pressure mercury lamp, and development processing was performed. Subsequently, after performing an electron beam irradiation treatment of 25 Mrad, heat treatment was performed in an oven for 20 minutes under the temperature conditions shown in Table 3. When the OD value (optical density) of the black matrix was measured, it was 6. Since it had sufficient light-shielding properties, it was confirmed that any of them could be used as a black matrix.

  Moreover, when colored ink was printed on the board | substrate which has this black matrix using the ink jet apparatus, the white spot generate | occur | produced in Comparative Examples 9-11. On the other hand, in Examples 4 to 6, no white spots or mixed colors occurred, and no unevenness occurred on the surface of the black matrix, and a good color filter was obtained.

<Examples 7 to 8>
(Create black matrix)
As the transparent substrate, alkali-free glass (“# 1737” manufactured by Corning) was used.
Further, a photosensitive resin composition having the following composition ratio was sufficiently kneaded with three rollers, and then applied to a film thickness of 2.0 μm.
[Photosensitive resin composition C]
・ Cresol-novolak resin “EP4050G” (Asahi Organic Materials Co., Ltd.)
20 parts by weight / melamine resin “MX-706” (manufactured by Sanwa Chemical Co., Ltd.) 4 parts by weight / radical polymerizable compound “trimethylolpropane triacrylate” (manufactured by Osaka Organic Industries)
5 parts by weight, carbon pigment “MA-8” (manufactured by Mitsubishi Materials) 23 parts by weight, dispersant “Solsperse # 5000” (manufactured by Zeneca) 1.4 parts by weight, fluorine-containing compound “F179” (Dainippon Ink Chemical) 0.5 parts by weight After that, the transparent substrate was pre-baked, and then exposed to 100 mJ / cm ² with an ultrahigh pressure mercury lamp using a photomask having a lattice pattern, and developed. Subsequently, the partition wall pattern was exposed to 1000 mJ / cm ² with an ultra-high pressure mercury lamp, and heat-treated in an oven for 20 minutes under the temperature conditions shown in Table 4.
Subsequently, when the OD value (optical density) of the black matrix was measured, it was 6, and it was confirmed that any of them could be used as a black matrix because it had sufficient light shielding properties.

  Moreover, when colored ink was printed on the board | substrate which has this black matrix using an ink jet apparatus, the black matrix produced in Examples 7-8 did not generate | occur | produce neither a white spot nor a color mixture, but on the surface of a black matrix. An excellent color filter was obtained without causing unevenness.

Hereinafter, the process of forming a colored layer using an ink jet apparatus in the above-described embodiment will be described in detail.
(Preparation of colored ink)
0.75 parts by weight of azobisisobutylnitrile was added to the following composition under a nitrogen atmosphere and reacted at 70 ° C. for 5 hours to obtain an acrylic copolymer resin.
-20 parts by weight of methacrylic acid-10 parts by weight of methyl methacrylate-55 parts by weight of butyl methacrylate-15 parts by weight of hydroxyethyl methacrylate-300 parts by weight of butyl lactate

The obtained acrylic copolymer resin was diluted with propylene glycol monomethyl ether acetate so as to be 10% by weight with respect to the whole to obtain a diluted solution of the acrylic copolymer resin.

  Add 19.0 g of color pigment and 0.9 g of polyoxyethylene alkyl ether as a dispersant to 80.1 g of this diluted solution, and knead with three rolls to obtain red, green and blue colored varnishes. It was. As a red pigment, Pigment Red 177, Pigment Green 36 as a green pigment, and Pigment Blue 15 as a blue pigment were used.

  Propylene glycol monomethyl ether acetate is added to each colored varnish so that the pigment concentration is 12 to 15% by weight and the viscosity is 15 cps, thereby obtaining red, green and blue colored inks. It was.

  Specific examples of the color pigment added to the diluent include Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 215, 216, 208, 216, 217, 220, 223, 224, 226, 227, 228, 240, Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64, Pigment Green 7, 36, Pigment Red 20, 24 86, 93, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, 185, Pigment Orange 36, Pigment Violet 23, etc. Or mix two or more To be able to use.

As the solvent used in the colored ink, a solvent having a surface tension in a range suitable for the ink jet system, for example, 40 mN / m or less and a boiling point of 130 ° C. or more can be preferably used. If the surface tension exceeds 40 mN / m, there is a tendency to have a significant adverse effect on the stability of the dot shape during ink jet ejection, and if the boiling point is less than 130 ° C., the drying property near the nozzle becomes remarkably high. Therefore, there is a tendency to cause defects such as nozzle clogging.
Suitable solvents include, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether, 2- (2 -Ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol, and diethylene glycol dimethyl ether. If necessary, they can be used alone or in combination of two or more. In addition to solubility, the solvent is required to have stability over time, drying property, and the like, and is appropriately selected according to the characteristics of the colorant and binder resin used.

The above-mentioned colored ink can contain the following binder resins.
Examples of the binder resin for the colored ink include casein, gelatin, polyvinyl alcohol, carboxymethyl acetal, polyimide resin, acrylic resin, epoxy resin, and melamine resin, and can be appropriately selected according to the colorant used. For example, acrylic resin is preferable when heat resistance and light resistance are required.
A dispersant can be added to improve the dispersion of the pigment in the binder resin of the colored ink. Examples of the dispersant include a nonionic surfactant such as polyoxyethylene alkyl ether, and examples of the ionic surfactant include sodium alkylbenzene sulfonate, poly fatty acid salt, fatty acid salt alkyl phosphate, and In addition to tetraalkylammonium salts, organic pigment derivatives, polyesters, and the like can be given. A dispersing agent can be used individually or in mixture of 2 or more types.
The colored layers for each color can be adjusted according to the height of the black matrix, and can be formed with a thickness of 1 μm to 2 μm, for example.
(Production of color filter)
In the above embodiment, red (R), green (G), and red (R), green (G), and red (green) and blue (pi) colored inks are used for a transparent substrate having a black matrix, and a 12 pl and 180 dpi head is mounted. Each colored layer of blue (B) was formed.

  The color filters obtained in Examples 1 to 8 were free from white spots and color mixing, had good smoothness, and measured ΔEab in the pixels. As a result, all were less than 1, and good color filters with little color unevenness I found out that ΔEab (color difference) was measured with a microanalyzer.

It is explanatory drawing of the cross-sectional shape of the color filter provided with the black matrix of this invention. It is explanatory drawing of the color filter manufacturing method of this invention.

Explanation of symbols

1 ... Transparent substrate 2 ... Partition (black matrix)
DESCRIPTION OF SYMBOLS 3 ... Colored layer 4 ... Protective layer 5 ... Light irradiation or radiation irradiation 6 ... Photomask 7 ... Ink jet apparatus R ... Red colored layer G ... Green colored layer B ... Blue colored layer

Claims (3)

In the manufacturing method of the color filter that discharges ink by the ink jet method to form the colored layer in the pixels delimited by the partition walls,
1) a step of applying a photosensitive resin composition containing a material imparting ink repellency , a photosensitive resin, and a thermosetting resin to a substrate to form a coating film;
2) A step of pattern exposure and development on the coating film to form a partition wall pattern;
3) a) The partition pattern is subjected to light irradiation or radiation irradiation treatment to be photocured or radiation cured,
forming a partition wall b) the partition wall pattern light irradiation or irradiation subjected to a heat treatment at a temperature less than 140 ° C. or higher 160 ° C. is thermally cured,
4) Production of a color filter comprising at least a step of forming a colored layer by discharging an organic solvent-based pigment-dispersed ink that does not contain water by an ink jet method into pixels separated by the partition walls Method. The method for producing a color filter according to claim 1, wherein a part or all of the partition walls are black. The partition pattern has a multilayer structure of one layer or two or more layers, and the uppermost layer of the one layer or the multilayer structure is formed using a photosensitive resin composition containing an ink repellent agent. The manufacturing method of the color filter of Claim 1 or 2 .