JP2008209936A - Method for manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter by which a high definition color filter can be manufactured at a low cost. <P>SOLUTION: The method for manufacturing the color filter is characterized in that a colored layer pattern is formed by a screen printing method by using an ink composition for forming the colored layer containing pigment in a range of 24 to 95 wt.% by a solid content ratio. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a color filter used in a full-color liquid crystal display device or the like using a screen printing method.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having a high specific gravity.

  In such a color filter, it is usually provided with coloring patterns of three primary colors of red (R), green (G), and blue (B), and electrodes corresponding to the respective pixels of R, G, and B are turned on, By turning it off, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed.

  As a conventional method for producing a color filter, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.

  Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.

  However, in any method, it is necessary to repeat the photolithography process three times in order to color the three colors of R, G, and B, and there is a problem that the cost increases, and the yield decreases because the process is repeated. There's a problem.

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a color filter manufacturing method capable of manufacturing a high-definition color filter at low cost.

In order to achieve the above object, as described in claim 1, the present invention uses a colored layer forming ink composition containing a pigment within a range of 24 wt% to 95 wt% in terms of solid content. A method for producing a color filter for forming a patterned colored layer by a screen printing method, wherein the screen printing plate used in the screen printing method is filled in the gap between the ridge and the surface of the ridge is flattened. There is provided a method for producing a color filter, comprising: a planarizing layer; and a back cushion layer formed on a substrate-side surface of the planarizing layer. In the present invention, since the color filter is produced by the screen printing method, the pigment can be contained at a high concentration within the above-described range in the colored layer forming ink composition of the color filter. . Therefore, it is possible to manufacture a color filter with good color developability.
Further, by forming the back cushion layer in this way, a very good plate separation is achieved due to the resilience of the back cushion layer after screen printing. As a result, it is possible to prevent problems such as adhesion of the back side of the ink for forming the colored layer, so that it is possible to exhibit very high resolution during screen printing and form a high-definition colored layer pattern. Can do.
In the invention described in claim 1, as described in claim 2, it is preferable that the hardness of the back cushion layer is in a range of 30 to 65 in terms of needle penetration hardness. This is because the rebound of the back cushion layer can be set to an optimum value by setting the back cushion layer to a hardness within the above-described range.

  In the invention described in claim 1 or 2, as described in claim 3, the first adhesive layer is provided between the back cushion layer and the planarizing layer, The hardness is preferably less than 30 in terms of needle penetration hardness. Since the back cushion layer needs to have a predetermined hardness, the back cushion layer may have poor adhesion to the planarization layer filled and formed in the ridge. Further, although depending on the material and physical properties of the flattening layer, the back cushion layer needs to be in close contact with the substrate in order to prevent the back side during transfer during screen printing. In order to cope with such a necessity, it is preferable to form the first adhesive layer having the hardness in the above-described range.

  In the invention described in any one of claims 1 to 3, as described in claim 4, a photosensitive polymer layer is provided on a surface opposite to the substrate of the planarization layer. Preferably it is formed. Thus, by forming the photosensitive polymer layer on the surface opposite to the substrate, it is possible to improve the resolution during development. Therefore, a color filter having a high-definition colored layer pattern can be manufactured.

  In the invention described in any one of claims 1 to 4, as described in claim 5, a dry film resist may be used for the back cushion layer. This is because, since the back cushion layer is relatively thick, it may be preferable to use such a dry film rather than applying and applying a coating liquid.

  In the invention described in any one of claims 1 to 5, as described in claim 6, the actual printing region in the screen printing ridge used in the screen printing plate The wrinkle bias angle at is preferably 31 ° or more and less than 45 °. In the present invention, by setting the wrinkle bias angle, which has conventionally been 23 ° to 24 °, within the above-described range, ink can be satisfactorily dropped into the wrinkle, thereby enabling formation of a high-definition colored layer pattern. Because it becomes.

  In the invention described in the sixth aspect, as described in the seventh aspect, it is preferable that a mesh opening width of the screen printing ridge is in a range of 5 μm to 85 μm. This is because it is preferable to use a ridge having a mesh opening width as described above in order to form a colored layer pattern of a high-definition color filter.

  In the invention according to any one of claims 1 to 7, as described in claim 8, the ridge is a metal ridge, and the surface of the metal ridge on the substrate side is ground. And is preferably flattened. As described above, the back cushion layer needs to be in close contact with the substrate during printing. Therefore, by grinding and flattening the surface on the substrate side in this way, the back cushion layer formed on the surface can be adhered in parallel to the substrate. This is because it is possible to prevent the back of the ink around the back surface and to form a higher-definition colored layer pattern.

In the invention described in any one of claims 1 to 8, as described in claim 9, the colored layer forming ink composition includes at least a binder component and the binder component. When the rotational viscometer measurement method is used as the viscosity measurement method, the measurement part is measured at a temperature condition of 23 ° C. using a cone-disk type sample container. The measured value at a shear rate of 10 S ⁻¹ is in the range of 30,000 MPa to 100,000 MPa, and the measured value at the shear rate of 20 S ⁻¹ is in the range of 2,000 MPa to 7,000 MPa. A certain colored layer forming ink composition is preferred.

By using such a colored layer forming ink composition, the viscosity in a state where ink is dropped by a squeegee, that is, in a shear rate of 20S ⁻¹ (high speed state) is within the relatively low viscosity range as described above. Ink can be accurately dropped into the screen printing plate. In addition, since the viscosity at a state where the ink is transferred from the screen printing plate to the substrate, that is, at a shear rate of 10S ⁻¹ (low speed state) is in the relatively high viscosity range as described above, the ink is used for screen printing during the transfer. There is no problem of rotating around the back of the plate, and accurate transfer can be performed. Therefore, it is possible to form a high-definition colored layer pattern.

  In the invention described in claim 9, as described in claim 10, the binder component has a monomer component represented by the following chemical formula (1) within a range of 5 mol% to 95 mol%. And an acrylic copolymer having a monomer component represented by the following chemical formula (2) within a range of 5 mol% to 85 mol% and a weight average molecular weight in terms of polystyrene within a range of 10,000 to 1,000,000. A polymer is preferred.

(Here, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms. R ₁ is an aromatic or alicyclic compound.)
This is because, by using such an acrylic copolymer as a binder, it is possible to pattern a colored layer with higher definition.

  In the invention described in claim 10, as described in claim 11, the colored layer forming ink composition comprises an epoxy acrylate resin composition in a solid content weight ratio of 3 wt% to 55 wt%. It is preferable to contain within the range. Thus, the adhesiveness with respect to the base material of the ink composition for forming a colored layer is improved by including the epoxy acrylate resin composition.

  In the invention described in the tenth or eleventh aspect, as described in the twelfth aspect, the ink composition for forming a colored layer contains a polyfunctional acrylic acrylate monomer and a photopolymerization initiator. Preferably there is. This is because such a composition can be cured by exposure after screen printing, which is advantageous in terms of process.

  In the invention described in any one of claims 1 to 12, as described in claim 13, the width of the colored layer line to be obtained is in the range of 5 μm to 100 μm. Is preferred. This is because the feature of the present invention lies in the formation of such a high-definition colored layer pattern.

  In the present invention, since the color filter is produced by the screen printing method, the pigment can be contained at a high concentration in the color layer forming ink composition of the color filter. Therefore, it is possible to manufacture a color filter with good color developability. In addition, compared with the conventional pigment dispersion method, there is no photolithography process, so problems such as waste of raw materials and disposal of waste liquid do not occur. Furthermore, since the shape of the cross section of the colored layer obtained is a tapered shape, the possibility of disconnection or the like can be reduced when a transparent electrode layer or the like is formed thereon. Furthermore, when the obtained color filter is used in a liquid crystal display device, since the colored layer is formed without going through a photolithography process, there is an advantage that there is no impurity such as an alkali component, and thus the voltage holding ratio is high. I have it.

  As described above, the present invention includes a color filter manufacturing method and a color filter. These will be described separately.

A. Method for Producing Color Filter The method for producing a color filter of the present invention uses a colored layer forming ink composition containing a pigment in a solid content ratio of 24% by weight to 95% by weight, and is patterned by screen printing. The colored layer is formed.

  Since the method for producing a color filter of the present invention forms a colored layer pattern by the screen printing method as described above, the pigment content in the colored layer forming ink composition is set within the above-described range. It becomes possible. Thereby, it is possible to obtain a color filter that is highly transparent and excellent in color developability. In addition, the colored layer formed by the screen printing method is generally formed in a taper shape such that the width on the substrate side is wide and the width gradually decreases toward the surface side. Therefore, even when an ITO electrode or the like is formed thereon, for example, it is possible to reduce the possibility of disconnection. Furthermore, the color filter obtained by the method for producing a color filter of the present invention does not require a development step by a photolithography method, and therefore has a very low possibility of containing impurities. Therefore, when it is used as a liquid crystal display device, it has an advantage that it does not contain impurities that adversely affect the liquid crystal material in the liquid crystal layer (for example, a decrease in voltage holding ratio) as a colored layer.

1. Ink composition for forming colored layer In the method for producing a color filter of the present invention, a color layer forming ink composition suitable for screen printing is used in producing the color filter.

(1) Viscosity The viscosity of the ink composition for forming a colored layer used in the present invention is not particularly limited, but as a measured value at a shear rate of 10S- ¹ measured at a temperature condition of 23 ° C, Preferably it is in the range of 30,000 MPa to 100,000 MPa, and particularly preferably in the range of 60,000 MPa to 80,000 MPa.

The viscosity measured at 23 ° C. at a shear rate of 10S ⁻¹ is a state in which the colored layer forming ink composition has already been dropped into the screen printing plate during screen printing in the production of a color filter. That is, it corresponds to the viscosity in a low speed state. Therefore, when the viscosity is larger than the above range, it is not preferable because the colored layer forming ink composition filled in the screen printing plate may not be removed during transfer. On the other hand, when the viscosity is smaller than the above range, it is not preferable because there is a possibility that the colored layer forming ink composition filled in the screen printing plate may wrap around the back of the screen printing plate.

Furthermore, the measured value at a shear rate of 20 S ⁻¹ measured at a temperature condition of 23 ° C. in the ink composition for forming a colored layer used in the present invention is not particularly limited, but is preferably 2,000 MPa. It is preferably in the range of ˜7,000 MPa, particularly preferably in the range of 3,000 MPa to 5,000 MPa.

The viscosity measured at the temperature condition of 23 ° C. at a shear rate of 20S ⁻¹ is a state in which the colored layer forming ink composition is dropped into the screen printing plate by a squeegee at the time of screen printing at the time of manufacturing the color filter, that is, high speed It is to make the viscosity in the state. Therefore, when the viscosity is larger than the above range, it is not preferable because the ink may not be completely dropped into all the holes in the screen printing plate by the squeegee. The ink composition for forming a colored layer enters between the printing plate and the squeegee, which may cause problems such as an increase in printing resistance.

As the viscometry, in the rotation viscometer measurements, the shape of the measurement section is a cone - with sample containers of the disc type, measurements and shear rate at the shear rate 10S ^-1 of viscosity measured at temperature 23 ° C. The measured value at 20S- ¹ was determined as a predetermined range.

  Specifically, a rotational viscometer is used. The rotational viscometer is classified into a double cylinder type, a cone-disk type, a parallel disk type, and the like according to the shape of the measurement unit. For each, a shear rate and a shear stress are required, but the double cylinder type and the parallel disk type have a drawback that the shear rate cannot be uniquely determined in the sample container. On the other hand, when the viscosity is different depending on the shear rate, the cone-disk type is better than the parallel disk type having a different shear rate depending on the distance from the center. For details and measurement methods, etc., “Rheology for chemists” (Shigeharu Onoki, Kagaku Doujin, 1982) and this measurement method are well known in accordance with academic societies. Takeshi, Ichiro Watanabe, 10, 147, (1982)).

(2) Composition The colored layer forming ink composition used in the present invention has at least a pigment and a binder component.

a. Pigment In this colored layer forming ink composition, a pigment is blended in a solid content ratio of 24 wt% to 95 wt%, preferably 25 wt% to 93 wt%, particularly 27 wt%. It is preferable that it is mix | blended within the range of% -90 weight%. When the pigment content is higher than the above range, the viscosity of the colored layer forming ink composition is too high, and it may not be possible to sufficiently fill the ink in the holes of the screen printing plate during screen printing. . On the other hand, when the content of the pigment layer is lower than the above range, it is not preferable because there is a possibility that a color filter having high color developability cannot be obtained.

  The pigment used in the present invention is preferably a finely divided pigment in a processed pigment, for example, at least one resin selected from the group consisting of acrylic resin, vinyl chloride-vinyl acetate copolymer, maleic acid resin and ethyl cellulose. A powder or paste product produced by dispersing.

  Red pigments are, for example, anthraquinone type pigments alone, perylene type pigments alone or mixtures of at least one of them, and diazo type yellow pigments or isoindolinone type yellow pigments, in particular CI Pigment Red 177 alone, CI Pigment Red 155 Alone or at least one of CI Pigment Red 177, CI Pigment Red 155 and CI Pigment Yellow 83 or CI Pigment Yellow 139 ("CI" refers to the Color Index known to the public and publicly available) Contains a mixture.

  Other suitable examples of pigments are CI Pigment Red 105, 144, 149, 176, 177, 185, 202, 209, 214, 222, 242, 254, 255, 264, 272 and CI Pigment Yellow 24, 31, 53 , 83, 93, 95, 109, 110, 128, 129, 138, 139, 166 and CI Pigment Orange 43.

  Green pigments are, for example, halogenated phthalocyanine type pigments alone or mixtures with diazo type yellow pigments or isoindolinone type yellow pigments, in particular CIPigment Green 7 alone, CI Pigment Green 36 alone, CI Pigment Green 37 alone, or CI Contains a mixture of Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 136 and CI Pigment Yellow 83 or CI Pigment Yellow 139. Other suitable green pigments are C.I. Pigment Green 15 and 25.

  Suitable examples of blue pigments are phthalocyanine type pigments used alone or in combination with dioxazine type purple pigments, for example C.I. Pigment Blue 15: 3 and C.I. Pigment Violet 23. Another example of a blue pigment is, for example, C.I. Blue 15: 3, 15: 4, 15: 6, 16 and 60, ie phthalocyanine CI Pigment Blue 15: 3 or phthalocyanine C.I. Pigment Blue 15: 6. Other suitable pigments are, for example, C.I. Pigment Blue 22, 28, C.I. Pigment Violet 14,19, 23, 29, 32,37, 177 and C.I. Orange 73.

  In the present invention, combinations of two or more pigments can also be used. Particularly suitable for color filters are powder-like processed pigments produced by finely dispersing the pigment in a resin.

b. Binder Component As another essential component of the colored layer forming ink composition used in the present invention, a binder component can be exemplified.

  The binder component in the present invention is not particularly limited as long as the fine particles are dispersed, but those having the above-described viscosity characteristics after the pigment is dispersed are preferable. For example, a polymer material dissolved in a solvent may be used as a binder, and the solvent may be removed in a subsequent process. Alternatively, a monomer component may be used as a binder and cured in a subsequent process. A combination of these may also be used.

(Acrylic copolymer)
In the present invention, an acrylic copolymer is preferably used as the binder component that is preferably used. This is because when an acrylic copolymer is used as a binder, photopolymerization can be easily imparted by using a photopolymerization initiator, a polyfunctional acrylate monomer, or the like as described later.

  In the present invention, it is particularly preferable that the monomer component represented by the following chemical formula (1) is contained.

  Here, R in the chemical formula (1) (the same applies to the chemical formula (2)) is hydrogen or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, and n- Examples include propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like.

  Examples of the monomer component used for introducing the monomer component represented by the chemical formula (1) include acrylic acid, methacrylic acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, and 2-carboxy-1. -Hexene, 2-carboxy-1-heptene and the like are exemplified. The content of the monomer component represented by the chemical formula (1) is within the range of 5 mol% to 95 mol%, particularly within the range of 10 mol% to 85 mol%, and particularly within the range of 15 mol% to 70 mol%. It is preferable that

  Moreover, it is preferable that the acrylic copolymer used for this invention contains the monomer component shown by following Chemical formula (2) at least.

Here, examples of R ₁ in the chemical formula (2) include aromatic and alicyclic compounds such as a phenyl group and a naphthyl group. Monomers used for introducing this structural unit include styrene and α-methylstyrene, and the aromatic ring is a halogen atom such as chlorine or bromine, or an alkyl group such as a methyl group or an ethyl group. , An amino group such as an amino group or a dialkylamino group, a cyano group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

  The monomer component represented by the chemical formula (2) is a component that improves mechanical properties such as hardness in the acrylic copolymer used in the present invention.

  In the present invention, the content of the monomer component represented by the chemical formula (2) is adjusted according to the physical properties required for the printed matter obtained by screen printing, and is in the range of 5 mol% to 85 mol%, particularly 7 mol. It is preferable to set it within the range of% to 80 mol%, particularly within the range of 10 mol% to 75 mol%.

  As long as it has at least the monomer component shown by the said Chemical formula (1) and Chemical formula (2) as an acrylic copolymer used for this invention, the other monomer component may be contained. For example, urethane acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate, epoxy acrylate, and alkoxy acrylate are used.

  The molecular weight of the acrylic copolymer obtained by polymerizing the monomer components as described above is 10,000-1 in terms of polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight” or “Mw”). It is preferably in the range of 000,000, particularly preferably in the range of 20,000 to 100,000.

  This is because when the weight average molecular weight is out of the above range, the viscosity may not fall within the above range when the colored layer forming ink composition is used.

(Method for producing acrylic copolymer)
As the monomer components represented by the chemical formulas (1) and (2) described above, those exemplified above may be used alone or in combination.

  As a polymerization solvent used for producing a specific polymer having such monomer components represented by the chemical formulas (1) and (2) and other monomer components added as necessary, hydroxyl, amino Solvents having no active hydrogen such as a group are preferable, for example, ethers such as tetrahydrofuran; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; cellosolv esters such as methyl cellosolve acetate and propylene glycol monomethyl ether acetate And 3-methoxybutyl acetate, and aromatic hydrocarbons, ketones, esters and the like can also be used.

  As the polymerization initiator, those generally known as radical polymerization initiators can be used, and specific examples thereof include 2,2′-azobisisobutyronitrile, 2,2 ′. -Azo compounds such as azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, tert-butylperoxypivalate , Organic peroxides such as 1,1′-bis- (tert-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used as a redox polymerization initiator in combination with a reducing agent.

  In such a method for producing an acrylic copolymer, a molecular weight regulator can be used to adjust the weight average molecular weight, for example, halogenated hydrocarbons such as chloroform and carbon tetrabromide, n- Examples thereof include mercaptans such as hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid, xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide, terpinolene and α-methylstyrene dimer.

  Moreover, the acrylic copolymer obtained may be any of the above-described chemical formulas (1) and (2), and random copolymers and block copolymers of other monomer components added as necessary. .

  In the case of a random copolymer, the blended composition composed of each monomer component and catalyst is dropped in a polymerization tank containing a solvent over a period of 2 to 5 hours at a temperature of 80 to 110 ° C., and then aged. It can be polymerized.

(Other binder components)
Although the example of the said acrylic copolymer is a preferable example when making it photocurable, in this invention, it is not limited to photocurable, It is a film | membrane after hardening as a thermosetting resin composition. A binder component that can maintain strength can also be used.

  Examples include polycarbonate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, diethylene glycol bisallyl carbonate, acrylonitrile / styrene copolymer, poly (-4-methylpentene-1), and the like.

  Further, in order to improve the elasticity and impact resistance of the ink, a modified epoxy resin such as acrylonitrile, a modified epoxy combined with a butadiene copolymer (NBR), a chloroprene resin, and a cyanogen to improve the adhesive strength. In order to improve acrylate resins and water-based applications, styrene / butadiene emulsion copolymers, ethylene / vinyl acetate emulsion copolymers, acrylic acid esters or methacrylic acid esters, butadiene emulsion copolymers, etc. are used. Also good. Furthermore, polyurethane resin, alkyd resin, cyclized rubber, chlorinated polyolefin, polyester resin, or the like may be added.

c. Other components Other components of the ink composition for forming a colored layer used in the present invention include the following.

(Multifunctional acrylic acrylate monomer)
When the above acrylic copolymer is used as a binder component, it can be said that it is preferable because it can be made photocurable by using a polyfunctional acrylate monomer together with a photopolymerization initiator described later. This is because the color filter can be produced by a simple process after screen printing because photopolymerizability can be imparted to the applied colored layer forming ink composition. Further, since the curing can be completed by exposure as described above, it is possible to prevent the base material from being deteriorated by heat as compared with the case of thermosetting. In particular, it is preferable in the case of a resin substrate.

  Examples of such bifunctional or higher polyfunctional photopolymerizable acrylate monomers include dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), pentaerythritol triacrylate (PETTA), and trimethylolpropane triacrylate (TMPTA). ), Trimethylolpropane triacrylate (TMPTA) ethylene oxide 3 mol adduct, ethylene oxide 6 mol adduct, propylene oxide 3 mol adduct, propylene oxide 6 mol adduct, and the like.

  Other examples include isobutyl acrylate, t-butyl acrylate, stearyl acrylate, 2-methoxyethyl acrylate, and 3-methoxybutyl acrylate.

  In the present invention, when the polyfunctional acrylic acrylate monomer is added, the solid content ratio in the colored layer forming ink composition is 3% to 50% by weight, preferably 5% to 20% by weight. Contained.

(Photopolymerization initiator)
In this invention, it can be said that it is preferable to use a photoinitiator with the said polyfunctional acrylate monomer for the same reason as what was demonstrated in the said polyfunctional acrylate monomer.

  Specific examples include halomethylated triazine derivatives, halomethylated oxadiazole derivatives, imidazole derivatives, and benzophenone derivatives. These photopolymerization initiators are compounds capable of generating radicals that polymerize a polymerizable group of a photopolymerizable monomer with ultraviolet rays, and are used alone or in combination.

  As such a photopolymerization initiator, 2-methyl-1- [4-methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,4-diethylthioxanthone, 4,4-bis Examples include diethylaminobenzophenone. Such a polymerization initiator is preferably contained in the ink composition for forming a colored layer in a solid content ratio of 0.1 wt% to 20 wt%.

  Furthermore, in order to react the polymerizable compound rapidly by light irradiation, it is common to add another photopolymerization initiator, a sensitizer or a dye. Such a photopolymerization initiator is preferably dissolved or compatible with the polymerizable compound and mixed uniformly. Examples of such a photopolymerizable initiator include anthraquinones such as benzophenone, benzoin alkyl ether, Michler's ketone, benzyl, benzyl dialkyl ether, and tertiary butyl anthraquinone, and thioxanthone derivatives such as chlorothioxanthone and isopropylthioxanthone. Further, a photopolymerization accelerator such as p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester may be mixed. These are effective in increasing the polymerization curing rate when a benzophenone system or a thioxanthone system is used. The said photopolymerizable initiator is mix | blended in the ratio of 1-10 weight part generally with respect to 100 weight part of compounds which have an ethylenically unsaturated group.

(Epoxy acrylate resin composition)
In the present invention, an epoxy acrylate resin composition may be added to improve the adhesion to the substrate.

  Examples of the epoxy acrylate resin composition that can be used in the present invention include an ortho cresol novolak type, a bisphenol A novolak type, a phenol novolak type, a bisphenol A type epoxy resin, a cresol novolak type epoxy resin, and the like.

  Such an epoxy acrylate resin composition is preferably contained in the colored layer forming ink composition in a solid content ratio of 1 to 20% by weight, preferably 3 to 15% by weight. When the content of the epoxy acrylate resin composition is less than the above range, sufficient adhesion cannot be imparted between the colored layer and the substrate, while the content of the epoxy acrylate resin composition is within the above range. On the other hand, the storage stability and development suitability of the colored layer forming ink composition are lowered, which is not preferable.

  The epoxy acrylate resin composition is also effective for removing the tack of the dried coating film of the colored layer forming ink composition, and a sufficient effect is exhibited at an addition amount of about 3% by weight.

  In this invention, it replaces with the said epoxy acrylate resin composition, or it adds with the component shown by following Chemical formula (3) which improves adhesiveness with a base material by using with the said epoxy acrylate resin composition. preferable.

(Here, X represents a methyl group or a hydrogen atom, and R ₂ represents an alkyl group or a hydroxyalkyl group.)
Specific examples of such compounds include partially epoxy-modified acrylate EB3605 (UVAC 1561, manufactured by Daicel UCB Co., Ltd.) that can be used in combination with a cation, and epoxy epoxy acrylate that can improve adhesion to metal. RDX63182 (manufactured by Daicel Industries, Ltd.), Ebecryl 168 (manufactured by Daicel Industries, Ltd.) which is an acid-containing methacrylic compound, and examples of combinations of novolac epoxy acrylate and polyfunctional acrylate monomers include EB629, 30% TMPTA and Examples include those based on 5% HEMA, those based on EB1629, 40% TMPTA and 28% HEMA, and those based on EB3603 and 20% tripropylene glycol diacrylate (TPRGDA).

  The component represented by the chemical formula (3) is preferably contained in the ink composition for forming a colored layer in a solid content ratio of 1 to 65% by weight, preferably 5 to 55% by weight. . This is because if the amount added is less than the above range, the substrate adhesion and ink elasticity based on the epoxy group are low, resulting in a decrease in plate separation and ink transfer efficiency. In addition, when the addition amount is larger than the above range, the degree of curing of the ink film is too high, resulting in partial cracking and warping due to stress due to drying by UV and / or heat after pattern formation. Further, when the epoxy content is increased, the transparency is impaired, and since it is colored pale yellow, there is a possibility that accurate coloring cannot be obtained.

(Dispersant)
In the present invention, since a relatively large amount of pigment is preferably dispersed in the binder component, a dispersant is preferably used. Specifically, styrene / butyl styrene copolymer, long-chain polyaminoamide phosphate, polyamide, high molecular weight polycarboxylate, oleylamine acetate, tetraalkylammonium salt, sodium oleate, aminooleate oleate, phosphate ester Examples thereof include salts and alkylbenzene sulfonates. Such a dispersant can be contained in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the fine particles.

(solvent)
Moreover, as a solvent used for the ink composition for forming the colored layer, as long as the additive component is dispersed or dissolved as desired and does not react with these components, it has an appropriate volatility. Can be appropriately selected and used.

  Examples of such solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Ethylene glycol monoalkyl ether acetates such as monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol such as diethylene glycol mono-n-butyl ether Glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, Ethyl acetate, n-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyrate -Other esters such as butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene, xylene; N- Carbohydrates such as methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide And acid amides. These solvents can be used alone or in admixture of two or more.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate Further, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination. These high boiling point solvents can be used alone or in admixture of two or more.
Among the solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, i-propyl butyrate, ethyl butyrate, n-butyl butyrate, ethyl pyruvate Preferably, also mineral spirits as a high-boiling solvent, petroleum naphtha S-100, petroleum naphtha S-0.99, tetralin, turpentine oil, .gamma.-butyrolactone and the like are preferable. The usage-amount of a solvent is 100-10,000 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 500-5,000 weight part.

(Other)
In the ink composition for forming a colored layer used in the present invention, an additive component usually contained in this type of photosensitive resin composition can be optionally added. As such optional additive components, as with other printing inks, additives, antifoaming agents, leveling agents, pigment dispersants, etc. for imparting mechanical performance such as friction resistance and blocking resistance are added. can do. The most characteristic auxiliary in the screen ink is a thixotropy imparting agent for rheology modification. As the thixotropic agent, vegetable oils, surfactants, swollen waxes, extender pigments and the like used in paints are used. Further, a surface component for suppressing or eliminating foaming generated when the printing plate is separated from the printing surface and providing a smooth printing surface promptly is an essential component. In addition, matting agents, slip agents, ultraviolet absorbers, plasticizers, effect accelerators, and the like are used in some inks. In addition, a photopolymerization initiator (sensitizer) and a polymerization inhibitor are used for the UV curable ink.

2. Screen printing method The color filter production method according to the present invention is characterized in that the color layer is produced by printing on a substrate by the screen printing method using the ink composition for forming a colored layer as described above. is there. Hereinafter, the screen printing method used in the present invention will be described.

a. Screen printing wrinkle The screen printing wrinkle used in the method for producing a color filter of the present invention has a wrinkle bias angle in an actual printing region having a predetermined angle larger than the angle of a conventionally used wrinkle. Is preferred.

  In the present invention, it is possible to form a high-definition colored layer pattern by increasing the wrinkle bias angle in the actual printing region in this way.

  Hereinafter, such a screen printing bag will be described in detail.

(紗 bias angle)
In the present invention, the wrinkle bias angle of the screen printing wrinkle is preferably 31 ° or more and less than 45 °, and particularly preferably in the range of 33 ° to 39 °.

  Here, the wrinkle bias angle indicates an angle that is half of the angle on the acute angle side among the facing angles of the parallelogram formed by the wrinkle wire. This saddle bias angle will be described with reference to FIG. FIG. 1 is a plan view showing a conventional wrinkle. A wrinkle 32 is constituted by a wire 31, and an emulsion 33 formed in a pattern is provided on the wrinkle 32. In screen printing, ink is dropped in a portion where the emulsion 33 is not formed, and printing is performed on the substrate. The wrinkle bias angle in the present invention refers to an angle β that is half of the angle on the acute angle side among the opposing angles of the parallelogram α formed by the wire 31. In the present invention, a high-definition pattern can be formed by the screen printing method by setting the wrinkle bias angle β to a predetermined angle larger than the conventional one.

  In the present invention, the wrinkle bias angle indicates an angle in the actual printing area. Here, the actual print area indicates a part of the cocoon that is actually used for pattern formation, and specifically excludes an area that is not directly related to pattern formation in the vicinity of the cocoon frame. It is.

  As described above, in the present invention, it is possible to form a high-definition pattern by setting the heel bias angle in the above-described range. The reason for this is not clear, but Presumed to be the reason.

  In other words, by changing the heel angle to the wide angle side, the ink drops better and the openings during ink filling are less likely to occur. As a result, the amount of ink used to form a high-definition pattern is suppressed from passing. It is presumed that the opening rate of the cocoon to secure the

(Material of firewood)
In the method for producing a color filter of the present invention, it is necessary to form a very high-definition pattern. Therefore, a metal cocoon, a polyester cocoon, and a combination cocoon are preferably used as the cocoon material.

(Tail tension)
In the present invention, the tension of the screen printing gauze, preferably in the range of 1000N / mm ² ~3500mm ^2, in particular in the range of 1500N / mm ² ~3000mm ² is preferred. This is because it is possible to form a higher-definition pattern by using a heel having a heel bias angle as described above and applying a tension within the above range.

  The screen mesh is preferably 150 mesh to 800 mesh, particularly 250 mesh to 650 mesh.

(Aperture opening width)
In the present invention, since it is necessary to form a very high-definition colored layer pattern on the substrate as described above, the opening width of the screen printing ridge used is also a width that meets this purpose. preferable. Specifically, it is preferably in the range of 1 μm to 150 μm, particularly in the range of 3 μm to 100 μm.

b. Next, a screen printing plate used in the method for producing a color filter of the present invention will be described. A screen printing plate used in the present invention includes a ridge, a planarization layer that fills the gap between the ridges and planarizes the surface of the ridge, and a back cushion layer formed on the substrate-side surface of the planarization layer. The back cushion layer has a predetermined hardness.

  In the present invention, since the back cushion layer having a predetermined hardness is formed on the surface of the flattening layer on the substrate side, it is possible to achieve good separation by utilizing the elasticity of the back cushion layer during printing. it can. Therefore, good plate separation can be realized, and an extremely high-definition colored layer pattern can be formed by screen printing.

  FIG. 2 shows an example of such a screen printing plate. A flattened layer 2 is formed around the metal cage 1 to fill the gaps in the metal cage 1. A back cushion layer 4 is formed on the surface of the flattening layer 2 on the substrate side via the first adhesive layer 3. On the other hand, a photosensitive polymer layer 6 is formed on the surface of the planarizing layer 2 opposite to the base material via a second adhesive layer 5.

  All of the flattening layer 2, the first adhesive layer 3, the back cushion layer 4, the second adhesive layer 5, and the photosensitive polymer layer 6 are patterned in the same pattern, and the through holes 7 are formed. At the time of printing, the color filter is manufactured by filling the through hole 7 with the ink composition for forming the colored layer and transferring the ink composition onto the surface of the substrate.

  Hereinafter, the screen printing plate used in the method for producing a color filter of the present invention will be described in detail for each configuration.

(Back cushion layer)
As described above, the first feature of the screen printing plate used in the present invention is that a back cushion layer is formed on the base material side surface of the ridge.

  In the present invention, the back cushion layer has a needle penetration hardness of 30 to 65, particularly 33 to 60, and preferably 35 to 55. When the hardness is smaller than the above range, it is not preferable because the separation of the plate is deteriorated and the back of the ink may be generated. On the other hand, if the hardness is higher than the above range, it is not preferable because the back cushion layer cannot follow the movement of the heel and cracks may occur.

  Further, the film thickness of the back cushion layer is preferably in the range of 1 μm to 150 μm, particularly in the range of 3 μm to 100 μm. When the film thickness is thinner than the above range, the function as the back cushion layer cannot be exhibited, and the separation of the plate is deteriorated, which may cause the back of the ink and the like. On the other hand, when the film thickness is thicker than the above range, it is difficult to maintain pattern accuracy during pattern formation by photolithography, and as a result, it may not be possible to form a high-definition pattern, which is not preferable. .

  As is apparent from the example shown in FIG. 2, such a back cushion layer has a shape in which through-holes are formed in the same pattern as that of the planarization layer and are patterned in the same manner. At this time, in the case where a photosensitive polymer layer is formed on the surface opposite to the substrate side of the planarizing layer, the same patterning is performed on this photosensitive polymer layer.

  The back cushion layer preferably has a smooth surface. This is because if the surface is uneven, ink may ooze into the recess during transfer, which is not preferable.

  Furthermore, in the present invention, the back cushion layer is preferably formed so that the surface of the base material and the surface of the back cushion layer are parallel when in close contact with the base material. If it is not parallel at the time of transfer, it means that a gap is formed, and there is a possibility that the colored layer forming ink composition oozes out into the gap and a high-definition pattern cannot be formed.

  As a material for forming such a back cushion layer, for example, a copolymer with polyhydroxystyrene (Hitachi Chemical Co., Ltd.), as a positive type semiconductor resist, OFPR series, OFPR-800 (Tokyo Ohka Co., Ltd.) ), AZ series (Hoechst Co., Ltd.), NR-polymer (Mitsubishi Rayon Co., Ltd.), cationic curing resin, Epolide PB, Celoxide 2021P (all of which are Daicel UCB Co., Ltd.), UV1530, UV1534, UV1533 , Uvacure 1561, 1562, 1502, 1591 and the like.

  In addition, the back cushion layer in the present invention can be formed using a dry film resist. Since this back cushion layer has a predetermined film thickness, it is preferable to use a dry film resist advantageous in terms of process.

(For screen printing)
As the screen printing basket used in the present invention, those described in the above section “a. Screen printing basket” can be preferably used, but the screen printing basket is not particularly limited thereto.

  In the present invention, it may be preferable to flatten the ridges from the viewpoint of flatness of the back cushion layer. This will be described below.

  In the present invention, when a metal rivet is used, it is preferable to grind and flatten the surface of the heel on the substrate side. That is, for example, as shown in FIG. 3, one surface side of the metal rod 21 is flattened by a method such as performing a calendar smoothing process.

  The surface of the back cushion layer can be made smooth by arranging the ridges so that the flattened surface becomes the substrate side, forming the flattened layer, and providing the back cushion layer thereon. Because it becomes.

  Such a heel smoothing process depends on the distance between the meshes, but can be ground and flattened up to about one third of the diameter of the metal rivet wire.

(Flattening layer)
In the present invention, a flattening layer filled in the gap is formed on the ridge. This flattening layer may be the same as the emulsion used in conventional screen printing plates, but is not limited to this, so that the wrinkles can be smoothed as much as possible. It is preferable to be formed with an appropriate material and film thickness.

  The film thickness of such a flattened layer is preferably in the range of 14 μm to 50 μm, although it depends on the wire diameter of the ridge structure and the film thickness of the ridge.

  In addition, as described above, the material for forming such a flattening layer is an emulsion used in conventional screen printing, specifically, an aqueous emulsion sensitizer such as a polyester-acrylic aqueous emulsion or an aqueous epoxy resin. Epoxy resin water-based emulsions containing a rubber elastic emulsion copolymer and a curing agent, and modified epoxy emulsion polymer emulsions in which a high nitrile acrylonitrile-butadiene copolymer is bonded to an epoxy resin can be used. In addition, a styrene / butadiene emulsion copolymer system, an ethylene / vinyl acetate emulsion copolymer system, an acrylate ester, or a methacrylate ester / butadiene emulsion copolymer emulsion can be used.

(First adhesive layer)
In the present invention, a first adhesive layer may be formed between the planarizing layer and the back cushion layer. This is because the adhesion between the back cushion layer and the planarization layer can be improved by forming the first adhesive layer in this way. Furthermore, by forming the first adhesive layer with a low-hardness material as will be described later, it becomes possible to serve as a cushion for the back cushion layer at the time of transfer, and to improve the separation of the back cushion layer. In addition, the back cushion layer and the base material can be brought into close contact with each other at the time of transfer.

  As described above, the hardness of the first adhesive layer is preferably relatively low. Specifically, the needle penetration hardness is less than 30, preferably in the range of 10 to 28, particularly in the range of 15 to 25. Preferably there is. When the hardness is higher than the above range, it is not preferable because it cannot serve as a cushion for the back cushion layer as described above, and when the hardness is lower than the above range, there may be a problem in strength. Is not preferable.

  The film thickness of the first adhesive layer in the present invention is preferably in the range of 1 μm to 100 μm, particularly in the range of 3 μm to 70 μm. Further, as a matter of course, it is preferable that the first adhesive layer is patterned in the same pattern as the back cushion layer and the planarizing layer to form a through hole.

  The planarization layer may be formed of the same material as the first adhesive layer. Specifically, by forming the flattening layer thick and selecting a material to be used, it may be formed of a material having an appropriate hardness range and good adhesion to the back cushion layer. For example, the first adhesive layer and the planarizing layer may be the same.

  In the present invention, as described above, the material for forming the first adhesive layer is a material having good adhesion between the back cushion layer and the planarization layer and having a predetermined hardness range. Specific examples include, but are not limited to, acrylic types such as urethane acrylate, polyester acrylate, and silicon acrylate, and non-acrylic types such as unsaturated polyester / styrene and polyene / styrene. Of these, the acrylic type is preferred because of the wide range of UV curing rate and physical properties. Furthermore, in terms of elasticity, those having an appropriate molecular weight such as an oligomer and those having a mass average molecular weight (Mw) of about 5000 to 15000 are preferable.

(Photosensitive polymer layer)
In the present invention, a photosensitive polymer layer may be formed on the surface opposite to the substrate side of the planarizing layer. This is because by forming the photosensitive polymer layer in this way, it becomes possible to form a screen printing plate with a much higher definition than in the conventional screen printing plate. Further, by selecting the material of the photosensitive polymer layer, the solvent resistance can be improved and the printing durability can be further improved, so that the life of the screen printing plate can be greatly improved.

  The material for forming such a photosensitive polymer layer is not particularly limited as long as it has good developability and good printing durability and solvent resistance.

3. Color Filter According to such a method for producing a color filter of the present invention, an extremely high-definition colored pattern can be formed on a substrate by a screen printing method, and a high-quality color filter can be obtained. it can.

  As such a pattern of the colored layer, the width of the colored layer line is preferably within a range of 5 μm to 100 μm, particularly within a range of 7 μm to 85 μm, and more preferably within a range of 10 μm to 35 μm. This is because such a high-definition colored layer pattern is formed by a screen printing method.

  Since the thickness of the colored layer in the present invention is formed by screen printing, it can be very wide, specifically within the range of 1 μm to 30 μm, preferably 1 μm to It is preferably within a range of 10 μm, especially within a range of 2 μm to 7 μm, particularly within a range of 3 μm to 5 μm.

  The base material used in the method for producing the color filter of the present invention is not particularly limited as long as it is a transparent base material, and even if it is a base material having no flexibility such as glass, a transparent resin Even a flexible substrate such as a film-made film can be used. However, it is preferable to use a transparent base material having flexibility from the viewpoint of the extent of future application development.

  Specifically, thermoplastic elastomer, biaxially stretched polyester film (PET), biaxially stretched nylon film (ONY), biaxially stretched polypropylene film (OPP), unstretched polypropylene film (CPP), unstretched nylon film (CNY) In addition, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene film, ethylene copolymer film, ethylene-vinyl alcohol copolymer film, polysulfone film, cellulosic film, etc. Various transparent films are used. A glass plate or a plastic plate may be used.

  The substrate is usually a single layer, but may be a multilayer. Further, the thickness of the substrate is not particularly limited, but is usually about 6 to 300 μm, and generally 12 to 160 μm.

  In the method for producing a color filter of the present invention, the colored layer forming ink composition as described above is printed in a pattern on the substrate as described above using a screen printing method. Usually, the color filter is composed of three primary colors of red, green and blue. In the present invention, the color filter is formed by performing screen printing three times using the ink composition for forming a colored layer of the above three colors. To do.

B. Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter in which a colored layer is formed in a pattern on a substrate, and the line width of the colored layer is in the range of 5 μm to 100 μm, and the pigment concentration of the colored layer In the range of 30 wt% to 95 wt% (first embodiment), and a color filter in which a colored layer is formed in a pattern on a substrate, the colored layer Are formed by a screen printing method, and the line width of the colored layer is in the range of 5 μm to 100 μm (second embodiment).

  The first embodiment is characterized in that a high-definition colored layer pattern is formed on the substrate, and the pigment concentration of the colored layer is extremely high. Thus, since the density | concentration of the pigment contained in a colored layer is very high, it can have a very high color developability as a color filter.

  Although the manufacturing method of the color filter of this embodiment is not specifically limited, It can be manufactured by the screen printing method mentioned above.

  On the other hand, the second embodiment is characterized in that a high-definition colored layer pattern is formed on a substrate by a screen printing method. Therefore, compared with those manufactured by a conventional pigment dispersion method, there are advantages that there is no waste of materials and that there is no problem of waste liquid treatment at the time of manufacture. Furthermore, since the shape is tapered as described above, there is no fear of disconnection even when a transparent electrode layer is formed thereon. In addition, since a colored layer can be formed without passing through a photolithography process, when a color filter is used in a liquid crystal display device, there is an advantage that a voltage holding ratio is good.

  Also in the color filter of the second embodiment, the pigment concentration of the colored layer is preferably in the range of 30 wt% to 95 wt%. This is because, within this range, the color developability is extremely good and a high-definition pattern can be formed.

  The colored layers of the color filters of the first embodiment and the second embodiment are preferably prepared so that the NTSC ratio is 60% or more, particularly 65% or more. This is because, by using this range, practicality can be exhibited when used as a color display device.

  Here, the NTSC ratio means the ratio (%) of the area of the color triangle as a coordinate comparison for a certain color with respect to the area of the color triangle of the three primary colors defined by NTSC (National Television System Committee; USA). A larger NTSC ratio means a wider color reproduction range.

  Reflecting the recent improvement in quality of color imaging tube elements and color liquid crystal display devices and the expansion of applications, display panels are strongly required to have high brightness. The brightness of the display panel is evaluated by the stimulus value (Y) of white balance, and this stimulus value (Y) also correlates with a color reproduction range that is an indicator of a displayable color tone range. That is, if the color reproduction range is to be expanded, the pigment concentration has to be increased, but the white balance stimulation value (Y) is reduced accordingly. Therefore, in order to achieve high brightness of the display panel, it is a big problem to increase the white balance stimulation value (Y) as much as possible without reducing the NTSC ratio. For example, the NTSC ratio is 44%. When the color filter is manufactured, it is required that the white balance stimulation value (Y) be 37 or more. Therefore, various studies have been made to increase the white balance stimulation value (Y) for each of the blue, red, and green radiation-sensitive compositions. Even if the stimulation value (Y) in the color system can be increased, in the case of a blue radiation-sensitive composition, the stimulation value (Y) in the CIE color system is sufficient, and the stimulation value (Y) in white balance is sufficient. It is difficult to increase as much as possible, and in the color filter used in the conventional display panel, when the NTSC ratio is 44%, the stimulation value (Y) of the white balance is at most about 35. Therefore, there is a strong demand for a material that can provide a display panel having high luminance and a sufficient color reproduction range for a colored ink composition that gives a pixel of blue, in particular, red and green.

  The color reproducibility of liquid crystal display devices for desktop monitors is about 50% to 65% compared to NTSC (National Television System Committee), whereas LCD televisions require wider color reproducibility of 60% to 75%. Is done. In addition, liquid crystal televisions are required not only to increase color reproducibility, but also to match each of the red, green, and blue color tones with conventional CRT televisions. The color characteristics of a conventional CRT television are red, green, blue, and chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each color are red (0.640, 0.330) and green (0. 290, 0.600) and blue (0.150, 0.060), which is almost equivalent to the European Broadcasting Union (EBU) standard. Further, the color temperature in white display of the conventional CRT television is set to about 9000K to 10000K, which is higher than the color temperature in white display of the liquid crystal display device for desktop monitor. A liquid crystal television also requires a high color temperature for white display. FIG. 4 is a graph showing the chromaticity coordinates (x, y) and the color temperature in white display in the XYZ color system chromaticity diagram of each color of red, green, blue.

  Liquid crystal display devices usually perform color display by combining a three-wavelength type backlight light source and a color filter, but the conventional combination of a backlight light source and a color filter performs the color reproducibility, color tone, and whiteness required for a liquid crystal television. Nothing satisfying the color temperature in the display was obtained. Specifically, there are problems such as (1) the color reproduction range is narrow, (2) the chromaticity of each pixel is greatly deviated from the chromaticity of the EBU standard, and (3) the color temperature in white display is low. It was.

  On the other hand, when a backlight light source having a high color temperature (about 10,000 K) is used to improve the color temperature in white display, and a liquid crystal display device is manufactured in combination with a color filter for a conventional desktop monitor, Overall, the color is dragged by blue, and the color tone deteriorates. In particular, the red chromaticity is greatly shifted to blue as compared with the case of using a light source for a desktop monitor. For example, when a conventional desktop monitor color filter is combined with a backlight light source having a high color temperature, the red chromaticity, particularly the x value, is reduced to 0.590 to 0.615, which is a standard color of television. A large deviation from the EBU standard red chromaticity (0.640, 0.330) makes it impossible to perform display with high color reproducibility.

  In addition, in order to create a color filter that satisfies the chromaticity of the EBU standard using a backlight light source for a conventional desktop monitor, the thickness of the blue pixel is increased or the pigment concentration is increased to improve the color purity. It is necessary. However, in that case, the transmittance of the blue pixel is greatly reduced, and the white display is yellowish, and the display characteristics are remarkably deteriorated. In addition, the color temperature of white is low, and the required characteristics of a liquid crystal television cannot be satisfied.

  As described above, the combination of the conventional backlight and color filter satisfies both the color characteristics (color reproducibility, color tone, color temperature in white display) required for a liquid crystal display device having a wide color reproduction range, particularly a liquid crystal television. It was difficult.

  In view of the above, there is a demand for a colored ink composition for color filters having a high pigment content, that is, high coloring power and high transparency.

  Similarly, the thickness of the colored layer of the color filter is preferably in the range of 1 μm to 10 μm, more preferably in the range of 2 μm to 7 μm, and particularly preferably in the range of 3 μm to 5 μm.

  Since the color filter of the present invention, particularly the color filter of the second embodiment, is formed by a screen printing method, the adjustment of the thickness of the colored layer, the pigment in the colored layer forming ink composition, and the like. The degree of freedom for adjusting the content is extremely high. Therefore, it is possible to easily obtain the color-related characteristics such as the above-mentioned NTSC ratio of 60% or more.

  Other matters in the color filter of the present invention, for example, a preferable pigment concentration range, a preferable line width of the colored layer, a base material, and the like, are the same as those described in the above section “A. Color filter manufacturing method”. Therefore, explanation here is omitted.

C. Others As described above, the present invention can provide the following inventions.
1. Production of a color filter, wherein a colored layer is formed by screen printing using a colored layer forming ink composition containing a pigment in a solid content ratio of 24% by weight to 95% by weight Method.
2. The colored layer forming ink composition contains at least a binder component and the pigment dispersed in the binder component,
When the rotational viscometer measurement method is used as the viscosity measurement method, the measurement value at a shear rate of 10S ⁻¹ measured at a temperature condition of 23 ° C. using a cone-disk type sample container of the measurement part is , 30,000 MPa to 100,000 MPa, and a measured value at a share rate of 20 S ^-1 is a colored layer forming ink composition having a range of 2,000 MPa to 7,000 MPa. A method for producing a color filter.
3. The binder component has a monomer component represented by the chemical formula (1) within a range of 5 mol% to 95 mol%, and a monomer component represented by the chemical formula (2) of 5 mol% to 85 mol%. A method for producing a color filter, which is an acrylic copolymer having a polystyrene-reduced weight average molecular weight within a range of 10,000 to 1,000,000.
4). The method for producing a color filter, wherein the colored layer forming ink composition comprises an epoxy acrylate resin composition in a solid content weight ratio within a range of 3 wt% to 55 wt%.
5. The method for producing a color filter, wherein the colored layer forming ink composition contains the compound represented by the chemical formula (3) in a weight ratio of 1 to 65% by weight.
6). The method for producing a color filter, wherein the ink composition for forming a colored layer contains a polyfunctional acrylic acrylate monomer and a photopolymerization initiator.
7). A screen printing plate used in the screen printing method includes a ridge, a planarization layer that fills a gap between the ridges and planarizes the surface of the ridge, and a back cushion layer formed on the substrate-side surface of the planarization layer A method for producing a color filter, comprising:
8). A method for producing a color filter, wherein the back cushion layer has a needle penetration hardness of 30 to 65.
9. A method for producing a color filter, comprising a first adhesive layer between the back cushion layer and the planarizing layer, wherein the hardness of the first adhesive layer is less than 30 in terms of needle penetration hardness.
10. A method for producing a color filter, wherein a photosensitive polymer layer is formed on a surface opposite to the substrate of the planarizing layer.
11. A method for producing a color filter, wherein a dry film resist is used for the back cushion layer.
12 The method for producing a color filter, wherein the wrinkle bias angle in the actual printing region of the screen printing wrinkle used in the screen printing plate is 31 ° or more and less than 45 °.
13. A method for producing a color filter, wherein the mesh opening width of the screen printing ridge is in the range of 5 μm to 85 μm.
14 The method of manufacturing a color filter, wherein the ridge is a metal ridge, and a surface of the metal ridge on a substrate side is ground and flattened.
15. A method for producing a color filter, wherein the width of the resulting colored layer line is in the range of 5 μm to 100 μm.
16. A color filter in which a colored layer is formed in a pattern on a substrate, wherein the line width of the colored layer is in the range of 5 μm to 100 μm, and the pigment concentration of the colored layer is 30 wt% to 95 wt% A color filter characterized by being in the range of.
17. A color filter having a colored layer formed in a pattern on a substrate, wherein the colored layer is formed by a screen printing method, and the line width of the colored layer is within a range of 5 μm to 100 μm. A color filter characterized by being.
18. A color filter, wherein the pigment concentration of the colored layer is in the range of 30% by weight to 95% by weight.
19. The color filter, wherein the colored layer has an NTSC ratio of 60% or more.
20. The color filter, wherein the color layer has a thickness in a range of 1 μm to 10 μm.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  The following examples further illustrate the invention.

[Experimental example: Adjustment of binder component]
1. Synthetic composition of copolymer resin (1) benzyl methacrylate 264 g (15 mol%)
-Styrene 385g (37 mol%)
-Acrylic acid 216g (30 mol%)
・ 234g (18 mol%) of 2-hydroxyethyl methacrylate
A solution obtained by dissolving a mixture of the above composition in 650 g of 3-methoxybutyl acetate together with 5 g of azobisisobutyronitrile was placed in a polymerization tank containing 1000 g of 3-methoxybutyl acetate at 100 ° C. for 6 hours. The solution was dropped and polymerized to obtain a polymer solution.

The polymer solution has a solid content of 40% by weight and a viscosity of 1050 mPa · s (30 ° C., B-type viscometer). The acid value of the polymer is 152 mgKOH / g, the hydroxyl value is 90 mgKOH / g, and the weight average molecular weight is It was 37,000 in terms of polystyrene.
The obtained copolymer consists of 15 mol% of styrene units, 37 mol% of benzyl methacrylate units, 30 mol% of acrylic acid units, and 18 mol% of 2-hydroxyethyl methacrylate units.

Next, to the polymer solution obtained,
-270 g of 2-methacryloyl ethyl isocyanate
・ Dibutyltin laurate 1g
-Acetic acid-3-methoxybutyl 2230g
A mixture having the composition was added dropwise over 5 hours.
While the progress of the reaction was monitored by IR (infrared absorption spectrum), the peak due to the isocyanate group at 2200 cm ⁻¹ disappeared.
The obtained reaction solution had a solid content of 26% by weight and a viscosity of 500 mPa · s (30 ° C., B-type viscometer). The polymer had an acid value of 120 mgKOH / g, a hydroxyl value of 5 mgKOH / g, and a weight average. The molecular weight was 45,000 in terms of polystyrene and contained 17 mol% of (meth) acryloyl groups.

2. Synthetic composition of copolymer resin (2) styrene 540 g (52 mol%)
-Acrylic acid 216g (30 mol%)
・ 234g (18 mol%) of 2-hydroxyethyl methacrylate

A solution obtained by dissolving a mixture of the above composition in 650 g of 3-methoxybutyl acetate together with 5 g of azobisisobutyronitrile was placed in a polymerization tank containing 1000 g of 3-methoxybutyl acetate at 100 ° C. for 6 hours. The solution was dropped and polymerized to obtain a polymer solution.
The polymer solution has a solid content of 40% by weight and a viscosity of 950 mPa · s (30 ° C., B-type viscometer). The acid value of the polymer is 150 mgKOH / g, the hydroxyl value is 90 mgKOH / g, and the weight average molecular weight is It was 38,000 in terms of polystyrene.
The obtained copolymer consists of 52 mol% of styrene units, 30 mol% of acrylic acid units, and 18 mol% of 2-hydroxyethyl methacrylate units.
Next, to the polymer solution obtained,
-270 g of 2-methacryloyl ethyl isocyanate
・ Dibutyltin laurate 1g
-Acetic acid-3-methoxybutyl 2230g
A mixture having the composition was added dropwise over 5 hours.

While the progress of the reaction was monitored by IR (infrared absorption spectrum), the peak due to the isocyanate group at 2200 cm ⁻¹ disappeared.

  The resulting reaction solution had a solid content of 25% by weight and a viscosity of 490 mPa · s (30 ° C., B-type viscometer). The polymer had an acid value of 120 mgKOH / g, a hydroxyl value of 5 mgKOH / g, and a weight average. The molecular weight was 45,000 in terms of polystyrene, and 14.5 mol% of (meth) acryloyl groups were contained.

A. Screen printing plate [Example 1]
(Production of photosensitive resin composition)
A photosensitive resin having the following composition was applied on a glass substrate having a thickness of 1.1 mm (AL material manufactured by Asahi Glass Co., Ltd.) by a spin coating method (coating thickness: 1.5 μm), and thereafter 30 in an oven at 70 ° C. Dried for minutes. Next, the coated surface was exposed using a mercury lamp through a photomask having a predetermined pattern, and spray development with water was performed for 1 minute to form a screen evaluation pattern in a region where the formation and hardening pixels were to be formed. Furthermore, it was then heated at 150 ° C. for 30 minutes to perform a curing process.

Next, a screen evaluation pattern was formed in the same process as the pattern formation using a photosensitive resin having the following composition.
Composition: Copolymerized resin synthesized above (1) (solid content 25%) 46.8 parts by weight (Sartomer, SR399) 9.1 parts by weight Orthocresol novolac epoxy resin (Oilized Shell Epoxy) Epicote 180S70) 5.2 parts by weight 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropanone-1 1.8 parts by weight 2,2'-bis (o-chlorophenyl) -4 , 5,4 ', 5'-tetraphenyl-1,2'-biimidazole 1.3 parts by weight, diethylene glycol dimethyl ether 29.6 parts by weight, 3-methoxybutyl acetate 6.2 parts by weight The photosensitive resin composition of the present invention was prepared by stirring and mixing.
(Exposure and development process)
A photomask is placed at a distance of 100 μm from the coating film of the photosensitive resin composition, and ultraviolet rays are applied only to the region corresponding to the pattern formation region of the screen resin layer using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Irradiated for 2 seconds. Next, the film was immersed in a 0.05% aqueous sodium hydrogen carbonate solution (liquid temperature: 23 ° C.) for 2 minutes and developed with an aqueous solution to remove only the uncured portion of the coating film of the photosensitive resin composition.

  Thereafter, the substrate was left to stand in an atmosphere of 180 ° C. for 30 minutes to perform heat treatment to form a protective film, thereby obtaining a plate and a screen evaluation pattern of the present invention. Furthermore, 35 g of blocked isocyanate (Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed with 100 g of the photosensitive resin composition having the above composition and stirred for 10 minutes with a homomixer. As a result, a pale yellow milky white liquid (photosensitive resin Composition) was obtained. Using this liquid photosensitive resin composition, according to a conventional method for preparing a screen printing plate, a stainless mesh ST590CALH 320 □ 590 mesh (having a thickness of 28 μm, a wire diameter of 13 μm, a space ratio of 49%) and a thickness of a photosensitive resin solution of 14 μm. A positive film on which a test pattern is drawn is applied, and exposed at a distance of 1 M with a 2 kw ultra-high pressure mercury lamp. Water is sprayed with a spray gun to wash away the unexposed area, and a cured photosensitive film is formed. A test pattern image was obtained. Next, this image (plate) was placed in a hot air oven and subjected to heat treatment at 180 ° C. for 90 minutes. The obtained screen printing plate was evaluated according to the following method. The results are shown in Table 1.

[Example 2]
Instead of the photosensitive resin composition in Example 1, a plate and a screen evaluation pattern were prepared in the same manner except that the photosensitive resin composition prepared below was used in the same manner.
(Preparation of photosensitive resin composition)
Composition: copolymer resin synthesized above (2) (solid content 25%) 43.0 parts by weight dipentaerythritol pentaacrylate (manufactured by Sartomer, SR399)
9.1 parts by weight / orthocresol novolac type epoxy resin (manufactured by Yuka Shell Epoxy, Epicoat 180S70) 9.1 parts by weight / DPHA (made by Sartoma) 2.8 parts by weight / 2-methyl-1- [4 -Methylthio] phenyl] -2-morpholinopropanone-1 1.8 parts by weight. 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-bi 1.3 parts by weight of imidazole, Irgacure 907 (manufactured by Ciba Geigy) 1.0 part by weight, 29.6 parts by weight of diethylene glycol dimethyl ether, 6.2 parts by weight of the mixture of the above composition was stirred and mixed at room temperature, A photosensitive resin composition of the present invention was prepared.

A liquid photosensitive resin composition is prepared by mixing 35 g of blocked isocyanate (Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd.) and 240 g of vinyl acetate emulsion (MA-206 manufactured by Hoechst Synthesis Co., Ltd.) with 100 g of the above-described photosensitive resin. A screen printing plate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
(Alkali resistance, surface condition of protective film, dynamic hardness)
After immersing the sample in a 1% sodium hydroxide aqueous solution (liquid temperature: 23 ° C.) for 24 hours, the sample was pulled up, and the hardness of the protective film was changed to a dynamic hardness meter (Shimadzu Dynamic Ultra Hardness Meter DUH-201S, constant indentation load test: triangle Indenter: 115 °, load: 5 mN, load speed constant: 6, holding time: 5 sec), and the appearance was evaluated according to the following evaluation criteria. The dynamic hardness indicates the needle penetration hardness.
○: No change is observed in the cured protective film Δ: Roughness is generated on the surface of the cured protective film to generate bubbles X: A part or all of the cured protective film is peeled off (developability, edge shape)
The outer peripheral shape of the protective film pattern when immersed in a 0.05% aqueous potassium hydroxide solution (23 ° C.) for 1 minute to completely remove the unexposed portion was evaluated according to the following criteria.
○: The outer peripheral shape maintains linearity, and no waviness, wrinkles, etc. are observed.
The surface tack after the exposure and development processing was observed and evaluated according to the following criteria.
○: There is no tack.
X: There is a tack.

(Leveling)
The surface condition after dry coating was observed and evaluated according to the following criteria.
○: Flat.
X: The flatness is lacking, and the surface has a cocoon skin shape.

(Adhesion)
After cross-cutting, a peeling test was performed with an adhesive tape (manufactured by 3M, No. 610), and evaluation was performed according to the following criteria.
○: There is no peeling in each square.
X: Peeling occurred in each square eye.

(Photosensitive solution stability test)
The photosensitive solution was brought to 25 ° C. in a thermostatic bath, and the viscosity was measured using a B-type viscometer. The photosensitive solution was packed in a polyethylene bottle, placed in an environmental tester with a temperature of 30 ° C. and a humidity of 70%, taken out after 10 days, and the viscosity at 25 ° C. was measured using a B-type viscometer.

(Grayscale sensitivity)
In accordance with a conventional method for producing a screen plate, a photosensitive resin layer was applied to a thickness of 14 μm on a stainless steel mesh ST590CALH 320 □ 590 mesh (having a thickness of 28 μm, a wire diameter of 13 μm, a space ratio of 49%), and manufactured by Dai Nippon Printing Co., Ltd. Resolution chart and Kodak Photographic Step Table No. Two films (hereinafter referred to as gray scale) were vacuum-contacted and exposed to light having a wavelength of 300 nm or more with a 2 kw ultra-high pressure mercury lamp at a light quantity of 500 mJ / cm ₂ . After exposure, water was sprayed with a spray developing machine to wash away the unexposed area, and a test pattern image formed with a cured photosensitive film was obtained. The pattern portion of this image was observed, and the resist sensitivity was as high as 4.5 in the remaining gray scale (hereinafter, the exposure amount is doubled to increase the gray scale sensitivity by 2 steps).

(Resolution test)
Using the plate used for the gray scale sensitivity evaluation, the minimum line width capable of resolving the pattern with an appropriate exposure time was observed, and the line line width was determined as the resolution.

(Storage stability test)
In accordance with a conventional method for preparing a screen plate, a stainless mesh ST590CALH 320 □ 590 mesh (a thickness of 28 μm, a wire diameter of 13 μm, a space ratio of 49%) was applied to a thickness of a photosensitive resin layer of 14 μm. This plate was placed in an environmental tester at a temperature of 40 ° C. and a humidity of 70%, taken out after 5 days, and the change in the gray scale sensitivity was observed. A positive film on which a test pattern is drawn is closely attached, exposed with a 2 kW ultra-high pressure mercury lamp at a distance of 1 m, changing the exposure time, sprayed with water with a spray gun to wash away unexposed areas, and a cured photosensitive film A test pattern image formed in (1) was obtained. The pattern portion of this image was observed, and the pattern omission at the appropriate exposure time was evaluated according to the following criteria.
○: The minimum resolvable line width was the same.
Δ: The minimum resolvable line width increased below 15 μm.
X: The minimum resolvable line width increased by 15 μm or more.

Example 3
To 100 g of the photosensitive resin solution of Example 1, 35 g of blocked isocyanate (Coronate 2513 manufactured by Nippon Polyurethane Industry), 85 g of vinyl acetate emulsion (Hoechst Synthesis MA-206), photopolymerization initiator diethylthioxanthone (KAYACURE manufactured by Nippon Kayaku Co., Ltd.) 7 g of an acrylate oligomer (TMPTA manufactured by Shin-Nakamura Chemical Co., Ltd.) in which 0.2 g of DETX) and 0.1 g of an amine compound (KAYACURE-EPA manufactured by Nippon Kayaku Co., Ltd.) as a polymerization accelerator were mixed. A photosensitive resin composition was prepared, and a screen printing plate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
The photosensitive resin solution of Example 1 was mixed with 35 g of blocked isocyanate (Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd.), 240 g of vinyl acetate emulsion (MA-206 manufactured by Hoechst Synthetic Co., Ltd.), and 5 g of 10% diazo aqueous solution. A functional resin composition was prepared, and a screen printing plate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
When 35 g of blocked isocyanate (Nihon Polyurethane Industry Coronate 2513) was mixed with 100 g of the photosensitive resin solution of Example 1 and stirred for 10 minutes with a homomixer, a pale yellow milky white liquid (photosensitive resin composition) was obtained. It was. Using this liquid photosensitive resin composition, the thickness of the photosensitive resin layer 14 μm on the stainless steel mesh ST590CALH 320 □ 590 mesh (紗 thickness 28 μm, wire diameter 13 μm, space ratio 49%) in accordance with the usual method for preparing screen printing plates It was applied to. The positive film on which the test pattern was drawn was brought into close contact, and was brought into vacuum contact, and exposure was performed with a ² kw ultra-high pressure mercury lamp at a wavelength of 300 nm or more with a light amount of 500 mJ / cm ² . After exposure, water was sprayed with a spray gun to wash away the unexposed areas, and a test pattern image formed with a cured photosensitive film was obtained. This image (plate) was placed in a hot air oven and subjected to heat treatment at 180 ° C. for 90 minutes. The screen printing plate after the heat treatment was evaluated, and the results are shown in Table 1.

[Comparative Example 1]
Instead of the photosensitive resin composition in Example 1, the same process was carried out except that the photosensitive resin composition prepared below was used in the same manner.
(Preparation of photosensitive resin composition)
Composition: o-cresol novolac epoxy acrylate (reacted 50% of hydroxyl groups with phthalic anhydride) 8.8 parts by weight dipentaerythritol hexaacrylate 8.8 parts by weight Orthocresol novolac type epoxy resin 2.0 parts by weight -Initiator (Irgacure-369) 0.4 parts by weight-80 parts by weight of acetic acid-3-methoxybutyl alcohol A mixture of the above composition was stirred and mixed at room temperature to prepare a photosensitive resin composition.

  About the obtained hardening protective film for each screen plate, tack property, leveling property, alkali resistance, adhesion, developability, edge shape, surface state, and dynamic hardness were evaluated under the following conditions.

[Comparative Example 2]
To 100 g of the photosensitive resin solution of Example 1, 0.2 g of a photopolymerization initiator diethylthioxanthone (KAYACURE DETX manufactured by Nippon Kayaku Co., Ltd.) and an amine compound (KAYACUREEPA manufactured by Nippon Kayaku Co., Ltd.) 0. An acrylate oligomer (TMPTA manufactured by Shin-Nakamura Chemical Co., Ltd.) in which 1 g was dissolved and mixed was emulsified and mixed for evaluation. The results are shown in Table 1.

[Comparative Example 3]
100 g of the photosensitive resin solution of Example 1 was mixed with 240 g of vinyl acetate emulsion (MA-206 manufactured by Hoechst Synthesis Co., Ltd.) and 10 g of a 10% diazo aqueous solution to prepare a photosensitive solution. A version was created and evaluated. The results are shown in Table 1.

[Comparative Example 4]
In Example 2, it carried out like Example 2 except having implemented using the dichromate type photosensitive solution as a photosensitive solution. The results are shown in Table 1.

B. Production of high-definition screen printing plate for color filter production [Example]
A silicone thin film having a thickness of 1.5 mm was laid on the stretched face frame of the rectangular SUS404 mold 320 □. The tension was increased using a tensioning machine and fixed to 2000-2300 N / mm. Screen cage is stainless mesh ST590CALH 320 □ 590 mesh (Tokyo Process Service Co., Ltd., cage thickness 28μm, wire diameter 13μm, space ratio 49%), screen angle 35.1 degrees, back polished by alumina fine powder polishing Alternatively, or a double-sided 1/3 polishing (sintered at the intersection of wrinkles, average wire diameter 7 μm, space ratio 68% (calculated value)) was used after calendaring. A photosensitive resin layer having adhesive ability was coated on both sides of one of these ridges. The following were used as photosensitive resin (adhesion layer 1).
・ Acrylic-soluble resin Cyclo-P (manufactured by Daicel Industries, Ltd.) 30 parts by weight ・ Polyfunctional acrylate monomer
TMPTA + DPHA (mixing ratio 1: 3) 20 parts by weight / photopolymerization initiator Irgacure 907 (Ciba Geigy)
+ PAI-01 (mixing ratio 1: 0.01) 0.4 parts by weight / sensitizer mixed product ESACURE KTO46 (manufactured by Nippon Sebel Hegner)
0.6 parts by weight · PGMIA + cyclohexanone + toluene (mixing ratio 7: 2: 1) 49 parts by weight A mixture having the above composition was applied so as to have a dry film thickness of 5 μm, and a sealing treatment was performed. After removing the tackiness by drying at 70 ° C for 10 minutes with a dryer, use a large-scale UV aligner (DNP specification machine) made by Dainippon Screen using a chrome mask with the necessary patterns such as stripe patterns and alignment marks. Ultra high pressure mercury exposure was performed on both sides at once. After the exposure, 1% tetramethylhydroxyammonium (TMAH) added with 3% isopropyl alcohol was spray developed on the photosensitive resin surface. Brushing was performed as necessary, and development was performed so that there was no excess film of the remaining photosensitive material other than the pattern.

  Next, on the ink mounting surface side, the photosensitive resin composition of Example 1 was applied as a photosensitive resin layer so as to have a dry film thickness of 10 μm, and exposure and development processing were performed in the same manner as described above. The eyelid opening was observed with a microscope, and it was confirmed that the minimum opening width was resolved to 8 μm.

  Furthermore, on the other back surface, the photosensitive resin composition of Example 2 described above was applied as a photosensitive resin layer so as to have a dry film thickness of 3 μm, and dried at 70 ° C. for about 15 minutes so as not to cause tack. Further, a photosensitive resin (adhesive layer 1) was applied so as to have a dry film thickness of 5 μm, and dried at 70 ° C. for about 15 minutes so as to eliminate tack. Further, the photosensitive resin composition of Example 1 described above was applied as a photosensitive resin so as to have a dry film thickness of 3 μm, and dried at 70 ° C. for about 15 minutes so as to eliminate tack. The back cushion layer which follows a required pattern by the same development and exposure as described above was provided. The eyelid opening was observed with a microscope, and it was confirmed that the minimum opening width was resolved to 8 μm.

  Further, after the entire pattern was formed, drying was further performed at 120 ° C. for 5 hours in a dryer in order to completely cure the plate sensitizer.

  In addition, each photosensitive resin composition is highly transparent, and this process does not need to be individually exposed and developed. The photosensitive resin necessary for both sides of the plate is sequentially applied, dried to the extent that there is no tackiness, and photosensitive. After repeating the resin lamination, both sides are exposed simultaneously, and it is confirmed that the plate can be formed by batch development. Furthermore, it has been confirmed that even if the back cushion layer is made of the following material and laid on the upper surface of the adhesive layer 1, it is effective.

(Synthesis of photosensitive resin composition for back cushion layer)
Photosensitive epoxy acrylate DCR-43 (manufactured by Nippon Shokubai Co., Ltd.) 25 parts by weight DPHA (manufactured by Daicel Industries, Ltd.) 20 parts by weight Leveling agent 9038 + 937 (manufactured by Mino Co., Ltd., mixing ratio 4: 1) 3 1 part by weight, 1 part by weight Irgacure 907 (manufactured by Ciba Geigy) 1 part by weight ESACURE KTO46 (manufactured by Nippon Sebel Hegner)
PGMIA + cyclohexanone + toluene (mixing ratio 7: 2: 1) 48 parts by weight A mixture of the above composition was stirred and mixed at room temperature to prepare the photosensitive resin composition of the present invention.

C. Colored ink composition [Example 1: CF ink for resin BM]
As the transparent substrate, PET185 μm (manufactured by Toyobo Co., Ltd.) washed with a neutral detergent, washed with water, degreased, ozone treated and light washed was used. The black photosensitive pigment composition (resin BM) shown below was used. A pigment was added to the following alkali-soluble resin, mixed, kneaded and dispersed with two rolls or the like, further added with a PGMEA diluent, and dispersed with a paint shaker, bead mill or the like to obtain a pigment dispersion A. The particle size (d ₅₀ ) of the carbon black after dispersion was 0.051 μm.
Pigment dispersion A composition / pigment (carbon black, MA-8 manufactured by Mitsubishi Chemical) 23.0 parts by weight / benzyl methacrylate-styrene-acrylic acid copolymer (copolymerization ratio 1: 1: 1, molecular weight about 30,000, Molecular weight distribution Mw / Mn = 1.7)
7.0 parts by weight · DPHA (manufactured by Daicel Industries, Ltd.) 5.0 parts by weight · Dispersant: Disperbyk 161 (manufactured by Big Chemie) 3.0 parts by weight · propylene glycol monomethyl ether acetate (PGMEA)
55.0 parts by weight / isophorone 7.0 parts by weight This ink viscosity was measured using BH type 25 ° C. Using No. 7, the rheology with high thixotropy of 91000 at 10S ^{- 1} and 6400 at 20S- ¹ in mPa unit was shown.

  A 30 μmL & S resin BM pattern could be formed by the printing machine and printing conditions.

  Further, when the aspect ratio was determined with the present ink, a resin BM wall of 4 steps (an aspect ratio of 3), that is, 120 μm, could be produced in a straight shape without undulation or swimming with respect to an isolated line of 30 μm.

  Furthermore, as a printing condition, a large BM stripe having a width of 2 m could be produced by using the alignment mark and performing continuous printing in the horizontal width direction. This confirmed that the BM of the lenticular lens can prevent light leakage in the lateral direction and can be used without impairing the visibility.

[Example 2]
A pigment was added to the following alkali-soluble resin, mixed, kneaded and dispersed with two rolls, etc., further added with a PGMEA diluting solvent, and dispersed with a paint shaker, bead mill, etc. to obtain a pigment dispersion B. The particle size (d50) of the carbon black after dispersion was 0.13 μm.
Pigment dispersion B composition / pigment (carbon black, Degussa, SpecialBlack250) 10.0 parts by weight
Benzyl methacrylate-styrene-acrylic acid copolymer (copolymerization ratio 1: 1: 1, molecular weight about 30,000, molecular weight distribution Mw / Mn = 1.7)
5.0 parts by weight Dispersant: Disperbyk 161 (by Big Chemie) 1.0 part by weight propylene glycol monomethyl ether acetate (PGMEA)
20.0 parts by weight / isophorone 2.0 parts by weight This ink viscosity was measured using BH type 25 ° C. No. 7 used showed high thixotropy 5500 ^{10s -1} at 63000 and ^{20s -1} at mPa units rheology.

  A 30 μmL & S resin BM pattern could be formed in the same manner as in Example 1 by the above printing machine and printing conditions.

[Comparative Example 1]
In the following photosensitive resin, pigment dispersions A and B are mixed according to the following composition, and a diluent solvent such as ethyl cellosolve acetate is added thereto, and each is dispersed with a paint shaker, bead mill, etc. to prepare the resin BM of the present invention. did. The pigment dispersions A and B were dispersed by changing the blending ratio thereof so that the average particle diameter of the dispersed pigment in the following resin BM was 0.06 μm or less at d50. Confirmation of the particle size and particle size distribution was performed with a Microtrac UPA particle size analyzer manufactured by Nikkiso Co., Ltd.
Composition of black photosensitive resin composition, pigment dispersions A and B
(Dispersion A is 30 to 90%, Dispersion B is 10 to 70%) 84.0 parts by weight benzyl methacrylate-styrene-acrylic acid copolymer (copolymerization ratio 1: 1: 1, molecular weight about 30,000) Molecular weight distribution Mw / Mn = 1.7)
Solid content 40% (3-methoxybutyl acetate solution) 5.0 parts by weight, trimethylolpropane triacrylate (manufactured by Nippon Kayaku) 9.0 parts by weight, Irgacure 369 (manufactured by Ciba Geigy) 3.0 parts by weight, ethyl Cellosolve acetate 15.0 parts by weight The above composition ink was applied on a glass substrate to a thickness of 1.0 μm by spin coating. The film thickness was measured with a deck tack device using a stylus method. After coating, pre-baking was performed at 120 ° C. for 3 minutes in a CR dryer, and the pattern was baked by changing the exposure amount from 400 to 2000 mJ / cm ² with an aligner through a mask having a fine line pattern.

  The development was performed by dissolving the uncured black resin film with an aqueous alkaline solution using an automatic developing apparatus and then washing with water. After confirming the pattern thin line with a microscope, it was post-baked at 200 ° C. for 60 minutes. The pattern fine line was 2.5 μm or less, and a line and space pattern was resolved. Furthermore, it was confirmed that the film reduction rate after post-baking was 10% or less. O.D. of the obtained resin BM pattern part (film thickness 1 μm, P / V = 0.6). The change in D value is shown in FIG. From this result, the light-blocking effect is higher when the pigment dispersions A and B are used in combination than when they are used alone, and the black matrix pattern (film thickness) at a mixing ratio of 35:65 of the liquid A to the liquid B 1 μm, PV = 0.6) O.D. The D value was 3.22.

[Comparative Example 2]
Only the dispersion A was used as the pigment dispersion, and the rest of the O.D. was obtained in the same manner as in Example 1 with a pattern portion (film thickness: 1 μm, P / V = 0.6). The D value was 3.02. In addition, only the dispersion B was used as the pigment dispersion, and the rest was obtained by O.D. according to the pattern portion (film thickness 1 μm, P / V = 0.6) obtained in the same manner as in Example 1. The D value was 3.12.

[Comparative Example 3]
A black photosensitive resin composition was prepared in the same manner as in Example 1 except that the carbon black of the black photosensitive resin composition was changed to 10 parts of Raven 5000 (Degussa, pH value 2.8, BET surface area 430 m 2 / g). . Pattern preparation was performed after preparing this product. The exposure energy amount (sensitivity) required for forming the resin BM pattern was 800 mJ / cm ² or more. The development characteristics showed swelling peelability. Moreover, the adhesiveness with respect to a glass substrate and PET was low, and the complete pattern was not obtained.

[Comparative Example 4]
A black photosensitive resin composition was prepared in the same manner as in Example 1 except that the carbon black of the resin BM was changed to 10 parts of MA-600 (manufactured by Mitsubishi Kasei, pH value 7.5, BET specific surface area 153 m 2 / g). . The black photosensitive resin composition was not suitable for storage at room temperature, and after about one month, it agglomerated and precipitated. After the resin BM was prepared, the pattern of the resin BM pattern was prepared, but the development characteristics showed swelling peelability. Further, the adhesion to the glass substrate and PET was low, and an image pattern could not be formed. Furthermore, the light-shielding property was extremely inferior (OD value at 1 μm film thickness was 2.51).

[Comparative Example 5]
A black photosensitive resin composition was prepared in the same manner as in Example 1 except that the black photosensitive resin composition was changed to only 10 parts of a pseudo black organic pigment (R + G + B mixed pigment), and a pattern was produced for the resin BM pattern part. It was. However, although the solubility and the high resolution were ensured, the image pattern swim occurred, and the light shielding property was remarkably inferior (OD value at 1 μm film thickness was 2.3).

D. RGB colored ink composition [Example 1]
120 parts by weight of CI Pigment Blue 15: 6 as component (A), 40 parts by weight of copolymer resin 1 (copolymerization weight ratio = 25/65/10, Mw = 70,000) as component (B), (C) 50 parts by weight of dipentaerythritol pentaacrylate as component, Irgacure 907 (manufactured by Ciba Geigy) + PAI-01 (mixing ratio 1: 0.01) as component (D) 5 parts by weight + sensitizer mixture ESACURE KTO46 (Nippon Sebel Hegner) 10 parts by weight) and 400 parts by weight of ethylene glycol monoethyl ether acetate as a solvent were mixed, and a colored ink for a color filter was prepared by mechanical dispersion using a kneader and a bead mill together.
The ink viscosity was measured using BH type 25 ° C. Using No. 7, the rheology with high thixotropy of 42000 at 10S ^{- 1} and 7000 at 20S- ¹ in mPa unit was shown.

A CF pattern was prepared using the above-described plate with this colored ink. It was printed on a 185 μm PET film to form 20 μm independent fine lines, and a 25 μm independent thin line could be formed on the glass substrate. The printing machine produced a color filter on a DNP remodeling machine manufactured by Japan Neurong Co., Ltd. (equipped with a rotary stage mechanism, CCD reading and plate OFF control mechanism) 1.1 mm thick liquid crystal glass 300 × 400 mm. The printing conditions were a squeegee speed of 250 mm / S, a clearance of 1.0 mm, and a squeegee pressure of 20 kgf. By optimizing the clearance and plate OFF control, an independent fine wire of 15 μm was realized. Furthermore, because of the high-definition pattern, special alignment as shown in the figure for alignment of the color filter (three-color arrangement state), and a configuration in which verniers are arranged on the outer periphery so that each single-color arrangement can be easily inspected did. Using this alignment, continuous printing can be performed at high speed by using a rotary stage as a print control by the CCD reading method.
(By the following formula, the translation process is performed once so that the center of gravity is moved once so that the center of gravity becomes the origin. By rotating around the center of gravity and performing the original translation, an early processing system is obtained. (Shown in)
X = x cos α−ysin α
Y = xsinα + ycosα
Furthermore, the cross-sectional SEM photograph (pigment concentration 56 weight%) of the color filter obtained for each color is shown in FIG. Despite containing a pigment at a high concentration, a color filter having high coloring power and high transparency was obtained. FIG. 8 shows a cross-sectional SEM photograph of a color filter having a pigment concentration of 12% by weight and FIG. 9 having a pigment concentration of 35% by weight.

  Each print pattern obtained was air-dried and then post-baked at 180 ° C. for 30 minutes to produce a blue pixel pattern. For the obtained pixel, using a color analyzer (TC-1800M manufactured by Tokyo Denshoku Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree field of view ( When Y) was measured, it was (x, y, Y) = (0.145, 0.055, 23.9). Also, instead of CI Pigment Blue 15: 6, a mixture of CI Pigment Red 254, CI Pigment Red 177 and CI Pigment Yellow 139 (mixing ratio 85/10/5) was used, and CI Pigment Green 36 and CI Pigment Yellow were used. 150 using a liquid composition of a radiation-sensitive composition prepared in the same manner as described above except that a mixture with 150 (mixing ratio 70/30) was used, and red on a substrate on which the blue pixel array was formed. The pixel array and the green pixel array were sequentially formed to obtain a color filter in which each of the blue, red, and green pixel arrays was arranged on the same substrate. The chromaticity coordinate values of the red and green pixels used here are (x, y, Y) = (0.667, 0.345, 23.5) and (0.311, 0.683, 36. 9). This color filter had an NTSC ratio of 64% and a white balance stimulation value (Y) of 36.5.

  Further, as a pigment component, a mixture of C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23 (mixing ratio 80/20) was used and processed in the same manner as in Example 1 to form a blue pixel pattern. However, the film thickness was adjusted such that the chromaticity (x, y) in the CIE color system was the same as in Example 1. When the chromaticity coordinate value (x, y) and stimulus value (Y) in the CIE color system were measured for the obtained pixel, (x, y, Y) = (0.139, 0.155, 21. 9).

E. Preparation and evaluation of CF coating for LCD panel for comparison
First, a black resin BM (DNP prototype) was applied and dried at 110 ° C. for 5 minutes. It exposed with the ultraviolet-ray with an intensity | strength of 60 mJ / cm <2> and a wavelength of 365 nm through the chromium photomask. After exposure, spin development was performed with a developer composed of a 2.25% aqueous solution of tetramethylammonium hydroxide.

  Next, the blue photosensitive composition was applied with a spinner on a glass substrate and dried at 110 ° C. for 5 minutes. The blue coating film was developed and heat-treated in the same manner as described above to obtain a blue pixel. Similarly, a red pixel and a green pixel were obtained by applying, exposing, developing, and heat-treating a red colored photosensitive composition and a green colored photosensitive composition. On the color filter thus obtained, an overcoat agent optomer manufactured by JSR Co., Ltd. was formed into a film having a thickness of 1 μm, and an ITO film was further sputtered thereon to a thickness of 0.14 μm. The chromaticity (x, y) when passing the C light source on the glass substrate is red (0.651, 0.322), green (0.295, 0.591), and blue (0.136, 0), respectively. .102). Separately, a substrate on which TFT elements, pixel electrodes, etc. are formed on alkali-free glass is prepared as a counter substrate, and an alignment film is printed on the substrate coated with the color paste (colored layer substrate) and the counter substrate, and then aligned. I let you. A sealing agent in which microbeads were kneaded was printed on one of these two substrates, a spacer having a thickness of 5 μm was secured and adhered, and then UV cured and adhered to bond the two substrates together. Next, TN liquid crystal (refractive index anisotropy Δn to 0.1) compatible with 4V driving was injected to close the liquid crystal injection port with a sealing agent. A liquid crystal cell into which liquid crystal was injected was sandwiched between orthogonal polarizing films to prepare a liquid crystal cell for evaluation. A liquid crystal display device is completed by mounting an IC driver or the like on the liquid crystal cell.

  When a three-wavelength backlight source having chromaticity coordinates (x, y) of (0.280, 0.272) in the XYZ color system chromaticity diagram is placed under the prepared liquid crystal cell, the chromaticity is measured. , Red (0.640, 0.320), green (0.294, 0.597), blue (0.145, 0.061), and a colorful display equivalent to the EBU standard was obtained. Further, the color tone of white in the liquid crystal cell provided with the color filter was bluish-white, indicating a display with a good color balance. The color temperature in white display is 8500K, indicating the color characteristics required for a liquid crystal television.

  As a comparative example, a red pigment was added to C.I. Pigment Red254 and C.I. I Pigment Yellow 150 was changed to one containing 90/10, and the blue pigment was changed to C.I. A liquid crystal cell for evaluation was produced in the same manner as in Example 1 except that I Pigment Blue 15: 3 was changed to 100%. The chromaticities measured using a C light source were red (0.630, 0.335), green (0.298, 0.593), and blue (0.138, 0.125). In particular, Blue is yellowish and has a color shift. When a three-wavelength backlight source having chromaticity coordinates (x, y) of (0.280, 0.270) in the XYZ color system chromaticity diagram is placed under the prepared liquid crystal cell, the chromaticity is measured. , Red (0.612, 0.337), green (0.294, 0.605), blue (0.147, 0.085) and particularly red greatly deviate from the EBU standard to obtain a colorful display. I could not.

It is a top view for demonstrating the structure of a collar. It is a schematic sectional drawing which shows an example of the screen printing plate used for this invention. It is a schematic sectional drawing which shows an example of the metal punch used for the screen printing plate of this invention. It is a graph which shows the color temperature in a chromaticity coordinate (x, y) and white display in an XYZ color system chromaticity diagram. The O.D. It is a figure which shows the change of D value. It is a figure which shows the flow of the alignment process in this invention. It is a SEM photograph of the section of a color filter obtained by carrying out the present invention (pigment concentration 56% by weight). It is a SEM photograph of the section of a color filter (pigment concentration of 12% by weight). It is the SEM photograph of the cross section of a color filter (pigment concentration 35 weight%).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ...... …… 2 ...... Flattening layer 3 ...... First adhesive layer 4 ...... Back cushion layer 5 ...... Second adhesive layer 6 ...... Photopolymer layer

Claims (13)

A method for producing a color filter, which uses a colored layer forming ink composition containing a pigment in a solid content ratio of 24% by weight to 95% by weight, and forms a patterned colored layer by a screen printing method,
A screen printing plate used in the screen printing method includes a ridge, a planarization layer that fills a gap between the ridges and planarizes the surface of the ridge, and a back cushion layer formed on the substrate-side surface of the planarization layer A method for producing a color filter, comprising:   The method for producing a color filter according to claim 1, wherein the hardness of the back cushion layer is in the range of 30 to 65 in terms of needle penetration hardness.   The first adhesive layer is provided between the back cushion layer and the flattening layer, and the hardness of the first adhesive layer is less than 30 in terms of needle penetration hardness. The manufacturing method of the color filter of description.   The method for producing a color filter according to any one of claims 1 to 3, wherein a photosensitive polymer layer is formed on a surface of the flattening layer opposite to the substrate.   The method for manufacturing a color filter according to any one of claims 1 to 4, wherein a dry film resist is used for the back cushion layer.   6. The screen printing wrinkle used in the screen printing plate has a wrinkle bias angle in an actual printing region of 31 ° to less than 45 °. The manufacturing method of the color filter of Claim.   The method for producing a color filter according to claim 6, wherein a mesh opening width of the screen printing ridge is in a range of 5 µm to 85 µm.   The color filter according to any one of claims 1 to 7, wherein the ridge is a metal ridge, and a surface of the metal ridge on a substrate side is ground and flattened. Manufacturing method.   The colored layer forming ink composition contains at least a binder component and the pigment dispersed in the binder component, and when a rotational viscometer measurement method is used as a viscosity measurement method, The viscosity measured at a shear rate of 10S-1 using a cone-disk type sample container at a temperature condition of 23 ° C. is in the range of 30,000 MPa to 100,000 MPa, and the share rate is 20S. The measured value at -1 is an ink composition for forming a colored layer in a range of 2,000 MPa to 7,000 MPa. 9. Manufacturing method of color filter. The binder component has a monomer component represented by the following chemical formula (1) within a range of 5 mol% to 95 mol%, and a monomer component represented by the following chemical formula (2) of 5 mol% to 85 mol%. The method for producing a color filter according to claim 9, wherein the color filter is an acrylic copolymer having a polystyrene-reduced weight average molecular weight within a range of 10,000 to 1,000,000.

(Here, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms. R ₁ is an aromatic or alicyclic compound.)   11. The method for producing a color filter according to claim 10, wherein the colored layer forming ink composition contains the epoxy acrylate resin composition within a range of 3 wt% to 55 wt% in terms of solid content weight ratio. .   The said color layer formation ink composition contains a polyfunctional acrylic acrylate monomer and a photoinitiator, The manufacture of the color filter in any one of Claim 10 or Claim 11 characterized by the above-mentioned. Method.   The method for producing a color filter according to any one of claims 1 to 12, wherein the width of the obtained colored layer line is within a range of 5 µm to 100 µm.

Images