JP2011090089A - Photosensitive composition, color filter using the same, and liquid crystal display and organic el display using the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter high in transmittance and excellent in light resistance by improving photosensitive composition used as material of the color filter; and to provide a liquid crystal display and an organic EL display which is low in power consumption and bright by using the color filter. <P>SOLUTION: This photosensitive composition includes: (A) a transparent resin; (B) a photo-polymerizable monomer; (C) a dye; (D) a photo-initiator; and (E) a solvent. The number of functional groups of the photo-polymerizable monomers (B) is 4-6. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive composition used for a color filter used in a color liquid crystal display, an organic EL display, and the like, a color filter using the same, and a liquid crystal display and an organic EL display formed using the color filter. It is about.

  In recent years, with the diversification of information equipment and the like, the need for flat display displays that consume less power and occupy less space than conventional CRTs has increased, and liquid crystal displays are one of such flat display displays. In addition, color displays using organic electroluminescence (organic EL) elements have attracted attention.

  A simplified structure of a typical liquid crystal display is shown in the schematic cross-sectional view of FIG. A black matrix 7, a red colored layer 6a, a green colored layer 6b, and a blue colored layer 6c are patterned on a single transparent substrate 5, and each of these layers is covered with an overcoat layer 8 as necessary to form the uppermost layer. A color filter 1 having a transparent electrode 10 as a common electrode is disposed on one side, and a counter substrate disposed on the other side is a TFT array 3. The TFT array 3 includes a TFT (thin film transistor) 9 patterned as a pixel switching element on a transparent substrate 5 and a transparent electrode 10 for each pixel. After the alignment film 12 is provided on each surface layer of the substrate of the color filter 1 and the substrate of the TFT array 3, the liquid crystal 2 is sealed between the substrates so as to be sandwiched between the two alignment films 12. A polarizing plate is bonded to the outside of the cell structure, and a backlight 4 is provided on the outside of one of the cell structures formed as described above to form a typical liquid crystal display structure.

  In a liquid crystal display, display can be performed by applying a voltage to the electrodes on both sides of the liquid crystal, and making the light from the backlight bright and dark using the birefringence of the liquid crystal. In the figure, the light emitted from the backlight 4 is indicated by a block arrow from the bottom, and the light indicated by the upper block arrow selectively passes through the cell structure and displays an image. In this case, 50% of the backlight light is blocked by the polarizing plate, and 70% of the light is blocked by the color filter. At present, reduction of power consumption is also demanded for color displays as an environmental consideration. Therefore, a color filter having higher transmittance is required as a color filter to be used.

  A simplified structure of a typical organic EL display is shown in the schematic cross-sectional view of FIG. In the top emission structure of the organic EL display, the color filter 1 is formed on the basis of one transparent substrate 5 and the organic EL layer 21 is formed on the base of the opposing organic EL layer substrate 27, as in the liquid crystal display. . The organic EL layer 21 includes a TFT 9 patterned as a pixel switching element, a reflective cathode 25, red, green and blue light emitting layers 24 a, 24 b and 24 c and a transparent electrode 10. An adhesive layer is provided between the two substrates, and the end surface is sealed with a sealant 26. The block arrows indicate the light emission from the organic EL layer 21 and the selectively transmitted light from the color filter 1.

As an important problem of the organic EL display, there is reduction of power consumption along with extension of the life of the element. Therefore, active research has been conducted on improving the light emission efficiency of the device. Until now, it has been known that, in a light-emitting element using fluorescence emission, the generation probability of an excited singlet of an energy level necessary for emitting the fluorescence is statistically 25%. Therefore, theoretically, only 1/4 of the injected electrons and holes can be extracted as light. On the other hand, an organic EL element using phosphorescence from an excited triplet has been proposed (Patent Document 1).
In recent years, research on materials that exhibit phosphorescence at room temperature has been actively conducted.

  As described above, in the organic EL element, it is addressed as important issues to improve luminous efficiency, extend the lifetime of the element, and reduce power consumption. Therefore, sufficient performance has not been obtained in terms of color reproducibility. Therefore, a color filter is required in the sense of taking the role of correcting the color from the light emitting element. However, even if the color reproduction area can be expanded by the color filter, if the light from the EL element is blocked by the color filter, the effect of improving the light emission efficiency of the EL element becomes thin as an organic EL display. End up. Therefore, a color filter with higher transmittance is required as the color filter.

JP 2007-266021 A

M.A.Baldo et al Nature Vol.395 p151 (1998)

  In the conventional color filter, since the production by the photolithography method is mainstream, a photosensitive composition is often used, and a pigment having excellent light resistance and heat resistance is often used as a colorant of the photosensitive composition. Has been. However, the pigment is excellent in light resistance and heat resistance, but has a limit in improving the transmittance due to light scattering due to its large particle size. On the other hand, as described above, a color filter having a higher transmittance is required for both a liquid crystal display and an organic EL display.

  Therefore, in recent years, in order to obtain a color filter with higher transmittance, a color filter using a dye as a colorant has been developed. However, although the dye has a higher transmittance than a pigment, it has a problem that it is inferior in light resistance. There was a weak point in the reliability of display quality when used for a display.

  The present invention is proposed in view of the above-mentioned problems, and the problem to be solved by the present invention is to improve the photosensitive composition as a material for the color filter, thereby increasing the transmittance, and The object is to provide a color filter having characteristics excellent in light resistance. Another problem to be solved by the present invention is to provide a bright liquid crystal display and an organic EL display with low power consumption using the color filter.

  As means for solving the above problems, the invention described in claim 1 includes (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent. The photosensitive composition is a photosensitive composition characterized in that the number of functional groups of the photopolymerizable monomer (B) is 4 to 6.

  The invention described in claim 2 is characterized in that the photopolymerizable monomer (B) is contained in an amount of 20 wt% to 50 wt% in the solid content of the photosensitive composition. It is a photosensitive composition.

  The invention according to claim 3 is the photosensitive composition according to claim 1 or 2, wherein the (C) dye is a triarylmethane dye.

  The invention according to claim 4 is a color filter comprising the photosensitive composition according to any one of claims 1 to 3.

  The invention according to claim 5 is a liquid crystal display using the color filter according to claim 4.

  The invention according to claim 6 is an organic EL display using the color filter according to claim 4.

  According to the present invention, a color filter having a high transmittance by using a dye and an excellent light resistance can be obtained by improving the constituent material of the photosensitive composition, and such a color filter is used. By doing so, it is possible to provide a color display having a bright and clear color image with low power consumption, long life, and without lowering the efficiency during color display.

It is a cross-sectional schematic diagram for demonstrating the simple structure of a liquid crystal display. It is a cross-sectional schematic diagram for demonstrating the simple structure of an organic electroluminescent display.

  Hereinafter, the present invention will be summarized first, and then the details of the material surface, the general production method of the photosensitive composition, the production method of the color filter substrate, and the examples will be described in detail.

The photosensitive composition according to the present invention contains (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent as essential components. .
Moreover, you may contain additives, such as surfactant and a photosensitizer.

  In the photosensitive composition, (B) the number of functional groups of the photopolymerizable monomer is in the range of 4-6.

  When the number of functional groups of the photopolymerizable monomer is less than 4, patterning cannot be performed due to insufficient sensitivity in the exposure process, and when the number of functional groups exceeds 6, the transmittance is increased in the heating process when manufacturing the color filter. It will decline.

<Photopolymerizable monomer>
A photopolymerizable monomer is polymerized by irradiation with exposure light, and changes a colored photosensitive layer produced using the photosensitive coloring composition to be insoluble in a developer. Generally, it is a monomer whose polymerization is induced by radicals, but as the tetra- to 6-functional photopolymerizable monomer that can be used in the present invention, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprocalactone modified penta (meth) acrylate Typical examples include various acrylic esters and methacrylic esters.

In the present invention, the photopolymerizable monomer is desirably 20% to 50% in the solid content of the photosensitive composition.
This is because if it is less than 20%, the sensitivity in the exposure step decreases, which is not preferable. On the other hand, if it is more than 50%, the vicinity of the surface of the coating film is remarkably cured as compared with the deep part of the coating film, so that an overhang in which the pattern shape is reversely tapered tends to occur.

<Transparent resin>
The transparent resin used for the photosensitive composition is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a non-photosensitive resin such as a thermoplastic resin and a thermosetting resin, and a photosensitive resin. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

  The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polychlorinated resin. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, A polyimide resin etc. are mentioned. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin. However, these resins do not exhibit alkali solubility.

  At present, as the developer, an alkaline developer having a small influence on the environment is often used. For this reason, it is desirable to use an alkali-soluble resin as the resin binder. The alkali-soluble non-photosensitive transparent resin is a transparent resin having a property of dissolving in an alkaline aqueous solution and having no ethylenically unsaturated double bond. For example, an acidic functional group such as a carboxyl group or a sulfone group Non-photosensitive transparent resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000. Of the acidic functional groups, a carboxyl group is preferred. In order to stabilize dispersion and improve the development performance of the color filter coloring composition, the acid value of the non-photosensitive transparent resin is preferably higher than the acid value of the photosensitive transparent resin. The patterning property of the transparent colored coating film made of the composition is improved, and a transparent colored pixel having a stable shape is obtained.

  Specific examples of such alkali-soluble non-photosensitive resins include acrylic resins having acidic functional groups, α-olefin- (anhydrous) maleic acid copolymers, styrene- (anhydrous) maleic acid copolymers, Examples thereof include a styrene-styrene sulfonic acid copolymer, an ethylene- (meth) acrylic acid copolymer, and an isobutylene- (anhydrous) maleic acid copolymer. Among them, at least one kind selected from an acrylic resin having an acidic functional group, an α-olefin- (anhydrous) maleic acid copolymer, a styrene- (anhydride) maleic acid copolymer, and a styrene-styrene sulfonic acid copolymer. Resins are preferably used. Among these, acrylic resins having acidic functional groups are preferably used because of their high heat resistance and transparency. A resin having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000 can be preferably used.

  As the photosensitive resin, a linear polymer having a reactive functional group is reacted with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, cinnamic acid, etc. Examples thereof include resins in which a bond is introduced into the linear polymer. In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like, to thereby form an ethylenically unsaturated double bond. Resin introduced into the polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

  In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Those half-esterified with can be used as the photosensitive resin.

  The amount of ethylenically unsaturated double bonds introduced through a hydroxyl group or the like into the photosensitive transparent resin, which indicates the ease of photocuring, is indicated by the “double bond equivalent” of the resulting photosensitive transparent resin. . The double bond equivalent of the photosensitive transparent resin in the present invention is preferably 200 to 1200, and more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the ratio of the ethylenically unsaturated monomer having a reactive substituent for introducing an ethylenically unsaturated double bond is increased, and various characteristics are maintained. A sufficient amount of other ethylenically unsaturated monomers cannot be copolymerized. When it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small. Moreover, the weight average molecular weight (Mw) of photosensitive transparent resin becomes like this. Preferably it is 2000-200000, More preferably, it is 5000-50000.

<dye>
As the dye (C) of the present invention, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, triarylmethane dyes, oxazine dyes, thiazine dyes, methine dyes, quinoline dyes, perinone dyes and the like can be used. More preferably, a triarylmethane dye is used. Conventionally known triarylmethane-based coloring dyes can be widely used as the triarylmethane-based dye. Specifically, methyl violet, crystal violet, Victoria Blue B, OIL Blue 613 (manufactured by Orient Chemical Industries) VALIFAST Blue 1621 (manufactured by Orient Chemical Co., Ltd.), SBN Blue
701 (made by Hodogaya Chemical Co., Ltd.) and derivatives thereof are preferable. These triarylmethane dyes can be used alone or in combination of two or more.

<Photoinitiator>
(D) As a photoinitiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as' -methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2, 4, 6 -Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (P-Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6 Styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Riadin, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Triazine compounds such as methyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], o- (acetyl)- Oxime ester compounds such as N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4 Phosphine compounds such as 1,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, can Examples include quinone compounds such as furquinone and ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds. These can be used singly or in combination of two or more.

  The amount of the photoinitiator used is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight, based on the total solid content (components other than the solvent) of the photosensitive composition.

  As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like can also be used in combination.

<solvent>
Examples of the (E) solvent of the present invention include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, Examples include methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents, and these are used alone or in combination.

A surfactant or the like may be added to the photosensitive composition of the present invention. Surfactants include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amine halogens. Cationic surfactants such as acid salts and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as these can be used, and these may be used in combination.
Add conventional additives such as plasticizers, adhesion promoters, fillers, antifoaming agents, and leveling agents as needed, as well as thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and phenothiazine. be able to.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the photosensitive composition of this invention by the printing method or the photolithographic method. The transparent substrate is not particularly limited as long as it is transparent and has a certain degree of rigidity, but a film or thin plate of glass, polyester, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylic resin or the like is used. Can do.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter that can be manufactured using the photosensitive composition of the present invention is incorporated into the normal manufacturing process of the liquid crystal display shown in the schematic cross-sectional view of FIG. Thus, a color liquid crystal display having a bright and clear color image with low power consumption can be provided.

  The color filter that can be manufactured using the photosensitive composition of the present invention is incorporated into the normal manufacturing process of the organic EL display shown in the schematic sectional view of FIG. It is possible to provide an organic EL display having a low-power consumption, a long lifetime, and a bright and clear color image without reducing efficiency.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. [Adjustment of resin] and [Evaluation items] below are descriptions of materials and methods common to each Example, and [Preparation of photosensitive composition] is described in Examples 1 to 8 (including Examples 5 to 8). Is equivalent to Comparative Examples 1 to 4), and [Evaluation Result] is a comprehensive explanation for comparing the above results. In the examples, “parts” means “parts by weight”.

[Resin adjustment]
(Synthesis example of transparent resin)
70 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of benzyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 5.3 parts of methacrylic acid at the same temperature. 2 parts of a mixture of 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile as monomer (a) The polymerization reaction was carried out dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that a non-photosensitive resin solution was prepared. The weight average molecular weight Mw of the obtained transparent resin was 20000.

[Preparation of photosensitive composition]
A photosensitive composition was prepared as follows.

Photosensitive composition 1
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 1.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.8 parts Transparent resin (N.V20%) 38.4 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 3.84 parts Photopolymerizable Monomer (“Aronix M408” manufactured by Toagosei Co., Ltd .: ditrimethylolpropane tetraacrylate) 7.68 parts Cyclohexanone 49.28 parts

Photosensitive composition 2
Photosensitive composition 2 was obtained in the same manner except that the photopolymerizable monomer used in photosensitive composition 1 was changed to “Aronix M402” (dipentaerythritol penta and hexaacrylate) manufactured by Toagosei Co., Ltd.

Photosensitive composition 3
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 0.5 μm filter to obtain a blue photosensitive composition 3.
SBN Blue 701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.8 parts Transparent resin (N.V20%) 62.95 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 2.20 parts Photopolymerizable Monomer (“Aronix M402” manufactured by Toagosei Co., Ltd .: Dipentaerythritol penta and hexaacrylate) 4.41 parts Cyclohexanone 29.64 parts

Photosensitive composition 4
A mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain a blue photosensitive composition 4.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.8 part Transparent resin (N.V20%) 24.00 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 4.80 parts Photopolymerizable Monomer (“Aronix M402” manufactured by Toagosei Co., Ltd .: dipentaerythritol penta and hexaacrylate) 9.60 parts cyclohexanone 60.80 parts

<Comparative example 1>
Photosensitive composition 5
Photosensitive composition 5 was obtained in the same manner except that the photopolymerizable monomer of photosensitive composition 1 was changed to “Aronix M309” (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

<Comparative example 2>
Photosensitive composition 6
Photosensitive composition 6 was obtained in the same manner except that the photopolymerizable monomer of photosensitive composition 1 was changed to “UD408A” (dipentaerythritol pentaacrylate diisocyanate urethane prepolymer) manufactured by Osaka Organic Chemical Industry Co., Ltd.

<Comparative Example 3>
Photosensitive composition 7
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 7.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.8 parts Transparent resin (N.V20%) 69.82 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 1.75 parts Photopolymerizable Monomer (“Aronix M402” manufactured by Toagosei Co., Ltd .: dipentaerythritol penta and hexaacrylate) 3.49 parts cyclohexanone 24.15 parts

<Comparative example 4>
Photosensitive composition 8
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition 8.
SBN Blue701 (Triarylmethane dye manufactured by Hodogaya Chemical Co., Ltd.) 0.8 part Transparent resin (N.V20%) 17.45 parts Photoinitiator (“Irg907” manufactured by Ciba Specialty Chemicals) 5.24 parts Photopolymerizable Monomer (“Aronix M402” manufactured by Toagosei Co., Ltd .: dipentaerythritol penta and hexaacrylate) 10.47 parts cyclohexanone 66.04 parts

As photosensitive compositions for color filter production, photosensitive compositions 1 to 4 are examples 1 to 4,
The photosensitive compositions 5-8 were made into Examples 5-8 or Comparative Examples 1-4.

[Evaluation item]
(sensitivity)
About each photosensitive composition prepared by each said Example and comparative example, the sensitivity was evaluated as follows.
First, each of the photosensitive compositions 1-8 obtained in the above Examples and Comparative Examples was applied on a glass substrate by spin coating so as to have a film thickness of 2 μm, and then dried, and then at 70 ° C. After pre-baking for 20 minutes, UV exposure was performed through a photomask having a 50 μm fine line pattern by a proximity exposure method using a proximity aligner. The exposure amount was set to 11 levels of 10, 20, 30, 50, 80, 100, 150, ²⁰⁰ , 300, 400, and 500 mJ / cm ² .
Next, shower development was performed using a 1.25% by mass sodium carbonate solution, followed by washing with water to complete patterning. The film thickness of the obtained filter segment was divided by the film thickness of the unexposed / undeveloped portion to calculate the remaining film ratio. Then, the exposure sensitivity curve was plotted with the horizontal axis representing the common logarithm of the exposure dose and the vertical axis representing the remaining film ratio after development. From the obtained exposure sensitivity curve, the minimum exposure amount at which the post-development residual film ratio reaches 85% or more is the saturation exposure amount, that is, the sensitivity of the photosensitive composition, and the one less than 300 mJ / cm ² is good (◯) The thing of 300 mJ / cm < ² > or more was made into defect (x) determination.
(Pattern shape)
On the glass substrate, each of the photosensitive compositions 1 to 8 obtained in the above Examples and Comparative Examples was applied by spin coating so as to have a film thickness of 2 μm, and then dried, and then at 70 ° C. for 20 minutes. After performing pre-baking, it was exposed with a saturated exposure amount of each photosensitive composition by a proximity exposure method using a proximity aligner. Next, shower development was performed using a 1.25% by mass sodium carbonate solution, followed by washing with water to complete patterning, and then baking was performed at 180 ° C. for 20 minutes in a clean oven to obtain an evaluation substrate.
The shape of the obtained pattern was observed with an SEM, and the case where there was no peeling and the shape was a forward taper shape was marked with ◯, and the shape where the pattern was peeled or overhanged was marked with ×.
(Transmittance)
The spectral transmittance of the substrate patterned with the photosensitive compositions obtained in the above Examples and Comparative Examples was measured with “OSP-2000” manufactured by Olympus Corporation. A sample having a transmittance of 450 nm of 96.0% or more was evaluated as ◯, and a sample having a transmittance of less than 96.0% was evaluated as x.
(Light resistance)
The substrate on which the photosensitive composition was patterned was exposed to light with a light resistance evaluation apparatus (“Weather Meter Ci35A” manufactured by Atlas) for 100 hours, and the color difference ΔEab before and after the light resistance evaluation was measured.
A case where ΔEab was 5 or less was marked as “◯”, and a case where ΔEab was over “5”.

[Evaluation results]
The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.

From the results in Table 1, the following is clear. That is, in a photosensitive composition containing at least (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent, the photopolymerizable monomer (B) It can be seen that when the number of functional groups is 4 to 6, the color difference in the light resistance test is reduced, and a product with good sensitivity, pattern shape, and transmittance can be obtained. When the number of functional groups of the photopolymerizable monomer is smaller than 4, the light resistance improving effect is not sufficient, and when it exceeds 6, the transmittance is decreased.
If the ratio of the photopolymerizable monomer in the solid content is less than 20%, the exposure sensitivity is lowered, and if it exceeds 50%, the pattern shape is overhanged, making it difficult to produce a color filter substrate.

  By using a dye as the coloring material of the color filter, it has high transmittance, that is, high efficiency in color display and excellent light resistance, so that it has a low power consumption, long life, and a bright and clear color image. A device can be obtained.

1 ... Color filter 2 ... Liquid crystal 3 ... TFT array 4 ... Backlight 5 ... Transparent substrate 6a ... Red colored layer 6b ... Green colored layer 6c ... Blue colored layer 7 ... Black matrix 8 ... Over Coat layer 9 ... TFT
DESCRIPTION OF SYMBOLS 10 ... Transparent electrode 11 ... Polarizing plate 12 Alignment film 21 ... Organic EL layer 23 ... Barrier layer 24a ... Red light emitting layer 24b ... Green light emitting layer 24c ... Blue light emitting layer 25 ... Reflective cathode 26 ... Sealing Stopper 27 Organic EL layer substrate

Claims (6)

  In the photosensitive composition containing (A) a transparent resin, (B) a photopolymerizable monomer (C) dye, (D) a photoinitiator, and (E) a solvent, the number of functional groups of the (B) photopolymerizable monomer is The photosensitive composition characterized by being 4-6.   2. The photosensitive composition according to claim 1, wherein the photopolymerizable monomer (B) is contained in an amount of 20 to 50 wt% in the solid content of the photosensitive composition.   The photosensitive composition according to claim 1, wherein the (C) dye is a triarylmethane dye.   A color filter comprising the photosensitive composition according to claim 1.   A liquid crystal display using the color filter according to claim 4.   An organic EL display using the color filter according to claim 4.

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