JP2005292199A - Color filter manufacturing method, color filter manufactured using the same, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a color filter excellent in productivity, characterized in that a negative resist containing a resin having a phenolic hydroxyl group is used to form projections for liquid crystal alignment. Moreover, the color filter manufactured by it and also the liquid crystal display device using the same are provided.
SOLUTION: In a color filter having a colored layer composed of three primary colors and a conductive layer on the same substrate and further having projections for split orientation fixed on the conductive layer, the projections cap at least a phenolic hydroxyl group. It forms using the photosensitive resin composition containing resin capped with the agent. In addition, forming the protrusion for split orientation using a photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator in addition to a resin in which a phenolic hydroxyl group is capped with a capping agent is also included. .
[Selection] Figure 1

Description

  The present invention relates to a color filter having protrusions having a liquid crystal alignment dividing function, a manufacturing method thereof, and a liquid crystal display device using the same.

  Liquid crystal display devices are widely used from small-area devices such as watches and cameras to large-area devices such as computer terminal display devices and television image display devices. Is progressing rapidly. Color filters are indispensable for the color display of liquid crystal displays, and are important components that determine the performance of color liquid crystal displays. Finely patterned ones are used to display high-definition images. Yes. Known methods for producing a color filter include, for example, a dyeing method, an ink jet method, a printing method, a photolithography method, and an etching method.

  On the other hand, the liquid crystal display device has a problem that the viewing angle is narrow due to the birefringence of the liquid crystal. As means for solving this problem, IPS (In-Plane Switching), VA (Vertical Alignment), and the like have been proposed as liquid crystal driving methods. Among them, the VA method is a vertical alignment type liquid crystal display method that controls the liquid crystal molecules to have a plurality of tilt directions within one pixel so that uniform halftone display is possible in all directions, and has excellent contrast. A liquid crystal display device having both viewing angle characteristics and response speed is provided.

  A color filter used in a VA liquid crystal display device requires a strap-like or dot-like protrusion for controlling the alignment of liquid crystal.

  1A and 1B are explanatory views schematically showing the operation of a VA liquid crystal display device in cross section. As shown in FIGS. 1A and 1B, a VA liquid crystal display device (10) includes a TFT side substrate (11) provided with alignment control protrusions (13) via liquid crystal molecules (15). And the color filter side substrate (12) provided with the alignment control protrusions (14). However, the alignment control protrusions (13) and the alignment control protrusions (14) are in alternate positions. It is like that.

  FIG. 1A shows a state when no voltage is applied, and when no voltage is applied, the liquid crystal molecules (15) are aligned vertically between the two substrates, but the alignment control protrusion (13) and the alignment control protrusion The liquid crystal molecules in part (14) are slightly tilted due to the influence of the slopes of the protrusions. FIG. 1B shows a state when a voltage is applied. When a voltage is applied, the liquid crystal molecules on the inclined surface of the protrusion begin to be inclined, and the liquid crystal molecules other than the inclined surface are sequentially aligned in the same manner. That is, the alignment of liquid crystal molecules is controlled by providing protrusions instead of rubbing treatment.

  However, in such a VA liquid crystal display device, if a voltage is applied for a long period of time, charges may accumulate on the surface of the alignment control protrusion and an afterimage, i.e., burn-in, may occur. This phenomenon seems to be largely related to the electrical characteristics of the material forming the projections for aligning the liquid crystal, but it is difficult to judge with limited electrical characteristic values.

  At present, as a material for forming projections for liquid crystal alignment, a positive resist mainly composed of a phenol resin, which is a part that is irradiated with light, is known (for example, see Patent Document 1). .

  This is because heat flow occurs by heating after pattern formation, and an ideal bowl-like shape is obtained, so that alignment of liquid crystal can be controlled and no seizure occurs by using this material. But this is a big reason. Although the detailed factor is not well understood, it seems that it is largely due to the characteristics of the phenol resin.

  On the other hand, in the use of a positive resist, the photomask for forming the fine liquid crystal alignment protrusions is almost a bare glass in which only the protrusion forming part is shielded from light, and the occurrence of the same defect due to adhesion of foreign matter, Or there is a problem such as generation of a defect due to diffracted light wrapping around the light shielding portion.

In other words, as a protrusion material that controls the alignment of the liquid crystal, while maintaining its own electrical characteristics that do not cause seizure, the light-irradiated part, called a negative resist that is easy to use in production, becomes insoluble. The development of such resists is desired. However, in the case of a radical polymerization type photosensitive resin composition containing a resin having a phenolic hydroxyl group, since the phenolic hydroxyl group has a radical polymerization inhibitory effect, photocuring does not proceed and a negative resist is prepared. It was difficult.
JP-A-5-333540

  An object of the present invention is to provide a projection for liquid crystal alignment using a negative resist containing a resin having a phenolic hydroxyl group in order to maintain the above-described characteristics of the phenol resin and solve the above problems. Another object of the present invention is to provide a method for producing a color filter excellent in productivity, characterized in that it is formed, and to provide a color filter produced thereby and a liquid crystal display device using the color filter.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

  That is, the present invention provides a color filter having a colored layer composed of three primary colors and a conductive layer on the same substrate, and further having protrusions for split orientation fixed on the conductive layer, wherein the protrusions have at least a phenolic hydroxyl group. A method for producing a color filter, comprising a photosensitive resin composition containing a resin capped with a capping agent, a color filter produced by the production method, and a liquid crystal display device produced using the color filter Is the gist.

  The method for producing a color filter according to the present invention includes a photosensitive resin composition that can be photocured and alkali-developed as a negative resist in producing a color filter having protrusions for divisional orientation fixed on a conductive layer. By using it, it is excellent in productivity. In addition, the manufacturing method is useful because it is possible to form protrusions without variation in film thickness even with a thickness of several μm.

  The method for producing a color filter of the present invention includes a color filter having a colored layer of three primary colors and a conductive layer on the same substrate, and further having protrusions for divisional orientation fixed on the conductive layer. It consists of forming using the photosensitive resin composition containing the binder resin which capped the phenolic hydroxyl group with the cap agent.

  It includes forming using a photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator in addition to a binder resin capped with a phenolic hydroxyl group.

  Moreover, it includes desorbing 50% or more of the cap agent by heating the formed protrusions for split orientation at 150 to 250 ° C. for 30 to 60 minutes.

  Furthermore, a color filter manufactured by the manufacturing method and a liquid crystal display device using the color filter.

  The cap agent used in the present invention is a compound having a functional group capable of reacting with a phenolic hydroxyl group. Examples of the functional group capable of reacting with a phenolic hydroxyl group include an isocyanate group, an acid anhydride group, an acid halide group, and vinyl ether. Group, propenyl ether group and the like. In addition, high sensitivity can be expected by containing a (meth) acrylate group, and any of a (meth) acrylate group and at least an isocyanate group, an acid anhydride group, an acid halide group, a vinyl ether group, or a propenyl ether group. Mention may be made of compounds containing one functional group.

  Isocyanate groups react with phenolic hydroxyl groups to form urethane bonds. An acid anhydride group and an acid halide group react with a phenolic hydroxyl group to form an ester bond.

  Vinyl ether groups and propenyl ether groups react with phenolic hydroxyl groups to form acetal bonds. These bonds are preferable because they can be reversibly advanced by heating or the like.

  Examples of the isocyanate group-containing compound include isocyanate compounds having 4 to 50 (preferably 4 to 20) carbon atoms (for example, phenyl isocyanate, benzyl isocyanate, isocyanatoethyl (meth) acrylate, etc.).

  Examples of the acid anhydride group-containing compound include acid anhydrides having 4 to 50 (preferably 4 to 20) carbon atoms (for example, acetic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, anhydrous ( (Meth) acrylic acid).

  Examples of the acid halide group-containing compound include hydrocarbons (having 4 to 50 (preferably 4 to 20) carbon atoms) containing acid halide groups (for example, acetyl chloride, (meth) acryloyl chloride, etc.).

  Examples of the vinyl ether group-containing compound include hydrocarbons (4 to 50 (preferably 4 to 20) carbon atoms) containing vinyl ether groups (for example, methyl vinyl ether, butyl vinyl ether, 2- (meth) acryloyloxyethyl vinyl ether, etc.). It is done.

  Examples of the propenyl ether group-containing compound include a hydrocarbon containing a propenyl ether group (4 to 50 carbon atoms (preferably 4 to 20)) (for example, methyl propenyl ether, butyl propenyl ether, 2- (meth) acryloyloxyethyl propenyl). Ether).

  The resin having a phenolic hydroxyl group that can be used in the present invention is not particularly limited as long as it is an oligomer or polymer having a phenolic hydroxyl group. For example, a phenol resin, a cresol resin, a phenol-cresol resin, a hydroquinone-formaldehyde resin, polyvinylphenol, and the like can be given. Of these, phenol resins, cresol resins and polyvinylphenol are particularly preferable.

  The weight average molecular weight of these resins is usually 500 to 100,000, preferably 700 to 50,000, particularly preferably 1,000 to 30,000.

  A resin in which a phenolic hydroxyl group is capped with a capping agent is obtained, for example, by dissolving a resin having a capping agent and a phenolic hydroxyl group in the absence of a solvent or in the presence of a solvent, and heating and adding a reaction catalyst as necessary. I can do it. Examples of the solvent include esters, ethylene glycol monoalkyl ethers, ketones, ethylene glycol alkyl ether acetates and butyl acetates, preferably ketones and esters.

  The temperature at the time of heating is appropriately determined according to the easiness of the reaction, but the reaction temperature is usually 50 ° C. or higher and 90 ° C. or lower, and the reaction time is 1 to 6 hours.

  The reaction catalyst is appropriately set according to the functional group to be reacted. When the cap agent is an isocyanate group-containing compound, a metal catalyst, an amine catalyst, or the like can be used.

  Examples of metal catalysts include tin-based catalysts (for example, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, and dibutyltin maleate); lead-based catalysts (for example, Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate and the like). Examples of other metal catalysts include cobalt naphthenate.

  As the amine catalyst, tertiary amine (for example, triethylamine); diamine (for example, triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, etc.); morpholine (for example, N-methylmorpholine, N-ethylmorpholine, etc.) Alkanolamines (eg, diethylethanolamine, dimethylethanolamine, etc.); 1,8-diazabicyclo [5,4,0] undecene (Sanapro Corporation: DBU); amine carbonates and organic acid salts (eg, dimethylamino) Carbonate and organic acid salt of ethylamine, carbonate and organic acid salt of dimethylaminopropylamine, carbonate and organic acid salt of diethylaminopropylamine, carbonate and organic acid salt of dibutylaminoethylamine, carbonic acid of dimethylaminooctylamine And organic acid salts, carbonates and organic acid salts of dipropylaminopropylamine, carbonates and organic acid salts of 2- (1-aziridinyl) ethylamine, and carbonates of 4- (1-piperidinyl) -2-hexylamine And organic acid salts);

  When the capping agent is an acid anhydride group-containing compound or an acid halide group-containing compound, the above metal catalyst or the like can be used. When the cap agent is a vinyl ether group-containing compound or a propenyl ether group-containing compound, the above metal catalyst and the above amine catalyst can be used.

  The amount of cap by the capping agent in the resin capped with the phenolic hydroxyl group by the capping agent is usually 0.5 mol% to 95 mol% of the phenolic hydroxyl group. Preferably they are 3 mol%-90 mol, Most preferably, they are 5 mol%-85 mol%. If it is lower than 0.5 mol%, the effect is not exhibited. On the other hand, if it exceeds 95 mol%, the developability of the composition deteriorates, which is not preferable.

  The resin capped with the capping agent is obtained by reacting the phenolic hydroxyl group of the resin having a phenolic hydroxyl group with a capping agent, and a resin obtained by reacting a resin capped with the capping agent and an isocyanate group-containing compound is preferable. . Specific examples thereof include a reaction product of a phenol resin and an isocyanate group-containing compound, a reaction product of a cresol resin and an isocyanate group-containing compound, and a reaction product of polyvinylphenol and an isocyanate group-containing compound.

  The resin in which the phenolic hydroxyl group is capped with a capping agent may have a photosensitive group. The photosensitive group means a reactive group that can be polymerized by an active species generated by a photo radical generator, and includes a vinyl group, a (meth) acryloyl group, a vinyloxy group, a vinyloxycarbonyl group, a (meth) allyloxy group, ( And a (meth) allyloxycarbonyl group.

  Of these, a (meth) acryloyl group, a vinyloxy group and a (meth) allyloxy group are preferable, and a (meth) acryloyl group is more preferable.

  As a method for imparting a photosensitive group, for example, a method using a photosensitive group-containing compound as a cap agent is simple. Examples of the photosensitive group-containing compound (PS) include glycidyl (meth) acrylate and methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko). In order to improve alkali solubility, a carboxyl group may be introduced into a part of the phenolic hydroxyl group.

  A method for introducing a carboxyl group can be easily performed by a reaction between a phenolic hydroxyl group and an acid anhydride. Specific examples of the acid anhydride include acid anhydrides having 4 to 50 (preferably 4 to 20) carbon atoms (for example, acetic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, trimellitic anhydride, anhydrous ( (Meth) acrylic acid etc.).

  Furthermore, other binder resins may be included in addition to the resin capped with a cap agent as necessary. Examples of other binder resins include polymers obtained by (co) polymerizing at least one monomer selected from monomers containing an ethylenically unsaturated group. In particular, it is preferably alkali-soluble so as not to cause a problem in development.

  The alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline aqueous solution in the light irradiation part or the light shielding part. Such resins generally include (meth) acrylic acid, hydrophilic monomers represented by monomers having 2-hydroxyethyl, acrylamide, N-vinylpyrrolidone and ammonium salts, and (meth) acrylic acid. Known is a copolymer obtained by copolymerizing an oleophilic monomer represented by ester, vinyl acetate, styrene, N-vinylcarbazole and the like with an appropriate mixing ratio by a known method. Specific examples include those disclosed in JP-A-57-16408, JP-A-2-181704, JP-A-2-199403, and the like, but are not limited thereto.

  When other binder resins are used, the amount (% by weight) of the binder resin used is usually 1 to 70, preferably 5 to 60, based on the weight of the resin having a phenolic hydroxyl group capped with a cap agent. Moreover, these may have a photosensitive group. The photosensitive group means a reactive group that can be polymerized by an active species generated by a photo radical generator, and includes a vinyl group, a (meth) acryloyl group, a vinyloxy group, a vinyloxycarbonyl group, a (meth) allyloxy group, ( And a (meth) allyloxycarbonyl group.

  The resin in which the phenolic hydroxyl group of the present invention is capped with a capping agent can be cured and heated at 150 ° C. to 250 ° C. for 30 to 60 minutes to desorb 50% or more of the capping agent. Thereby, reaction inhibition is suppressed by a cap at the time of a curing reaction, and after the curing reaction, the phenolic hydroxyl group can be regenerated by removing the cap as necessary.

  At this time, the removed capping agent reacts with other reactive groups in the system, so that the phenolic hydroxyl groups can be efficiently regenerated without causing recombination with the phenolic hydroxyl groups.

  In the present invention, the ethylenically unsaturated compound used is a compound having at least one in the molecule, a substance that is polymerized by an active species generated by photolysis of a photopolymerization initiator, and a monofunctional vinyl monomer. In addition to these, a polyfunctional vinyl monomer may be contained, or a mixture thereof may be used. Moreover, the dimer and oligomer which have an ethylenically unsaturated double bond are included. Specifically, high-boiling vinyl monomers such as (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, and aliphatic polyhydroxy compounds, For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol and the like Or poly (meth) acrylic acid esters, alicyclic monomers such as dimethylol tricyclodecane monoacrylate and dimethylol tricyclodecane diacrylate, and aromatic polyhydroxy compounds such as hydroquinone, resorcin, catechol, pyrogallol, Examples include, but are not limited to, di- or poly (meth) acrylic acid esters such as bisphenol A, ethylene oxide-modified (meth) acrylic acid esters of isocyanuric acid, and the like. Among these, those having a boiling point of 100 ° C. or more at normal pressure are more preferred. Moreover, you may use these in mixture of 2 or more types as needed.

  Examples of the photopolymerization initiator used in the present invention include benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropylthioxanthone, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoinpropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiopheno 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, Diisopropylthioxanthone, Michler's ketone, benzyl-2,4,6- (trihalomethyl) triazine, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) ) Heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone and 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) - butan-1-one, and the like.

  In addition, commercially available products can be easily obtained. For example, Irgacure 651, 184, 1173, 907, 369, 819 manufactured by Ciba Specialty Chemicals, TGI manufactured by CGI124 or BASF, Nippon Kayaku Co., Ltd. An example is Kayacure DTEX manufactured by Kato Corporation. Moreover, you may make the composition of this invention contain well-known additives, such as a sensitizer, a polymerization inhibitor, an inorganic fine particle, and a well-known solvent as needed.

  The photocurable resin composition of the present invention can be cured by irradiating actinic rays after removing the solvent, if necessary, directly in a container and applied to a substrate.

  Moreover, it can also develop and use after exposure by arbitrary patterns as needed. Examples of the active light include visible light, ultraviolet light, and laser light. Examples of the light source include sunlight, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a semiconductor laser.

  A method for producing a color filter having projections for split orientation fixed on a conductive material using a photosensitive resin composition containing a resin in which the phenolic hydroxyl group of the present invention is capped with a capping agent is an ordinary method. A photolithography method is used on a colored layer composed of three primary colors, which is patterned on a transparent substrate such as glass or plastic, and a transparent conductive layer formed thereon.

  That is, a photosensitive resin composition containing a resin in which a phenolic hydroxyl group used in the present invention is capped with a capping agent is applied to a substrate having a colored layer and a transparent conductive layer using a coating apparatus.

  As the coating apparatus, a known coating apparatus can be used. For example, a spin coater, an air knife coater, a roll coater, a bar coater, a curtain coater, a gravure coater, a die coater, a comma coater, or the like is used.

  After coating on the substrate, vacuum drying or / and heat drying are performed. Drying by heating is preferably performed at 70 to 120 ° C. Thereafter, light irradiation is performed through a photomask having a predetermined pattern, and development is performed to form protrusions for controlling the alignment of liquid crystal on the transparent conductive layer of the substrate.

  The development uses alkaline water having a pH of 4 to 10, and examples include those containing water as a main component and containing sodium hydroxide, sodium carbonate, sodium bicarbonate, hydrochloric acid and the like, a surfactant, a water-soluble organic solvent, and the like.

  As the surfactant, known anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants and the like can be used. As a developing method, a dip method or a shower method can be used. The development time is appropriately determined according to the film thickness and the solubility of the resist.

  As needed, when baking, it is 100-250 degreeC, Preferably it is 150-240 degreeC, Most preferably, it is 180-230 degreeC.

  The baking time is 5 minutes to 6 hours, preferably 15 minutes to 4 hours, particularly preferably 30 minutes to 3 hours.

  The method for producing a color filter of the present invention is a method for producing a color filter having protrusions for divisional orientation fixed on a conductive layer. The present invention provides a production method having excellent productivity by using a possible photosensitive resin composition.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, the part means part by weight. A production example of a resin in which a phenolic hydroxyl group is capped with a capping agent is shown.
<Production Example 1>
To Kolben, 20 parts of cresol novolac resin (Asahi Organic Materials Co., Ltd .: EP-4020G) and 80 parts of cyclohexanone were charged and stirred until evenly dissolved. 0.05 part of BHT and 1 part of isocyanatoethyl methacrylate were added and heated to 60 ° C. 0.2 parts of dibutyltin laurate was added as a catalyst and reacted at 60 ° C. for 3 hours. Thereafter, 1 part of trimellitic anhydride was added, and the mixture was further reacted for 3 hours. Thereafter, the solution was diluted with cyclohexanone so that the resin concentration became 20% by weight to obtain a cyclohexanone solution of the target polymer (A-1).
<Production Example 2>
A cyclohexanone solution of the target polymer (A-2) was obtained in the same manner except that the amount of isocyanatoethyl methacrylate in Production Example 1 was changed from 1 part to 10 parts.
<Production Example 3>
A cyclohexanone solution of the target polymer (A-3) was obtained in the same manner except that the amount of isocyanatoethyl methacrylate in Production Example 1 was changed from 1 part to 19 parts.
<Production Example 4>
In Kolben, 20 parts of polyvinylphenol (manufactured by Maruzen Chemical Co., Ltd .: Marcalinker S-4P) and 80 parts of cyclohexanone were charged and stirred until evenly dissolved. 0.05 part of BHT and 5 parts of isocyanatoethyl methacrylate were added and heated to 60 ° C. 0.2 parts of dibutyltin laurate was added as a catalyst and reacted at 60 ° C. for 3 hours.

Thereafter, 1 part of trimellitic anhydride was added, and the mixture was further reacted for 3 hours. Then, it diluted with cyclohexanone so that the resin concentration might be 20 weight%, and the cyclohexanone solution of the target polymer (A-4) was obtained.
<Production Example 5>
To Kolben, 20 parts of cresol novolac resin (Asahi Organic Materials Co., Ltd .: EP-4020G) and 80 parts of cyclohexanone were charged and stirred until evenly dissolved. 0.05 part of BHT and 10 parts of isocyanatoethyl methacrylate were added and heated to 60 ° C. 0.2 parts of dibutyltin laurate was added as a catalyst and reacted at 60 ° C. for 3 hours.

Then, it diluted with cyclohexanone so that the resin concentration might be 20 weight%, and the cyclohexanone solution of the target polymer (A-5) was obtained.
<Production Example 6>
To Kolben, 20 parts of polyvinylphenol (manufactured by Maruzen Chemical Co., Ltd .: Marcalinker S-4P) and 80 parts of cyclohexanone were charged and stirred until evenly dissolved. 0.05 part of BHT and 5 parts of isocyanatoethyl methacrylate were added and heated to 60 ° C. 0.2 parts of dibutyltin laurate was added as a catalyst and reacted at 60 ° C. for 3 hours.

  Then, it diluted with cyclohexanone so that the resin concentration might be 20 weight%, and the cyclohexanone solution of the target polymer (A-6) was obtained.

The manufacture example of the photosensitive resin composition for forming the processus | protrusion for liquid crystal orientation control is shown below.
<Production Example 7>
In a glass container, 500 parts of polymer (A-1) for the produced example, 150 parts of DA-600 (manufactured by Sanyo Chemical) as an ethylenically unsaturated compound, and Irgacure 907 (Ciba Specialty) as a photopolymerization initiator (Chemicals Co., Ltd.) 25 parts was added, stirred until uniform, and further cyclohexanone was added so as to be 25% by weight to obtain a photocurable resin composition (P-1).
<Production Examples 8 to 20>
The photocurable resin composition (P-) was prepared in the same manner as in Production Example 5 with a combination of the types and amounts of polymers (A-1) to (A-6), ethylenically unsaturated compounds and photopolymerization initiators shown in Table 1. 2) to (P-14) were produced. In addition, the photosensitive resin composition was adjusted with cyclohexanone so that all would be 25 weight%.
<Preparation of coloring material>
The following were used as the coloring agents for coloring the coloring material used for producing the color filter.

Red pigment: C.I. I. Pigment Red 254 (“Ilgar Forred B-CF” manufactured by Ciba Specialty Chemicals) and C.I. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
Green pigment: C.I. I. Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink) and C.I. I. Pigment Yellow 150 (Bayer's “Funcheon First Yellow Y-5688”)
Blue pigment: C.I. I. Pigment Blue 15 (“Rionol Blue ES” manufactured by Toyo Ink) C.I. I. Pigment Violet 23 (manufactured by BASF “Paliogen Violet 5890”)
Red, green, and blue coloring materials were prepared using the respective pigments.
-Red coloring material After stirring and mixing the mixture of the following composition uniformly, it disperse | distributed with the sand mill for 5 hours using the glass bead of diameter 1mm, Then, it filtered with a 5 micrometer filter, and produced the dispersion of the red pigment.

Red pigment: C.I. I. Pigment Red 254 18 parts by weight Red pigment: C.I. I. Pigment Red 177 2 parts by weight Acrylic varnish (solid content 20%) 108 parts by weight Thereafter, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a red colored material.

150 parts by weight of the above dispersion 13 parts by weight of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photoinitiator 3 parts by weight (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 1 part by weight Cyclohexanone 253 parts by weight, green coloring material The same method as that for the red coloring material was used so that the composition would be the following composition.

Green pigment: C.I. I. Pigment Green 36 16 parts by weight Yellow pigment: C.I. I. Pigment Yellow 150 8 parts by weight Acrylic varnish (solid content 20%) 102 parts by weight Trimethylolpropane triacrylate 14 parts by weight (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photoinitiator 4 parts by weight (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by weight Cyclohexanone 257 parts by weight, blue coloring material Each of the compositions was prepared in the same manner as the red coloring material so that the composition was as follows.

Blue pigment: C.I. I. Pigment Blue 15 50 parts by weight Purple pigment: C.I. I. Pigment Violet 23 2 parts by weight Dispersant (“Solce Birds 20000” manufactured by Zeneca) 6 parts by weight Acrylic varnish (solid content 20%) 200 parts by weight Trimethylolpropane triacrylate 19 parts by weight (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.) )
Photoinitiator 4 parts by weight (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by weight Cyclohexanone 214 parts by weight <Colored layer formation and transparent conductive film formation>
A colored layer was formed using the obtained coloring material.

A red coloring material was applied to a glass substrate by spin coating so that the finished film thickness was 1.8 μm. After drying at 90 ° C. for 5 minutes, light from a high-pressure mercury lamp is irradiated through a striped photomask for forming a colored layer at 300 mJ / cm ² and developed with an alkali developer for 60 seconds to obtain a striped red colored layer. It was. Then, it baked at 230 degreeC for 30 minutes.

  Next, the green coloring material was similarly applied by spin coating so that the finished film thickness was 1.8 μm. After drying at 90 ° C. for 5 minutes, a green colored layer was obtained by exposing and developing through a photomask so that a pattern was formed adjacent to the above-mentioned red colored layer. Then, it baked at 230 degreeC for 30 minutes.

  Further, in the same manner as in red and green, a blue colored material having a finished film thickness of 1.8 μm and adjacent to the red and green colored layers was obtained. Thus, a color filter having a striped colored layer of three colors of red, green, and blue on the transparent substrate was obtained. Then, it baked at 230 degreeC for 30 minutes. The alkaline developer has the following composition.

Sodium carbonate 1.5% by weight
Sodium bicarbonate 0.5% by weight
Anionic surfactant (Kao Perillex NBL) 8.0% by weight
90% by weight of water
Indium tin oxide (ITO) was formed on this color filter by 1500 Å by a general sputtering method.
<Manufacture of color filter having protrusions for controlling liquid crystal alignment>
<Example 1>
The photosensitive resin composition (P-1) was spin-coated on the above-mentioned color filter with ITO so as to have a finished film thickness of 1.3 to 1.7 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming protrusions at 100 mJ / cm ² . The exposure was performed with a gap (exposure gap) between the photomask and the substrate of 100 μm. Thereafter, development was performed using an alkali developer, and after washing with water, post-baking was performed at 230 ° C. for 45 minutes to form a color filter having protrusions for controlling liquid crystal alignment.
<Examples 2 to 14>
In the same manner as in Example 1, the photosensitive resin compositions (P-2) to (P-14) in Table 1 were used to form liquid crystal alignment control protrusions on a color filter in the same manner.

  The protrusions formed in Examples 1 to 10 were good because the dot-like protrusions had a bowl-like shape, and the stripe-like protrusions had a bowl-like shape.

It is a cross-sectional schematic diagram of a liquid crystal panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... VA type liquid crystal display device 11 ... TFT side substrate 12 ... Color filter side substrate 13 ... Alignment control protrusion 14 ... Alignment control protrusion 15 ... Liquid crystal molecule

Claims (13)

  A color filter having a colored layer and a conductive layer on the same substrate and further having protrusions for split orientation fixed on the conductive layer, wherein the protrusions include a resin in which at least a phenolic hydroxyl group is capped with a cap agent. A method for producing a color filter, which is characterized by using a functional resin composition.   The protrusion for split orientation according to claim 1 is formed using a photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator in addition to a resin having a phenolic hydroxyl group capped with a capping agent. A method for producing a color filter characterized by the above.   The capping agent for a phenolic hydroxyl group according to claim 1 or 2 is any one of an isocyanate group-containing compound, an acid anhydride group-containing compound, an acid halide group-containing compound, a vinyl ether group-containing compound, and a propenyl ether group-containing compound. A method for producing a color filter, comprising forming a color filter having protrusions for split orientation fixed on a conductive layer using a photosensitive resin composition.   The capping agent for a phenolic hydroxyl group according to claim 1 or 2 is a (meth) acrylate group and at least one functional group of an isocyanate group, an acid anhydride group, an acid halide group, a vinyl ether group, or a propenyl ether group. A method for producing a color filter, comprising forming a color filter having protrusions for divisional orientation fixed on a conductive layer using a photosensitive resin composition which is a compound containing s.   5. A binder resin having a phenolic hydroxyl group capped with a cap agent according to claim 1, wherein the binder resin is fixed on the conductive layer using a photosensitive resin composition in which a carboxyl group is introduced into a part of the uncapped phenolic hydroxyl group. A method for producing a color filter, comprising forming a color filter having protrusions for split orientation.   Using a photosensitive resin composition in which a carboxyl group is introduced into a part of a phenolic hydroxyl group by a reaction between a phenol hydroxyl group and an acid anhydride, a color filter having protrusions for split orientation fixed on the conductive layer is formed. The method for producing a color filter according to claim 5.   In addition to a resin having a phenolic hydroxyl group capped with a capping agent, a photosensitive resin composition containing another resin is used to form a color filter having protrusions for split orientation fixed on a conductive layer. The method for producing a color filter according to claim 1.   A photosensitive resin composition in which the resin other than a resin in which a phenolic hydroxyl group is capped with a capping agent is at least one of a novolak resin, a phenol resin, a polyvinylphenol resin, and an acrylic resin in which the phenolic hydroxyl group is not capped with a capping agent. The method for producing a color filter according to claim 7, wherein a color filter having protrusions for divisional orientation fixed on the conductive layer is formed by using.   Using a photosensitive resin composition containing inorganic fine particles composed of a metal oxide and a metal salt having a volume primary particle diameter of 1 nm to 200 nm, a color filter having protrusions for split orientation fixed on a conductive layer is formed. The method for producing a color filter according to claim 1, wherein:   A color filter having protrusions for split orientation fixed on a conductive layer is formed using a photosensitive resin composition in which inorganic fine particles are any of calcium carbonate and barium sulfate such as titanium oxide, silicon oxide, and aluminum oxide. The method for producing a color filter according to claim 9.   A method for producing a color filter, wherein 50% or more of the cap agent is desorbed by heating the protrusions for split orientation according to claim 1 at 150 to 250 ° C for 30 to 60 minutes. .   A color filter produced by the method for producing a color filter according to claim 1.   A liquid crystal display device using the color filter according to claim 12.

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