JP4742789B2 - Photosensitive transparent resin composition for alkali development and transflective liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive transparent resin composition and a transflective liquid crystal display device using the same.

  Currently, liquid crystal display devices are used in various applications such as notebook personal computers, portable information terminals, desktop monitors, and digital cameras, taking advantage of characteristics such as light weight, thinness, and low power consumption. Among liquid crystal display devices, a transmissive liquid crystal display device using a backlight is characterized by good visibility when the surroundings are dark and poor visibility when the surroundings are bright. On the other hand, a reflective liquid crystal display device using external light has a feature that visibility is poor when the surroundings are dark and visibility is good when the surroundings are bright. Further, as a method for obtaining good visibility even when the surroundings are bright or dark, there is a transflective liquid crystal display device in which a reflective type and a transmissive type are mixed in one display device.

However, in the transflective liquid crystal display device, the color is displayed by light that has passed through the colored layer once in the transmissive display portion and light that has passed through the colored layer twice (one reciprocation) in the reflective display portion. When the transmissive display unit and the reflective display unit of the filter unit are made of the same coloring material, there is a problem that the brightness of the reflective display unit becomes extremely poor. In addition, when the thickness of the liquid crystal layer of the reflective display unit is the same as that of the transmissive display unit, the optical path length in the liquid crystal layer of the reflective display unit is twice that of the transmissive display unit. Only one of them has a problem that the optical characteristics can be optimized. As a means for solving this problem, as shown in FIG. 1, in the six-color method in which the transmissive display portion colored layer and the reflective display portion colored layer are formed of different coloring materials, the reflective display portion of at least one substrate is used. By creating a transparent resin layer and making the thickness of the liquid crystal layer of the reflective display part half of the thickness of the liquid crystal layer of the transmissive display part, the optical path length of the transmissive display part and the reflective display part is made the same, and both are optimal optical A technique for obtaining characteristics is known (Non-Patent Document 1).
Further, as shown in FIG. 2, in the perforation method in which the transmissive display portion colored layer and the reflective display portion colored layer are formed of the same coloring material and a through hole is provided in the colored layer of the reflective display portion, at least one substrate A good effect can also be obtained by providing a transparent resin layer on the reflective display portion. Furthermore, as another method for making the display colors of the transmissive region and the reflective region the same, as shown in FIG. 3, a transparent resin layer made of a transparent resin material is formed below the colored layer of the reflective display portion, and reflective display is performed. There is a film thickness variable method for adjusting the thickness of the colored layer by reducing the thickness of the partially colored layer.

  In the above three methods, a transparent resin layer is provided to adjust the optical path length in the liquid crystal layer and the thickness of the colored layer. However, if the transparent resin layer has a tapered portion at the boundary between the transmissive display portion and the reflective display portion, the tapered portion has insufficient function of adjusting the optical path length in the liquid crystal layer and the thickness of the colored layer. If the length (hereinafter referred to as taper length) is large, there is a problem that usefulness as a transflective liquid crystal display device is lowered. Further, when the transparent resin layer is colored, the color characteristics of the reflective display portion are deteriorated, so that the usefulness as a transflective liquid crystal display device is lowered.

In addition, for the purpose of improving the light resistance of a pixel of a color filter for a liquid crystal display device, a technique of adding an organic compound having an ultraviolet absorbing ability as a light stabilizer to a photopolymerizable composition for forming a pixel (Patent Document 1), In a color filter for a liquid crystal display device, a technique (Patent Document 2) is known in which an overhang-like protruding portion having a spacer function is formed using a photosensitive resin having UV absorption, both of which are transparent resin compositions In addition, a transparent resin layer having a small taper length can be obtained by adding an organic compound-based ultraviolet absorber, and a semi-transparent film having excellent display performance by providing a transparent resin layer having a small taper length. There is no description that a liquid crystal display device can be obtained.
Nikkei Microdevices separate volume "Flat-Panel Desplay 2003 Practice" (page 109, Fig. 2 etc.) JP 2000-214580 (Claim 1 etc.) JP 2000-171786 (Claim 1 etc.)

  The problem to be solved by the present invention is to provide a transflective liquid crystal display device having good display performance in both the reflective display portion and the transmissive display portion, and a photosensitive transparent resin composition suitable for realizing the same. It is in.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that the following photosensitive transparent resin composition and transflective liquid crystal display device have excellent characteristics.
1. A photosensitive transparent resin composition for alkali development containing at least a resin, a polyfunctional monomer, a solvent, a photopolymerization initiator, and an organic compound ultraviolet absorber, wherein the organic compound ultraviolet absorber is at least a benzotriazole organic compound, benzophenone-based organic compounds, triazine 1 Tanedea selected from organic compounds is, alkali developing photosensitive transparent resin composition a polyfunctional monomer is characterized that you containing a fluorene-based monomer.
2. 2. The photosensitive transparent resin composition for alkali development according to 1 above, wherein the resin is an acrylic resin in which an ethylenically unsaturated group is added to a side chain, and a double bond equivalent is 340 to 1200. .
3 . 3. The photosensitive transparent resin composition for alkali development according to 1 or 2 above, which contains barium sulfate particles.
4 . 4. A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the reflective display portion of at least one of the two substrates sandwiching the liquid crystal layer is provided in any one of items 1 to 3 . It has a rectangular or forward tapered transparent resin layer having a film thickness of 1.0 μm or more and a taper length of 2.0 μm or less, formed of a photosensitive transparent resin composition for alkali development. A transflective liquid crystal display device having a stimulation value decrease index ΔZ of 4.0 or less.
5 . A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the transmissive display portion colored layer and the reflective display portion colored layer of the color filter are made of the same coloring material, and a through hole is formed in the reflective display portion colored layer. The film thickness formed by the photosensitive transparent resin composition for alkali development in any one of said 1-3 in the reflective display part of at least one board | substrate among two board | substrates which have liquid crystal layer in between Is a rectangular or forward-tapered transparent resin layer having a taper length of 2.0 μm or less and a tristimulus value decrease index ΔZ of the transparent resin layer is 4.0 or less. A transflective liquid crystal display device.
6 . A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the transmissive display portion colored layer and the reflective display portion colored layer of the color filter are made of the same coloring material, and the reflective display portion colored layer of the color filter, A rectangle formed from the photosensitive transparent resin composition for alkali development according to any one of Items 1 to 3 between the substrates, having a thickness of 1.0 μm or more and a taper length of 2.0 μm or less. A transflective liquid crystal display device comprising a tapered transparent resin layer, wherein the tristimulus value lowering index ΔZ of the transparent resin layer is 4.0 or less.

  By using the photosensitive transparent resin composition mentioned in the present invention, it is possible to form a transparent resin layer with a small taper length and reduced coloring, and display characteristics are good in both the reflective display portion and the transmissive display portion. A transflective liquid crystal display device can be provided.

  The transparent resin composition referred to in the present invention is applied to a transparent substrate such as glass and dried to give a coating film having a specific total light transmittance of 85% or more when a coating film having a thickness of 10 μm is obtained. Such a transparent resin composition is said. Here, the specific total light transmittance is the ratio of the total light transmittance in the laminated state of the 10 μm thick coating film and the transparent base material to the total light transmittance of the transparent base material single layer, for example, turbidity manufactured by MYSEC Co., Ltd. It can be measured with a meter.

  The photosensitive transparent resin composition of the present invention needs to contain at least a resin, a polyfunctional monomer, a solvent, a photopolymerization initiator, and an organic compound ultraviolet absorber.

  As the resin contained in the photosensitive transparent resin composition of the present invention, materials such as a polyimide resin, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a polyolefin resin can be used. An acrylic resin is preferably used from the viewpoint of versatility. Although there is no limitation in particular as acrylic resin which can be used, the copolymer of unsaturated carboxylic acid and an ethylenically unsaturated compound can be used preferably. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having a methacryloyl group Etc. Although the like, but is not limited to these.

  Although it does not necessarily limit regarding the acrylic resin to be used, 5000-30000 are preferable and 7000-20000 are more preferable. If the molecular weight is 5000 or less, pattern formation is hindered, and if the molecular weight is 30000 or more, pattern chipping is likely to occur during development. Furthermore, the resin acid value of the acrylic resin is preferably 30 to 120, more preferably 40 to 90. If the resin acid value is 30 or less, the solubility of unexposed areas in development is hindered, and if the resin acid value is 120 or more, pattern deficiency is likely to occur during development.

  Further, it is preferable to use an acrylic resin polymer having an ethylenically unsaturated group added to the side chain, because the sensitivity during exposure and development is improved, and a forward taper can be formed even if the pattern is a thick film. The range of preferable unsaturated equivalent is 340 to 1200, and more preferably 350 to 700. When the unsaturated equivalent is 340 or less, the internal stress at the time of exposure increases, and the pattern is easily peeled off. Further, when the unsaturated equivalent is 1200 or more, a reverse taper shape tends to be formed at a film thickness of 2 μm or more. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method of adding such a side chain to an acrylic (co) polymer, when the acrylic (co) polymer has a carboxyl group, a hydroxyl group, or the like, an ethylenically unsaturated compound having a glycidyl group therein In general, an addition reaction of acrylic acid or methacrylic acid chloride is used. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having glycidyl group and acrylic acid or methacrylic acid chloride include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, glycidyl isocrotonic acid Examples include ether, acrylic acid chloride, and methacrylic acid chloride.

  The polyfunctional monomer used in the photosensitive transparent resin composition of the present invention refers to a compound having at least two ethylenically unsaturated double bonds in the molecule, such as bisphenol A diglycidyl ether (meth) acrylate, Poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, 1,6-hexanediol (meth) acrylate with adipic acid, propylene oxide (meth) acrylate with phthalic anhydride, diethylene glycol trimellitic acid (meth) Acrylic ester, rosin modified epoxy di (meth) acrylate, oligomer such as alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Sphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, And polyfunctional monomers such as dipentaerythritol penta (meth) acrylate and [9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. These can be used alone or in combination. Monofunctional monomers such as ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl methacrylate, glycidyl methacrylate, lauryl (meth) acrylate, stearyl ( (Meth) acrylate, isobornyl (meth) acrylate, and the like can be used in combination, and a mixture of two or more of these or a mixture with other compounds is used.

  In particular, it is preferable to contain a fluorene monomer as a highly functional polyfunctional monomer. Here, the fluorene monomer refers to a compound having a fluorene skeleton and at least two ethylenically unsaturated double bonds in the molecule. For example, [9,9-bis [4- (2-acryloyloxyethoxy] ) Phenyl] fluorene, [9,9-bis [4- (2-acryloyloxyethoxy) -3-hydroxyphenyl] fluorene, etc., among which [9,9-bis [4- ( 2-acryloyloxyethoxy) phenyl] fluorene is preferred.

  When adding a fluorene monomer, it is preferable to add 10-90 mass% in the total amount of resin, a polyfunctional monomer, and a fluorene monomer. If the content of the fluorene monomer is less than the above range, the effect of improving transparency tends to be reduced, and if it is more, the solubility during development tends to be lowered.

  There are no particular limitations on the photopolymerization initiator, and known ones can be used, such as benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 , 2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, t-butylanthraquinone, 1-chloroanthraquinone, 2, 3-dichroic Loanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -S-triazine and the like can be mentioned, and these photopolymerization initiators can be used in combination.

  The addition amount of the photopolymerization initiator is preferably 1 to 30% by mass, more preferably 2 to 10% by mass, based on the total solid content in the photosensitive transparent resin composition. The greater the amount of photopolymerization initiator added, the better the sensitivity. However, if it exceeds 30% by mass, the coloration is large and the taper length after development tends to be too large, which is not preferable. On the other hand, if it is less than 1% by mass, the transparent resin layer is insufficiently cured and may be dissolved during development.

  As the solvent used in the present invention, a solvent that easily dissolves the resin component can be used.

  For example, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and other ethylene glycol or propylene glycol derivatives, or propylene glycol monoethyl ether acetate, ethyl acetoacetate, Aliphatic esters such as methyl-3-methoxypropionate, 3-methyl-3-methoxybutylacetate, or aliphatic alcohols such as ethanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, etc. Ketones, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and other amino acids Systems polar solvents, beta-propiolactone, .gamma.-butyrolactone, .gamma.-valerolactone, .delta.-valerolactone, .gamma.-caprolactone, may be used lactones such as ε- caprolactone. It is preferable to use a single solvent or a mixed solvent of two or more solvents that dissolve these resin components in an appropriate combination. In this case, a poor solvent for the resin to be used can be used as the auxiliary solvent. Preferred solvent combinations are not particularly limited. For example, cyclopentanone or the like having a boiling point of 180 ° C. or lower is 70 to 95% by mass, and N-methylpyrrolidone or the like has a boiling point of 180 ° C. or higher. Is a mixed solvent composed of 5 to 30% by mass, and is effective for good coatability and suppression of chipping during development. In particular, when the solvent having a boiling point of 200 ° C. or more is contained in an amount of 5 to 20% by mass, chipping hardly occurs during development, which is more preferable.

  The photosensitive transparent resin composition of the present invention may contain a highly transparent filler. By adding a highly transparent filler, the resin content in the transparent resin layer can be reduced, and the amount of the photopolymerization initiator that causes coloring can be reduced accordingly. As the highly transparent filler, materials such as inorganic oxide particles such as silica, alumina, titania, and barium sulfate, metal particles, resin particles such as acrylic, styrene, silicone, and fluorine-containing polymer can be used. From the viewpoint of properties, barium sulfate particles are preferred. The filler diameter is preferably smaller than the film thickness of the transparent resin material, and the weight average diameter is preferably 4 μm or less.

  When the filler is used, the addition amount is preferably 10 to 80% by mass in the total weight of the resin, the polyfunctional monomer and the filler. If the added amount of the filler is less than 10% by mass, the effect of reducing the initiator tends to be small, and if the filler exceeds 80% by mass, the self-retaining property tends to decrease when the coating is formed.

  The photosensitive transparent resin composition of the present invention can form a transparent resin layer having a particularly high definition and a small taper length after development by containing an organic compound-based ultraviolet absorber. There are no particular limitations on the organic compound-based ultraviolet absorber, and known ones can be used, but benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used from the viewpoints of transparency and non-coloring properties.

  Examples of organic compound ultraviolet absorbers of benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis ( 1-methyl-1-phenylethyl) phenol, 2- [5 chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tertbutylphenol), 2,4 di-tertbutyl-6- (5 -Chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-theomethylbutyl) phenol, 2 (2H-benzotriazo 2-yl) -6-dodecyl-4-methylphenol, 2 [2-hydroxy-3- (3,4,5,6 tetrahydrophthalimide - methyl) -5-methylphenyl] benzotriazole.

  Examples of the organic compound ultraviolet absorber of the benzophenone compound include octabenzone and 2-hydroxy-4-n-octoxybenzophenone.

  Examples of organic compound ultraviolet absorbers of triazine compounds include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  Of the organic compound ultraviolet absorbers, benzotriazole organic compound ultraviolet absorbers are most preferably used from the viewpoint of transparency. A preferable addition amount of the organic compound-based ultraviolet absorber is 0.3 to 10% by mass, more preferably 2.0 to 8.0% by mass, based on the total weight of the resin and the polyfunctional monomer. When the organic compound-based ultraviolet absorber is 0.3% by mass or less, the effect of shortening the tapered portion is small, and when it exceeds 10% by mass, the sensitivity tends to be lowered.

  In the photosensitive transparent resin composition resin of the present invention, a polymerization inhibitor, a surfactant, and an adhesion improving agent may be appropriately used as necessary.

  Next, the configuration of the transflective liquid crystal display device of the present invention will be described.

  As shown in FIG. 1, the first embodiment of the transflective liquid crystal display device of the present invention is a dark colored resin composition and a light colored resin composition for each color of red (R), green (G), and blue (B). Each of the objects is adjusted to an optimum composition, and the transmissive display portion 61 on the color filter side substrate 2 is formed on the transmissive display portion colored layer 21 made of a dark colored resin composition, and the reflective display portion 62 is made of a light colored colored resin composition. In the method of forming the display portion colored layer 22 (hereinafter referred to as the six-color method), the thickness of the liquid crystal layer is adjusted to the reflective display portion 62 of at least one of the two substrates sandwiching the liquid crystal layer. A transparent resin layer 30 is provided to adjust the optical path length in the liquid crystal layer.

  In the second embodiment of the transflective liquid crystal display device of the present invention, as shown in FIG. 2, the transmissive display portion colored layer 21 and the reflective display portion colored layer 22 on the color filter side substrate 2 are formed of the same coloring material. In the method of providing the through hole 23 in the reflective display portion colored layer 22 (hereinafter referred to as a perforating method), a transparent resin layer 30 is provided in the reflective display portion of at least one substrate to adjust the optical path length in the liquid crystal layer. To do.

  Further, in the third embodiment of the transflective liquid crystal display device of the present invention, as shown in FIG. 3, the transmissive display portion colored layer 21 and the reflective display portion colored layer 22 on the color filter side substrate 2 are made of the same coloring material. And a transparent resin layer 30 is provided between the reflective display portion colored layer 22 and the transparent substrate 10, and the thickness of the reflective display portion colored layer 22 is reduced to adjust the film thickness in the colored layer ( Hereinafter, this is referred to as a variable film thickness method.

  In the above three forms, by using the photosensitive transparent resin composition of the present invention, it is possible to form a transparent resin layer having a short taper length 63 and being transparent and having a small tristimulus value decrease index ΔZ.

  Any film thickness can be used for the transparent resin layer 30 as long as the cell gap can be secured, but it is 0 in any of the 6-color method, the perforation method, and the film thickness variable method. It is practical that it is 0.5 μm or more, and more preferably 1.0 to 3.0 μm.

  The pattern obtained by observing the transparent resin layer in parallel with the substrate may be a stripe, a round shape, a square shape, a rounded square shape, or any other pattern depending on the application. The cross-sectional shape of the transparent resin layer observed perpendicularly to the substrate has the same length (rectangular shape) at the top of the transparent resin layer and the bottom, or the length of the bottom is longer than the length of the top of the transparent resin layer. It needs to be tapered.

  The shape of the transparent resin layer 30 is an inversely tapered shape, that is, when the length of the top of the transparent resin layer is longer than the length of the bottom, a rubbing cloth is caught on the transparent resin layer, resulting in poor alignment. Even in the case of the forward taper shape, if the taper length is too large, the area where the optical path length in the liquid crystal layer and the thickness adjusting function of the colored layer are insufficient increases, and good display characteristics cannot be obtained. Therefore, the taper length needs to be 2.0 μm or less, and more preferably 1.0 μm or less.

  Here, the taper length is the side of the transparent resin layer where the film thickness of the transparent resin layer is 0 to 94% of the average film thickness of the transparent resin layer when cross-sectional observation or two-dimensional surface roughness measurement is performed. The projection length of the part onto the substrate surface. The taper length can be measured by a stylus film thickness meter, a laser microscope, a scanning electron microscope (SEM), or the like.

Further, the tristimulus value lowering index ΔZ of the transparent resin layer 30 needs to be 4.0 or less, preferably 2.0 or less.
Here, the tristimulus value decrease index ΔZ of the transparent resin layer 30 is a value representing how much the tristimulus value Z decreases due to the presence of the transparent resin layer, and the tristimulus value of the transparent resin layer alone. When Z1 can be measured, it can be obtained by the following formula (1).
ΔZ = 118.0−Z1 (1)
The tristimulus value Z can be measured using a microspectrophotometer “LCF2100” manufactured by Otsuka Electronics Co., Ltd.

  When the test pattern of only the transparent resin layer is present in the substrate, the tristimulus value Z1 of the transparent resin layer alone is measured using the glass substrate as a reference, and ΔZ can be obtained using the above formula (1). Moreover, when there exists a lamination pattern of a transparent electrode and a transparent resin layer, it can obtain | require by measuring the laminated body of a transparent electrode and glass as a reference.

In addition, when the transparent resin layer is laminated with another material, the tristimulus value Z2 in the state where the transparent resin layer and the other material are laminated and the tristimulus value Z3 of the other material where the transparent resin is not laminated are measured. The tristimulus value decrease index ΔZ can be obtained using the following formula (2).
ΔZ = Z3-Z2 (2)
In the case of a color filter in which the transparent display portion colored layer and the reflective display portion colored layer have the same thickness and a transparent resin layer is provided on the reflective display portion of the color filter side substrate, The tristimulus value of the display part (blue colored layer part where the transparent resin layer is not formed) is measured as Z3 by using the glass substrate as a reference, and no through hole is formed in the reflective display part in the same pixel. The tristimulus value of the part (the part where the transparent resin layer and the blue colored layer are laminated) is measured by using the glass substrate as a reference to be Z2, and the tristimulus value decrease index ΔZ is obtained using the above formula (2). Can do.

  In the case of a color filter produced by the variable film thickness method, the tristimulus value is reduced by the following method because the colored layer thickness is different between the area where the transparent resin layer is formed and the area where the transparent resin layer is not formed. An index ΔZ can be calculated.

A. From the transmittance spectrum TT (λ) of the transmissive display portion (the blue colored layer portion where the transparent resin layer is not formed) in the blue pixel of the color filter, the absorbance spectrum εT (λ) is converted using the following equation (3) To do. Here, (λ) indicates the measurement wavelength.
εT (λ) = − log10 (TT (λ)) (3)
B. Using a scanning electron microscope (SEM) or the like, the blue colored layer thickness tR of the reflective display portion of the blue colored layer and the blue colored layer thickness tT of the transmissive display portion are measured, and the film thickness ratio α is measured.
α = tR / tT (4)
The transmittance spectrum TR ′ (λ) of the reflective display portion of the blue pixel after thickness conversion obtained using the following formula (5) is obtained.
TR ′ (λ) = 10 ^ (− εR (λ) × (α) (5)
C. An actually measured transmittance spectrum TR (λ) of the reflective display portion (the portion where the transparent resin layer and the blue colored layer are laminated) in the blue pixel is obtained.

D. The tristimulus value Z4 of the reflection display unit blue pixel after conversion is calculated from TR ′ (λ). Similarly, the tristimulus value Z5 of the reflective display portion (portion where the transparent resin layer and the blue colored layer are laminated) is calculated from TR (λ), and the tristimulus value decrease index ΔZ is obtained using the following equation (6). be able to.
ΔZ = Z5-Z4 (6)
Any known resin, color material, and production method can be used for producing the colored layer of the color filter for transflective liquid crystal display used in the present invention. In addition, a black matrix 50, a planarization protective film, and a transparent electrode can be produced as necessary.

  Next, although the manufacturing method of the liquid crystal display device using the photosensitive resin composition of this invention is demonstrated, it is not limited to this. The transparent resin layer comprising the photosensitive transparent resin composition of the present invention is used by being incorporated in a transflective liquid crystal display device. Here, the transflective liquid crystal display device includes a reflective film 41 made of an aluminum film, a silver film, or the like on a reflective display portion of a counter substrate or a color filter, and the transmissive display portion has no such reflective film. This is a liquid crystal display device. The photosensitive transparent resin composition of the present invention is not limited to a driving method and a display method of a liquid crystal display device, and is an active matrix method, a passive matrix method, a TN (Twisted Nematic) mode, an STN (Super Twisted Nematic) mode, an ECB. The present invention is applied to various liquid crystal display devices such as (Electrically Controlled Birefringence) mode, OCB (Optically Compensated Bend) mode, VA (Vertical Alignment) mode, and IPS (In-Plane-Switching) mode. Moreover, it can be used without being limited to the structure of the liquid crystal display device, for example, the number of polarizing plates, the position of the scatterers, and the like.

  A method for forming a transparent resin layer using the photosensitive transparent resin composition of this patent will be described. Depending on the application, the substrate may be a transparent substrate, a transparent substrate with a black matrix, a substrate with a reflective display portion colored layer and a transmissive display portion colored layer, a color filter, or a color filter counter substrate. Can also be made. The photosensitive transparent resin composition of this patent is applied onto a substrate and heat-dried (prebaked) using a hot plate, oven, or vacuum drying. After pre-baking, mask exposure, alkali development, and subsequent heat-curing are performed to obtain a transparent resin layer.

  As a method for applying the photosensitive transparent resin composition, a dip method, a roll coating method, a spin coating method, a die coating method, a die coating and spin coating combined method, a wire bar coating method, or the like is preferably used. After apply | coating the photosensitive transparent resin composition on a board | substrate, a solvent is removed by air drying, reduced pressure drying, heat drying, etc., and the coating film of the photosensitive transparent resin composition is formed. In particular, after the vacuum drying step is provided, additional heating and drying in an oven or a hot plate is preferable because the coating defects caused by convection are eliminated. Subsequently, an exposure process of photolithography processing is performed. A mask is placed on the coating film of the photosensitive transparent resin composition and selectively exposed to ultraviolet rays using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp or the like.

  The amount of exposure is not particularly limited, but is preferably 50 to 200 mJ / cm 2 when expressed by a time integral value of irradiance at 365 nm. The exposure gap is not particularly limited, but is preferably 50 μm or more from the viewpoint of mask contamination.

  As the alkali developer, either an organic alkali developer or an inorganic alkali developer can be used. In the inorganic alkaline developer, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferably used. In the organic alkali developer, an aqueous amine solution such as an aqueous tetramethylammonium hydroxide solution or methanolamine is preferably used.

  The concentration of the alkaline substance in the developer is not particularly limited, but is usually 0.01 to 50% by mass, preferably 0.05 to 5% by mass. Further, a surfactant is also preferably used in the developer, and the pattern shape is improved by adding a nonionic surfactant or the like in an amount of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass. You can also.

  Alkali development can be performed by dip development, shower development, paddle development or the like, and these may be combined. After the development, a washing step with pure water or the like may be appropriately added to remove the alkali developer.

  The coating film pattern of the obtained transparent resin layer is then heat-treated. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at a temperature of 150 to 300 ° C, preferably 180 to 260 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

  An example of a transflective liquid crystal display device manufactured using the color filter thus obtained will be described with reference to FIG. Semi-transmissive with color filter side substrate 2, reflective film 41 patterned with metal deposition film, transparent insulating film on semi-transmissive reflective film, and transparent electrode (not shown) such as ITO film formed thereon The reflective substrate 1 is further passed through a liquid crystal alignment film (not shown) subjected to a rubbing process for liquid crystal alignment provided on those substrates, and a spacer (not shown) for maintaining a cell gap. Then, seal and paste them together. On the transflective substrate, in addition to the reflective film and the transparent electrode, a light diffusion projection (not shown), a thin film transistor (TFT) element or a thin film diode (TFD) element (not shown), and scanning A TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing lines, signal lines, and the like (not shown). Next, after injecting liquid crystal from the injection port provided in the seal portion at the outer periphery of the image display region, the injection port is sealed. Next, a module is completed by mounting an IC driver or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these.

Example 1
A. Preparation step of acrylic copolymer solution 14 parts by weight of methyl methacrylate, 14 parts by weight of styrene, 48 parts by weight of methacrylic acid, 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile), and γ-Butyrolactone was charged into a 150 weight part polymerization vessel, stirred at 90 ° C. for 2 hours, further raised to 100 ° C. and reacted for 1 hour. Next, 57 parts by weight of glycidyl methacrylate, 1.1 parts by weight of dimethylbenzylamine, and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution and stirred at 90 ° C. for 4 hours. 29 g of γ-BL was added to obtain an acrylic copolymer solution (T-1, solid content 43 mass%, acid value 68, molecular weight 18000).

  33 parts by weight of methyl methacrylate, 33 parts by weight of styrene, 34 parts by weight of methacrylic acid, 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile), and 150 parts by weight of γ-butyrolactone are polymerized. The mixture was placed in a container and stirred at 90 ° C. for 2 hours, and the liquid temperature was further raised to 100 ° C. to react for 1 hour. Next, 33 parts by weight of glycidyl methacrylate, 1.1 parts by weight of dimethylbenzylamine and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution, and the mixture was stirred at 90 ° C. for 4 hours. 29 g of γ-BL was added to obtain an acrylic copolymer solution (T-2, solid content 43 mass%, acid value 70, molecular weight 18000).

  47 parts by weight of methyl methacrylate, 47 parts by weight of styrene, 23 parts by weight of methacrylic acid, 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile), and 150 parts by weight of γ-butyrolactone are polymerized. The mixture was placed in a container and stirred at 90 ° C. for 2 hours, and the liquid temperature was further raised to 100 ° C. to react for 1 hour. Next, 16 parts by weight of glycidyl methacrylate, 1.1 parts by weight of dimethylbenzylamine and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution, and the mixture was stirred at 90 ° C. for 4 hours. 29 g of γ-BL was added to obtain an acrylic copolymer solution (T-3, solid content 43 mass%, acid value 67, molecular weight 19000).

  51 parts by weight of methyl methacrylate, 51 parts by weight of styrene, 20 parts by weight of methacrylic acid, 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile), and 150 parts by weight of γ-butyrolactone are polymerized. The mixture was placed in a container and stirred at 90 ° C. for 2 hours, and the liquid temperature was further raised to 100 ° C. to react for 1 hour. Next, 11 parts by weight of glycidyl methacrylate, 1.1 parts by weight of dimethylbenzylamine, and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution and stirred at 90 ° C. for 4 hours. 29 g of γ-BL was added to obtain an acrylic copolymer solution (T-4, solid content 43 mass%, acid value 71, molecular weight 17000).

  27 parts by weight of methyl methacrylate, 27 parts by weight of styrene, 46 parts by weight of methacrylic acid, 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile), and 150 parts by weight of γ-butyrolactone are polymerized. The mixture was placed in a container and stirred at 90 ° C. for 2 hours, and the liquid temperature was further raised to 100 ° C. to react for 1 hour. Next, 11 parts by weight of glycidyl methacrylate, 1.1 parts by weight of dimethylbenzylamine, and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution and stirred at 90 ° C. for 4 hours. 29 g of γ-BL was added to obtain an acrylic copolymer solution (T-5, solid content 43 mass%, acid value 128, molecular weight 19000).

B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-meryl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 2- (2H-benzotriazol-2-yl as an ultraviolet absorber ) -4- (1,1,3,3-tetramethylbutyl) phenol (3 g) and cyclopentanone (217.5 g) as a solvent were added, and the acrylic resin concentration (total concentration of acrylic copolymer and monomer) was 20% by mass. A photosensitive transparent resin composition (TAC-1) was obtained.

  Except for using (T-1), (T-2), (T-3), (T-4) or (T-5) instead of (ACA-250) as the acrylic copolymer solution. Thus, a photosensitive transparent resin composition (TAC-2), (TAC-3), (TAC-4), (TAC-5) or (TAC-6) was obtained.

  Acrylic copolymer solution (T-2, 43% by mass solution) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as polyfunctional monomer, 2-methyl-1- "4- (methylthio) phenyl as photopolymerization initiator 10.0 g of 2-morpholinopropan-1-one and 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol as the UV absorber 3 g, 192.5 g of cyclopentanone and 25.0 g of N-methylpyrrolidone as a solvent, and a photosensitive transparent resin composition (TAC-7) having an acrylic resin concentration (total concentration of acrylic copolymer and monomer) of 20% by mass Got.

C. Step of preparing polyamic acid solution 95.1 g of 4,4′-diaminodiphenyl ether and 6.2 g of bis (3-aminopropyl) tetramethyldisiloxane were charged together with 525 g of γ-butyrolactone and 220 g of N-methyl-2-pyrrolidone, After adding 144.1 g of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and reacting at 70 ° C. for 3 hours, adding 3.0 g of phthalic anhydride and further reacting at 70 ° C. for 2 hours. 25% by mass of polyamic acid solution (PAA) was obtained.

D. Step of synthesizing polymer dispersant 161.3 g of 4,4′-diaminobenzanilide, 176.7 g of 3,3′-diaminodiphenylsulfone, and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane were added to 2667 g of γ-butyrolactone. , N-methyl-2-pyrrolidone, 527 g, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 439.1 g was added, reacted at 70 ° C. for 3 hours, and then phthalic anhydride 2 .2 g was added and further reacted at 70 ° C. for 2 hours to obtain a polymer dispersant (PD) as a 20% by mass polyamic acid solution.

E. Preparation of Black Resin Composition 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane were mixed with N-methyl-2- Pyrrolidone was reacted as a solvent to obtain a polyimide precursor (polyamic acid) solution.

  4.6 g of carbon black “MA100” manufactured by Mitsubishi Chemical Corporation, 24 g of polyimide precursor solution and 61.4 g of N-methylpyrrolidone were dispersed with a homogenizer at 7000 rpm for 30 minutes, and the glass beads were filtered to obtain a black resin. A composition was prepared.

F. Step for preparing coloring resin composition Pigment Red PR254, 3.6 g, Pigment Red PR177, 0.9 g, Polymer Dispersant (PD) 22.5 g and γ-butyrolactone 42.8 g, 3-methoxy-3-methyl-1 -20.2 g of butanol was charged together with 90 g of glass beads, and after dispersing for 5 hours at 7000 rpm using a homogenizer, the glass beads were filtered and removed. Thus, a pigment dispersion (RD) having a pigment concentration of 5% by mass was obtained.

  A dark red resin composition having a pigment / resin ratio of 25/75, in which 45.6 g of dispersion (RD) is mixed with a solution obtained by diluting 18.2 g of polyamic acid solution (PAA) with 39.52 g of γ-butyrolactone. (NR) was obtained. Further, the mixing ratio of the dispersion (RD) and the polyamic acid solution (PAA) was changed to obtain a light red resin composition (TR) having a pigment / resin ratio of 20/80.

  Similarly, a dark green resin composition (NG) having a weight mixing ratio (G / Y) of Pigment Green PG36 and Pigment Yellow PY150 of 60/40 and a pigment / resin ratio of 35/65, and a pigment / resin ratio. A light green resin composition (TG) having a pigment / resin ratio of 20/80, a pigment / resin ratio of 17 / A light blue resin composition (TB) of 83 was obtained. The solid content concentration of each color paste was adjusted to 5.3%.

G. Color filter production process The black resin composition was applied to a glass substrate with a spinner so as to have a thickness of 1.0 μm, and the coating film was dried in an oven at 120 ° C. for 20 minutes. On top of that, a positive resist “SRC-200” manufactured by Shipley Far East was applied and dried in an oven at 90 ° C. for 10 minutes. Using a UV exposure machine “PEM-6M” manufactured by Union Optical Co., Ltd., exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chromium photomask. After exposure, the substrate is dipped in a developer composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, washed with pure water, water removed by air blow, heated in an oven at 250 ° C. for 30 minutes, and then applied to a 300 × 350 mm substrate. A black matrix with 60 inch color filters was obtained.

  A dark green resin composition (NG) was applied to a glass substrate on which a black matrix was formed with a spinner so as to have a thickness of 2 μm, and the coating film was dried in an oven at 120 ° C. for 20 minutes. A positive resist was applied on the coating film and dried in an oven at 90 ° C. for 10 minutes. Using an exposure machine, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chromium photomask in which the transmissive region green colored layer portion was shielded from light. After exposure, the sample is dipped in a developer composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, heated in an oven at 250 ° C. for 30 minutes, and then a green color pattern on the transmissive display portion Got. Next, using the light green resin composition (TG), a reflective display portion green colored layer was prepared in the same manner as (NG) except that a photomask having a light shielding portion in the reflection display portion green layer portion was used. Similarly, a transmissive display portion red colored layer, a reflective display portion red colored layer, a transmissive display portion blue colored layer, and a reflective display portion blue colored layer were sequentially prepared. On the substrate on which the black matrix and the transmissive display portion green colored layer, the reflective display portion green colored layer, the transmissive display portion red colored layer, the reflective display portion red colored layer, the transmissive display portion blue colored layer, and the reflective display portion blue colored layer are formed. , Photosensitive transparent resin composition (TAC-1), (TAC-2), (TAC-3), (TAC-4), (TAC-5), (TAC-6) or (TAC-7) Each of the layers was spin-coated so as to have a thickness of 2 μm, 3 μm, or 4 μm, and dried in an oven at 90 ° C. for 10 minutes. Through a chromium photomask, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm. The mask pattern has 12 types of transmission patterns in increments of 1 μm from 6 μm smaller to 5 μm larger than the size of the reflective display part, and there are 5 sets of each size pattern on a 300 × 350 mm substrate, and screen display It has a test transmission pattern with stripes of 10 μm, 20 μm, 30 μm, 40 μm and 50 μm in width. Hereinafter, the evaluation of the translucent photosensitive transparent resin composition was performed using a transparent resin layer having a size in which the size of the reflection region and the uniform thickness of the top of the transparent resin layer coincided with each other using the same mask. After the exposure, the film was immersed in a developer composed of an aqueous solution of 0.3% by mass of tetramethylammonium hydroxide, washed with pure water, water was removed by air blow, and then heated in an oven at 250 ° C. for 30 minutes. A transparent electrode was prepared on this substrate by a sputtering method, and a spacer for holding the substrate was arranged to obtain a transflective liquid crystal display color filter.

H. Observation of transparent resin taper shape and lack of test pattern Of the above-prepared color filter substrate with 60 2 inch screens, 12 patterns with different mask sizes for forming a transparent resin layer (prepared near the center of the substrate) The pattern produced using a mask having the same width as the reflective display portion is cut in the radial direction, and parallel to the substrate and in the pattern normal direction by SEM “S-2300” manufactured by Hitachi Measurement Service. The shape, especially the taper shape was observed. Here, the width of the portion where the transparent resin layer is in contact with the colored layer is smaller than the width of the transparent resin layer at other heights, and the reverse taper shape is used. . We also confirmed the lack of test patterns.

I. Measurement of transparent resin performance Among the above-prepared color filter substrates on which 60 screens of 2 inch screens were prepared, 12 patterns with different mask sizes (near the center of the base material) on the substrate on which the transparent resin layer was formed with TAC-1. When the shape parallel to the substrate and observed in the pattern normal direction is observed with a SEM “S-2300” manufactured by Hitachi Measurement Service, the size of the reflective display portion is 3 μm. In a portion using a small mask pattern, a flat portion on the top of the substrate covers the reflective display portion, and a pattern in which the tapered portion protrudes from the transmissive display portion is formed. Furthermore, the shape of the remaining four transparent resin layers was observed at a location where a mask pattern 3 μm smaller than the size of the reflective display portion was used. As a result of measuring the shape of five points in the same substrate of the transparent resin layer produced from TAC-1, the average film thickness near the top was 2.00 μm (standard deviation σ = 0.031, maximum value 2.06 μm, minimum value) 1.93 μm), and the average taper length was 1.00 μm (standard deviation σ = 0.036). Further, for the purpose of measuring the variation for each color filter, the film thickness and the taper length were measured at the same place where the mask pattern of the transparent resin layer near the center of the five substrates was 3 μm smaller than the size of the reflective display portion. The average film thickness in the vicinity of the top of the head is 2.00 μm (standard deviation σ = 0.032), the average taper portion of 0 to 94% of the film thickness is 1.00 μm (standard deviation σ = 0.035, maximum value 1.05 μm, minimum value 0. 95), and it was produced uniformly.

  The ITO / TAC-1 / glass part of the test pattern produced outside the display area of the measurement substrate was measured with a microspectroscopy apparatus “LCF2100” manufactured by Otsuka Electronics using ITO / glass as a reference. Similar to the shape measurement, the tristimulus value Z measured for 5 substrates on the same substrate and 5 substrates at the same location is 116.2 (σ = 0.072, maximum value Z116.6, minimum value 115.9), and is produced uniformly. It had been. The tristimulus value decrease index ΔZ determined using the formula (1) was 1.8.

  Separately, spin coating was performed on a glass substrate so that the film thickness would be 10 μm when dried in a 90 ° C. oven for 10 minutes, and then dried in a 90 ° C. oven for 10 minutes. It was 92.8 when the total light transmittance was measured for this with the turbidimeter "NDH2000" by Mysec Co., Ltd. The total light transmittance of the glass substrate not coated with the transparent resin was 93.3. Therefore, the specific total light transmittance of this photosensitive transparent resin composition was 99.5%.

J. et al. Panel manufacturing process On the driving element substrate composed of a thin film diode (TFD) element, a scanning line, a signal line, and a transparent electrode, a resin projection layer for light diffusion provided with a contact hole, and further an aluminum vapor deposition film was patterned thereon. A semi-transmissive reflective film and a liquid crystal alignment film subjected to rubbing treatment for liquid crystal alignment provided on those substrates were formed to produce a semi-transmissive counter substrate. The color filter side substrate was also rubbed for liquid crystal alignment. The transflective counter substrate and the color filter substrate were opposed to each other and bonded together using a sealing material. Next, after injecting liquid crystal from the injection light provided in the seal portion, the injection light was sealed. Next, a liquid crystal display device was completed by mounting an IC driver or the like.

K. Appearance Observation Ten sets of the above-described transflective liquid crystal display devices were manufactured, and visual inspection was performed by relative evaluation of three evaluators at five locations on the mask portion where the TAC-1 mask size was 3 μm smaller than the reflective display portion.

  First, as an appearance observation at the time of reflection display, visual inspection was performed outdoors on a sunny day (illuminance of 100,000 lx). This sample and later-described Examples 2 to 9 and Comparative Examples 1 to 6 were evaluated, and the evaluation was made in a five-step evaluation with 1 point being the darkest (Comparative Example 2) and 5 points being the brightest (Example 6). The average value of three people was used.

  Next, as an appearance observation at the time of transmissive display, visual evaluation was performed in a room (illuminance 500 lx) with fluorescent lamp illumination. This sample and later-described Examples 2 to 9 and Comparative Examples 1 to 6 were evaluated, and the evaluation was made in a five-step evaluation with 1 point being the darkest (Comparative Example 2) and 5 points being the brightest (Example 6). The average value of three people was used.

  Furthermore, the total of the evaluation points at the time of reflection display and transmission display was obtained and set as the overall evaluation (10 points maximum).

  The average film thickness, taper length, and tristimulus decrease index ΔZ in five points in the substrate of the transparent resin layer of the color filter produced using the photosensitive transparent resin composition for a transflective liquid crystal display device, and The appearance evaluation results of the liquid layer display device are summarized in Table 1. A transparent resin layer having a small taper length and a small ΔZ can be formed, and the obtained transflective liquid crystal display device has excellent display performance in both reflective display and transmissive display.

Example 2
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 2- (2H-benzotriazol-2-yl as an ultraviolet absorber ) -4-6bis (1-methyl-1-phenylethyl) phenol (3 g) and cyclopentanone (217.5 g) as a solvent were added to obtain a photosensitive transparent resin composition (TAC-8).

  The steps C to G, I, and J use TAC-8 as the photosensitive transparent resin composition, which is formed so that the film thickness becomes 2 μm, and the mask size used for the evaluation is the reflective display portion and the transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 3
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 2- (2H-benzotriazol-2-yl as an ultraviolet absorber ) -4,6-di-tert-pentylphenol and 217.5 g of cyclopentanone as a solvent were added to obtain a photosensitive transparent resin composition (TAC-9) having a concentration of 20% by weight.

  The steps C to G, I, and J use TAC-9 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 4
A. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator, 3 g of octabenzone as a UV absorber, and cyclopentanone as a solvent. 5 g was added to obtain a photosensitive transparent resin composition (TAC-10) having a concentration of 20% by mass.

  The steps C to G, I, and J use TAC-10 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. A transparent resin layer having a relatively large ΔZ as compared with Example 1 was obtained, and the obtained transflective liquid crystal display device was slightly inferior in brightness at the time of reflective display, but was sufficiently practically bright.

Example 5
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 2- (2H-benzotriazol-2-yl as an ultraviolet absorber ) -4- (1,1,3,3-tetramethylbutyl) phenol (1.5 g) and cyclopentanone (219.0 g) as a solvent were added, and a photosensitive transparent resin composition (TAC-11) having a concentration of 20% by weight. Got.

  The steps C to G, I, and J use TAC-11 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A transflective liquid crystal display device was produced in the same manner as in Example 1 except that the sizes of the tops of the layers were the same. A transparent resin layer having a slightly larger taper length than that of Example 1 was obtained, and the obtained transflective liquid crystal display device was slightly inferior in brightness at the time of transmissive display. However, the brightness was practically sufficient. It was.

Example 6
B. Production process of photosensitive transparent resin composition 70.0 g of acrylic copolymer solution (Daicel Chemical Industries, Ltd., Cyclomer P, ACA-250, 43 mass% solution), 15.0 g of dipentaerythritol hexaacrylate as a polyfunctional monomer And [9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 15.0 g As a photopolymerization initiator 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropane-1 10.0 g of -one, 3 g of 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol as an ultraviolet absorber, and cyclopentanone as a solvent. 5 g was added to obtain a photosensitive transparent resin composition (TAC-12).

  The steps C to G, I, and J use TAC-12 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Compared with Example 1, it became a transparent resin layer having a smaller ΔZ, and the obtained transflective liquid crystal display device was more excellent in brightness during reflective display.

Example 7
B. Production process of photosensitive transparent resin composition 14.4 g of barium sulfate and 106 g of acrylic copolymer solution (Daicel Chemical Industries, Ltd., Cyclomer P, ACA-250, 43 mass% solution), and 122 g of cyclopentanone as a solvent are made of glass. The mixture was charged together with 90 g of beads and dispersed at 7000 rpm for 5 hours using a homogenizer, and then the glass beads were filtered and removed to obtain a barium sulfate dispersion. To 218.16 g of this barium sulfate dispersion, 45.6 g of dipentaerythritol hexaacrylate, 9.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one, 2- ( 3 g of 2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol was added to obtain a photosensitive transparent resin composition (TAC-13).

  Steps C to G, I, and J use TAC-13 as the photosensitive transparent resin composition, and the liquid crystal for semi-transmission is exactly the same as in Example 1 except that it is formed to have a film thickness of 2 μm. A liquid crystal display device for display was produced. Compared with Example 1, it became a transparent resin layer having a smaller ΔZ, and the obtained transflective liquid crystal display device was more excellent in brightness during reflective display.

Example 8
The process from B to F was made in exactly the same way as in Example 1.

G. Color filter manufacturing process The black resin composition was applied onto a glass substrate with a spinner so as to have a thickness of 1.0 μm, and the coating film was dried in an oven at 120 ° C. for 20 minutes. A positive resist was applied on the coating film and dried in an oven at 90 ° C. for 10 minutes. Using an exposure machine, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chromium photomask. After exposure, the substrate was immersed in a developer composed of a 2.0% by weight aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, and heated in an oven at 250 ° C. for 30 minutes to obtain a black matrix. .

  The dark green resin composition (NG) was applied on the glass substrate on which the black matrix was formed with a spinner so as to have a film thickness of 1 μm, and the coating film was dried in an oven at 120 ° C. for 20 minutes. A positive resist was applied on the coating film and dried in an oven at 90 ° C. for 10 minutes. Using an exposure machine, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chromium photomask in which the entire area of the transmissive display portion green colored layer and the area of the reflective display portion green colored layer were shielded from light by 40%. After exposure, the film is dipped in a developer composed of a 2.0% aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, heated in an oven at 250 ° C. for 30 minutes, and then the transparent display portion green colored layer Then, a green colored layer of the reflective display portion with through holes was obtained in a lump. Next, green color is used except that a dark red colored resin composition (NR) is used and a photomask having a light-shielding portion in 20% of the total area of the transmissive display portion red layer portion and the reflective display portion red region portion is used. In the same manner as the colored layer manufacturing step, a transmissive display portion red colored layer and a reflective display portion red colored layer having a through hole were obtained in a lump. Further, using the dark blue resin composition (NB), a green colored layer manufacturing process except that a photomask having a light shielding portion in 15% of the entire area of the transmissive display portion blue colored layer and the reflective display portion blue colored layer is used. In the same manner, a transmissive display portion blue colored layer and a reflective display portion blue colored layer having a through hole were obtained in a lump.

  A photosensitive transparent resin composition (TAC-1) was spin-coated on the substrate so as to have a film thickness of 2 μm, and dried in an oven at 90 ° C. for 10 minutes. Next, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chrome photomask that passed through the reflective region. After exposure, the film is immersed in a developer composed of a 0.3% aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, heated in an oven at 250 ° C. for 30 minutes, and the transparent electrode is sputtered Thus, a color filter for a transflective liquid crystal display device was obtained.

H. Transparent resin performance measurement process When the shape was observed with SEM, the transparent resin layer produced with TAC-1 had a film thickness of 2 μm and the taper portion was 1 μm. Further, the chromaticity spectrum of the transparent display portion blue colored layer, and the portion where the transparent resin layer and the transparent display portion blue colored layer are laminated is measured, and the tristimulus value decrease index Δ of the transparent resin layer obtained by the above formula (2) Z was 1.8.

In step H, a transflective liquid crystal display device was produced in exactly the same manner as in Example 1, and the panel was visually inspected. The results are shown in Table 1. By using the photosensitive transparent resin composition of the present invention, it was possible to obtain a bright transflective liquid crystal display device for both reflective display and transmissive display even by the perforation method.
Example 9
From the process of B to F, it produced exactly the same as Example 1 except having formed the photosensitive transparent resin composition so that a film thickness might be set to 2 micrometers.

G. Color filter production process The black resin composition was applied onto a glass substrate with a spinner so as to have a film thickness of 1.0 μm, and the black coating film was dried in an oven at 120 ° C. for 20 minutes. A positive resist was applied thereon and dried in an oven at 90 ° C. for 10 minutes. Using an exposure machine, exposure was performed at 100 mJ / cm ² and a gap of 100 μm through a chromium photomask. After exposure, the substrate was immersed in a developer composed of a 2.0% by weight aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, and heated in an oven at 250 ° C. for 30 minutes to obtain a black matrix. .

The photosensitive transparent resin composition (TAC-1) was applied to the glass substrate on which the black matrix was formed with a spinner so as to have a film thickness of 1 μm, and 100 mJ was passed through a chromium photomask having openings only for the reflective display portions of the respective colors. / Cm ² and exposure with a gap of 100 μm. After the exposure, the film was immersed in a developer composed of an aqueous solution of 0.3% by mass of tetramethylammonium hydroxide, washed with pure water, water was removed by air blow, and then heated in an oven at 250 ° C. for 30 minutes.

    The dark green resin composition (NG) was applied on a glass substrate with a spinner so as to be 2 μm, and the coating film was dried in an oven at 120 ° C. for 20 minutes. A positive resist was applied on the coating film and dried in an oven at 90 ° C. for 10 minutes. Using an exposure machine, exposure was performed at 100 mJ / cm 2 and a gap of 100 μm through a chromium photomask in which both the transmissive display portion green colored layer portion and the reflective region green colored layer portion were shielded from light. After exposure, the film is immersed in a developer composed of a 2.0% by weight aqueous solution of tetramethylammonium hydroxide, washed with pure water, drained with air blow, heated in an oven at 250 ° C. for 30 minutes, and a film thickness of 2 μm. A transparent display portion green colored layer made of a dark green resin composition, a photosensitive transparent resin layer having a thickness of 1 μm, and a reflective display portion colored layer made of a dark green resin composition having a thickness of 1 μm were obtained. Similarly, a transmissive display portion red colored layer, a reflective display portion red colored layer, a transmissive display portion blue colored layer, and a reflective display portion blue using a dark red resin composition (NR) and a dark blue resin composition (NB). A colored layer was obtained.

  The transmittance spectrum TT (λ) of the transmissive display portion blue colored layer (blue colored layer portion where the transparent resin layer is not formed), the blue colored layer thickness tT here, and the reflective display portion blue colored layer (transparent The measured transmittance spectrum TR (λ) of the portion where the resin layer and the blue colored layer are laminated), and the film thickness tR of the blue colored layer here, ΔZ according to the procedures of the above formulas (3) to (7) Asked.

  Here, Z5 was 114.9, Z4 was 113.9, and ΔZ was 1.0.

  In step H, a transflective liquid crystal display device was produced in exactly the same manner as in Example 1, and the panel was visually inspected. The results are shown in Table 1. By using the photosensitive transparent resin composition of the present invention, it was possible to obtain a bright transflective liquid crystal display device for both reflective display and transmissive display even by the film thickness variable method.

Example 10
The steps C to G, I, and J use TAC-2 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 11
The steps C to G, I, and J use TAC-3 as the photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is the reflective display portion and the transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 12
The steps C to G, I, and J use TAC-4 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 13
The steps C to G, I, and J use TAC-5 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 14
The steps C to G, I, and J use TAC-6 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Example 15
The steps C to G, I, and J use TAC-7 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A liquid crystal display device for transflective liquid crystal display was produced in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Similar to Example 1, a transparent resin layer having a small taper length and a small ΔZ could be formed, and the obtained transflective liquid crystal display device was bright during both reflective display and transmissive display.

Comparative Example 1
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 10.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 220.5 g of cyclopentanone as a solvent were added, and a photosensitive transparent resin A composition (TAC-14) was obtained.

  The steps C to G, I, and J use TAC-14 as a photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the mask size used for the evaluation is a reflective display portion and a transparent resin. A transflective liquid crystal display device was fabricated in exactly the same manner as in Example 1 except that the sizes of the tops of the layers were the same. Since the organic compound ultraviolet absorber is not contained, the taper length of the transparent resin layer is increased, and the obtained transflective liquid crystal display device is inferior in brightness during transmissive display.

Comparative Example 2
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 25.0 g of 2-methyl-1- “4- (methylthio) phenyl” -2-morpholinopropan-1-one as a photopolymerization initiator and 220.5 g of cyclopentanone as a solvent were added, and a photosensitive transparent resin A composition (TAC-15) was obtained.

  In the steps C to G, I, and J, TAC-15 was used as the photosensitive transparent resin composition, and the mask size used for the evaluation was a size in which the top of the reflective display portion and the top of the transparent resin layer were matched. A transflective liquid crystal display device was produced in the same manner as in Example 1 except that. Does not contain an organic compound UV absorber, the transparent resin layer has a large taper length, and becomes a transparent resin layer having a large ΔZ, and the obtained transflective liquid crystal display device has brightness in transmissive display and reflective display. Both were inferior.

Comparative Example 3
Processes B to F, G, and J were produced in exactly the same manner as in Comparative Example 2.

  In step G, the TAC-15 exposure gap was changed from 100 μm to 0 μm, and the mask size portion where the top of the reflective display portion and the transparent resin layer coincided with each other was used for evaluation. A liquid crystal display device for liquid crystal display was produced. Since the exposure gap was set to 0 μm, the taper length was reduced, and it was very bright during transmissive display. However, it does not contain an organic compound ultraviolet absorber and becomes a transparent resin layer having a large ΔZ, and the brightness of the obtained transflective liquid crystal display device is greatly inferior at the time of reflective display. Furthermore, when the mask was observed with an optical microscope after preparing 20 substrates, a large number of foreign matters were adhered because the mask and the transparent resin layer were in contact.

Comparative Example 4
B. Production process of photosensitive transparent resin composition Acrylic copolymer solution (Cyclomer P, ACA-250, 43% by mass solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, dipentaerythritol hexaacrylate 30.0 g as a polyfunctional monomer 1 and 2-octadione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) 5.0 g as a photopolymerization initiator, and 220.5 g cyclopentanone as a solvent were added to form a photosensitive transparent resin. A composition (TAC-16) was obtained.

  In the steps C to G, I, and J, TAC-16 is used as the photosensitive transparent resin composition, which is formed so as to have a film thickness of 2 μm, and the tops of the reflective display portion and the transparent resin layer coincide with each other. A transflective liquid crystal display device was produced in the same manner as in Example 1 except that the mask size portion was used for evaluation. Since the organic compound ultraviolet absorber is not contained, the taper length of the transparent resin layer is increased, and the obtained transflective liquid crystal display device is inferior in brightness during transmissive display.

Comparative Example 5
The steps C to G, I, and J were prepared in the same manner as in Example 8 except that TAC-14 was used as the photosensitive transparent resin composition and the film was formed to have a thickness of 2 μm. A transparent resin layer having a large ΔZ without containing an organic compound ultraviolet absorber was obtained, and the transflective liquid crystal display device obtained by the perforating method was also inferior in brightness at the time of irradiance display.

Comparative Example 6
The steps C to G, I, and J were produced in the same manner as in Example 9 except that TAC-14 was used as the photosensitive transparent resin composition. A transparent resin layer having a large ΔZ without containing an organic compound ultraviolet absorber was obtained, and the transflective liquid crystal display device obtained by the film thickness variable method was also inferior in brightness at the time of projection display.

Schematic sectional view of the color filter of the present invention using the 6-color method Schematic sectional view of the color filter of the present invention using the perforation method Schematic sectional view of the color filter of the present invention using the variable film thickness method

Explanation of symbols

1: counter substrate 2: color filter side substrate 10, 11: base material 21: transmissive display portion colored layer 22: reflective display portion colored layer 23: through hole 30: transparent resin layer 41: reflective layer 42: drive circuit 50: black Matrix 61: Transmission display unit 62: Reflection display unit 63: Taper length

Claims (6)

A photosensitive transparent resin composition for alkali development containing at least a resin, a polyfunctional monomer, a solvent, a photopolymerization initiator, and an organic compound ultraviolet absorber, wherein the organic compound ultraviolet absorber is at least a benzotriazole organic compound, benzophenone-based organic compounds, triazine 1 Tanedea selected from organic compounds is, alkali developing photosensitive transparent resin composition a polyfunctional monomer is characterized that you containing a fluorene-based monomer. 2. The photosensitive transparent resin composition for alkali development according to claim 1, wherein the resin is an acrylic resin in which an ethylenically unsaturated group is added to a side chain, and a double bond equivalent is 340 to 1200. 3. . Alkaline developing the photosensitive transparent resin composition according to claim 1 or 2, characterized in that it contains a barium sulfate particles. 4. A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the reflective display portion of at least one of the two substrates sandwiching the liquid crystal layer is provided in any one of claims 1 to 3 . It has a rectangular or forward tapered transparent resin layer having a film thickness of 1.0 μm or more and a taper length of 2.0 μm or less, formed of a photosensitive transparent resin composition for alkali development. A transflective liquid crystal display device having a stimulation value decrease index ΔZ of 4.0 or less. A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the transmissive display portion colored layer and the reflective display portion colored layer of the color filter are made of the same coloring material, and a through hole is formed in the reflective display portion colored layer. And the reflective display part of at least one of the two substrates sandwiching the liquid crystal layer is formed of the photosensitive transparent resin composition for alkali development according to any one of claims 1 to 3 . It has a rectangular or forward tapered transparent resin layer with a film thickness of 1.0 μm or more and a taper length of 2.0 μm or less, and the tristimulus value decrease index ΔZ of the transparent resin layer is 4.0 or less. A transflective liquid crystal display device. A transflective liquid crystal display device having a transmissive display portion and a reflective display portion, wherein the transmissive display portion colored layer and the reflective display portion colored layer of the color filter are made of the same coloring material, and the reflective display portion colored layer of the color filter, A rectangular or sequential film having a film thickness of 1.0 μm or more and a taper length of 2.0 μm or less, formed from the photosensitive transparent resin composition for alkali development according to any one of claims 1 to 3 between the substrates. A transflective liquid crystal display device comprising a tapered transparent resin layer, wherein the tristimulus value lowering index ΔZ of the transparent resin layer is 4.0 or less.

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