JP5736691B2 - Color filter for liquid crystal display - Google Patents

Description

  The present invention relates to a color filter for a liquid crystal display device of a lateral electric field drive system, which includes a base material, a colored layer, a light shielding portion, and a spacer on the base material.

  Conventionally, a color liquid crystal display device has been used as a flat display. In such a liquid crystal display device, a color filter and a thin film transistor (TFT) substrate face each other with a predetermined gap, and a liquid crystal material is injected into the gap to form a liquid crystal layer. In order to maintain the distance between the TFT substrate and the color filter facing each other, a spacer is provided between them, thereby maintaining the thickness of the liquid crystal layer between them uniformly in the plane.

  In particular, in a color filter used in a lateral electric field drive (IPS) type liquid crystal display device, a color filter is manufactured by providing a light shielding portion on a base material of the color filter and further providing a spacer on the light shielding portion. (For example, see Patent Document 1). By this spacer, the distance between the thin film transistor (TFT) substrate and the color filter 100 is maintained. However, providing a spacer in a limited region on the light shielding portion has a problem that it is difficult to secure a sufficient spacer height (cell gap).

  Therefore, in order to obtain a sufficient cell gap, it has been studied to form a spacer by laminating a colored layer on a light shielding portion of a color filter and further providing a transparent protective layer thereon. As a means for forming a transparent protective layer, it has been proposed to use a UV curable resin by photolithography (see, for example, Patent Document 2). It has also been proposed to form a transparent protective layer made of an inorganic material by a dry film forming method such as sputtering, vacuum deposition, or plasma CVD (see, for example, Patent Document 3). However, since either method requires an additional process for providing a transparent protective layer, shortening of the manufacturing process and cost reduction are desired.

  Therefore, development of a color filter for a liquid crystal display device of a lateral electric field drive system having a spacer capable of obtaining a sufficient cell gap without requiring an additional process is eagerly desired.

JP 2009-2111005 A JP 2008-90191 A JP 2009-169064 A

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a color filter for a liquid crystal display device of a lateral electric field drive system, which includes a spacer capable of obtaining a sufficient cell gap. is there.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific thermosetting resin composition in order to form a transparent protective layer. It came to be completed.

That is, according to one aspect of the present invention,
A color filter for a liquid crystal display device driven by a horizontal electric field,
Comprising a base material, a light shielding part, a colored layer, and a spacer on the base material;
The spacer has a laminated column formed by laminating two or more colored layers, and a transparent protective layer formed on the laminated column,
The transparent protective layer is formed from a thermosetting resin composition containing a binder resin and a polymerization initiator,
A color filter in which the thermosetting temperature of the thermosetting resin composition is 80 ° C. or higher and 135 ° C. or lower is provided.

  In the color filter for a liquid crystal display device of the horizontal electric field driving system of the present invention, the spacer can obtain a sufficient cell gap by forming the transparent protective layer with a specific thermosetting resin composition.

1 is a schematic cross-sectional view illustrating an example of a color filter for a liquid crystal display device of a lateral electric field drive system according to the present invention. It is a figure which shows the DSC curve of the thermosetting resin compositions 1-7. It is a figure which shows the observation point in the measurement of a base-material temperature rise. It is a figure which shows the temperature rising curve of the base material obtained by the measurement of base-material temperature rise. It is a figure which shows the relationship between the variation in the height of a spacer, and the thermosetting temperature of a thermosetting resin composition.

Color filter In this invention, a color filter has a light-shielding part, a colored layer, and a spacer on a base material and a base material. Specifically, FIG. 1 shows a schematic sectional view of an example of the color filter according to the present invention. The color filter 10 shown in FIG. 1 includes a light shielding part 30 having an opening on a base material 20, and colored layers 40 of each color in the opening (a red colored layer 41, a green colored layer 42, and a blue colored layer 43). And a spacer 70 on the light-shielding portion 30. The spacer 70 includes a laminated column 50 in which the colored layer 40 is laminated on the light shielding unit 30 and a transparent protective layer 60 on the laminated column 50. Further, the transparent protective layer 60 is also formed on the peripheral portion other than the top of the laminated pillar 50 so as to cover the colored layer 40 and the light shielding portion 30 of each color. Each configuration will be described below.

Substrate According to a preferred embodiment of the present invention, since the substrate is on the light emitting side, a transparent substrate having high light transmittance is used. For example, the transparent base material which consists of material with high light transmittances, such as glass, quartz, or various resin, is mentioned. Moreover, the thickness of a base material is 0.1-10.0 mm normally.

Light-shielding part According to a preferred embodiment of the present invention, the light-shielding part is formed on the substrate and has an opening. As the light-shielding portion, one in which openings having the same shape are formed in a pattern at equal intervals is used. The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. A method for forming the light shielding part is not particularly limited as long as it can pattern the light shielding part, and a known method can be used. For example, it may be formed by a photolithography method using a black dispersion liquid containing a black coloring material and a photosensitive resin composition.

Colored layer According to a preferred embodiment of the present invention, the colored layer is formed in the opening of the light-shielding part on the substrate, and includes, for example, three colored patterns of red, green, and blue. Is good. The coloring pattern may be four colors of red, green, blue, and yellow, and five colors of red, green, blue, yellow, and cyan. Moreover, the colored layer of each color can be formed using the resin composition for colored layers containing the coloring material of each color. The colored layer is usually formed with a thickness of 1 μm to 5 μm. The method for forming the colored layer is not particularly limited as long as it can pattern the colored layer, and a known method can be used. For example, a photolithography method using a photosensitive resin composition is preferable because a stacked column on which a colored layer is stacked can be accurately formed at a desired position.

Colored Layer Resin Composition According to a preferred embodiment of the present invention, the colored layer resin composition for forming the colored layer of the color filter is a dispersion in which colored materials of respective colors are dispersed in a solvent. The method for dispersing the coloring material is not particularly limited, and the coloring material can be dispersed using a known disperser. Examples of the red coloring material include perylene pigments, lake pigments, azo pigments, quinacdrine pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. Examples of the green coloring material include phthalocyanine pigments, triphenylmethane pigments, isoindoline pigments, and isoindolinone pigments. Examples of blue coloring materials include phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, and dioxazine pigments. These coloring materials may be used alone or in combination of two or more. Moreover, the colored layer resin composition for each color contains a solvent, a dispersant, a monomer, a polymer, a polymerization initiator, and the like as necessary in addition to the above-described coloring material.

Spacer According to a preferred aspect of the present invention, the spacer is formed on a portion other than the opening of the light shielding portion on the substrate. The spacer has a stacked column formed by stacking two or more colored layers and a transparent protective layer formed on the stacked column. In the present invention, the “spacer height” is formed on the stacked column in the vertical direction from the peripheral portion of the spacer (the surface of the transparent protective layer formed on the colored layer and / or the light shielding portion of each color). This is the distance (thickness) to the surface of the transparent protective layer. For example, as shown in FIG. 1, a distance 80 from the transparent protective layer 60 around the spacer in the vertical direction to the top of the spacer. In the present invention, the height of the spacer is preferably 1 to 10 μm, and more preferably 1.5 to 5 μm. This is because a sufficient cell gap can be obtained if the height of the spacer is in the above range.

In the laminated columns present invention, laminated pillars, two or more colors, preferably not colored layer 2 color 5 colors are laminated. When the coloring pattern formed on the substrate has three colors of red, green, and blue, the stacked pillar is preferably formed by stacking colored layers of three colors of red, green, and blue. This is because it is not necessary to provide an additional layering step in order to form the layered column.

  According to the preferable aspect of this invention, the number of lamination | stacking of the colored layer of a lamination pillar is 2 layers or more, More preferably, it is 2-5 layers. Further, if two or more colored layers are laminated, two or more colored layers of the same color may be present in the laminated column. In the present invention, it is preferable to set the number of laminated columns depending on the number of colored patterns of the colored layer. If the number of stacked layers is in the above range, a sufficient height can be obtained. Note that the number of stacked columns provided on the light shielding portion may be the same or different.

  In the present invention, the planar shape of the colored layer constituting the laminated column is not particularly limited as long as it can stably form the laminated column, and examples thereof include a circle, an ellipse, and a polygon. Moreover, it is preferable to form so that the area of the plane of the colored layer which comprises a lamination | stacking pillar may become the narrowest in order by the uppermost layer with the widest colored layer of the lowest layer. This is because the stacked pillars can be formed stably.

Transparent protective layer In this invention, a transparent protective layer is formed from the thermosetting resin composition containing binder resin and a polymerization initiator. In this invention, the reliability in a manufacturing process can be improved (decrease in a defect) by forming a transparent protective layer using a thermosetting resin composition. Moreover, the number of steps can be reduced as compared with the case of using the UV curable resin composition, and the cost can be suppressed by simplifying the production equipment. According to a preferred embodiment, the transparent protective layer formed on the laminated pillar has a film thickness of 0.35 μm or more, preferably 0.45 μm or more and 5 μm or less, more preferably 0.55 μm or more and 2 μm or less. A sufficient cell gap can be obtained because the transparent protective layer has a film thickness in the above range. A transparent protective layer may also be formed on the light shielding portion and the colored layer that are the peripheral portions of the spacer. In addition, the film thickness of the transparent protective layer formed on the laminated pillar is the film thickness of the laminated pillar before application of the thermosetting resin composition using a film thickness measuring device (manufactured by KLA-Tencor, P-15). It can calculate from the difference of the film thickness of the lamination | stacking column after thermosetting resin composition application | coating.

Thermosetting resin composition In the present invention, the thermosetting resin composition is characterized by a caloric displacement (exotherm) generated when a binder resin and a polymerization initiator cause a polymerization reaction, and uses a differential scanning calorimeter. And having a characteristic transition heat curve (DSC curve). For this reason, the thermosetting resin composition starts curing at a specific temperature, and this temperature is referred to as a thermosetting temperature. The thermosetting temperature of the thermosetting resin composition is 80 ° C. or higher and 135 ° C. or lower, preferably 100 ° C. or higher and 130 ° C. or lower. If the thermosetting temperature is 135 ° C. or lower, the cell gap approaches substantially uniform by shortening the time until curing, and if it is 80 ° C. or higher, the storage stability is improved. Therefore, if the thermosetting temperature is in the above range, in order to shorten the time to start curing of the thermosetting resin composition and to suppress the decrease in viscosity, flow and diffusion of the thermosetting resin composition is prevented. Can be prevented. As a result, a transparent protective layer having a film thickness in the above range that can provide a sufficient cell gap can be formed on the stacked pillars.

  Here, in the present invention, “thermosetting temperature” means the peak top of the calorific value in a DSC curve measured when heated to 30 ° C. at a rate of temperature increase of 10 ° C./min after being held at 30 ° C. for 5 minutes. It is the temperature at the time. DSC is Differential scanning calorimetry (differential scanning calorimetry).

In addition, since the thermosetting resin composition is cured at a lower temperature (135 ° C. or lower) than the conventional thermosetting temperature (for example, about 150 ° C.) in the manufacturing process, the color filter base when forming the transparent protective layer is used. The temperature variation on the material can be adjusted within a narrow range. Thereby, the variation in the height of the spacer can be suppressed. According to a preferred aspect of the present invention, the spacer height variation 3σ is preferably 0.09 or less, and more preferably 0.08 or less. If the variation 3σ is 0.09 or less, since the cell gap approaches substantially uniform, the occurrence of defects such as unevenness can be suppressed, and clear image quality display becomes possible. In the present invention, the spacer height variation 3σ can be obtained by the following equation (1).
Formula 1
3σ = 3 × σ
σ = {Σ (x _i −x _A ) ² / (n−1)} ^1/2
In the formula, 3σ: variation in spacer height σ: standard deviation (positive square root of unbiased dispersion)
n: Number of measurements (for example, 20 to 100)
x _i : each measured value (spacer height), (i: 1 to n)
x _A : Average value of each measurement

Binder resin According to a preferred embodiment of the present invention, the binder resin is a thermosetting compound having an unsaturated double bond, specifically a compound obtained by reacting an epoxy compound and acrylic acid, and subjected to this reaction. Specific examples of the epoxy compound include bisphenol component of epoxy as aromatic epoxy, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3) , 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxy) Phenyl) hexafluoropropane, bis (4-hydroxy-3,5- Methylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) Methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Propane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3) -Chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3) -Methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, and 4,4′-biphenol, 3,3 ′ -There are epoxy resins containing biphenol and the like. Furthermore, a phenol novolak type epoxy, a cresol novolak type epoxy, a polycarboxylic acid glycidyl ester, a polyol polyglycidyl ester, an aliphatic or alicyclic epoxy resin, and an amine epoxy resin are also included. By using such a compound of epoxy resin and acrylic acid, a cured product excellent in moisture resistance, transparency, surface curability, and chemical resistance can be formed.

Polymerization initiator According to a preferred embodiment of the present invention, the polymerization initiator is t-amylperoxyneodecanoate, t-butylperoxyneodecanoate, di (2-ethylhexyl) peroxydicarbonate, di ( Secondary butyl) peroxydicarbonate, t-butylperoxyneoheptanoate, t-amylperoxypivalate, t-hexylperoxypivalate, t-butylperoxypivalate, diisononanoyl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-amylperoxy 2-ethylhexanoate, t-butylperoxy-2-ethylhe Sanoate, t-butylperoxyisobutyrate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexano And di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, and 1,1-di (t-butylperoxy) -2-methylcyclohexane. Particularly preferred polymerization initiators are selected from the group consisting of t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, disuccinic acid peroxide, dibenzoyl peroxide, and mixtures thereof. It is what is done. By using such a polymerization initiator, the thermosetting temperature of the thermosetting resin composition can be adjusted within a desired range. In the present invention, commercially available polymerization initiators can also be used, and examples thereof include perbutyl PV, paroyl 355, paroyl SA, and niper BW (manufactured by Nippon Oil & Fats Co., Ltd.). In a preferred embodiment, the content of the polymerization initiator is 0.1 to 10% by mass with respect to the binder resin.

Manufacturing method of color filter The manufacturing method of the color filter of the present invention is not particularly limited, and examples thereof include a photolithography method, a spin coating method, a printing method, an ink jet method, a bar coating method, a spray method, and a die coating method. In the present invention, it is preferable to form a transparent protective layer by thermosetting after forming the light-shielding portion, the colored layer, and the laminated column by a photolithography method using the photosensitive resin composition. As in the prior art, when forming a transparent protective layer on the stacked pillars by photolithography, an additional step is required. In the present invention, however, the transparent protective layer is thermally cured, so that an additional step is required. Since the process is omitted and the thermosetting resin composition is cured at a low temperature, the manufacturing process can be shortened.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to the content of the following Examples, and is not interpreted.

Example 1
Preparation of photosensitive resin composition First, 63 parts by weight of methyl methacrylate (MMA), 12 parts by weight of acrylic acid (AA), 6 parts by weight of 2-hydroxyethyl methacrylate (HEMA), diethylene glycol in a polymerization tank After 88 parts by weight of dimethyl ether (DMDG) was added and stirred to dissolve, 7 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. Further, 7 parts by weight of glycidyl methacrylate (GMA), 0.4 parts by weight of triethylamine, and 0.2 parts by weight of hydroquinone were added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution ( A solid content of 50%) was obtained. Next, the following materials were stirred and mixed at room temperature to obtain a photosensitive resin composition.
Composition of photosensitive resin composition / copolymer resin solution (solid content 50%): 16 parts by weight / dipentaerythritol pentaacrylate (manufactured by Sartomer Co., Ltd., SR399):
24 parts by weight-orthocresol novolac type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 180S70): 4 parts by weight-2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one : 4 parts by weight ・ Diethylene glycol dimethyl ether: 52 parts by weight

Formation of light-shielding part First, the following components were mixed and sufficiently dispersed in a sand mill to prepare a black pigment dispersion.
Composition of black pigment dispersion : Black pigment: 23 parts by weight Polymer dispersion material (Disperbyk 111, manufactured by Big Chemie Japan Co., Ltd.):
2 parts by weight / solvent (diethylene glycol dimethyl ether): 75 parts by weight

Next, the following amount of components were sufficiently mixed to obtain a resin composition for a light shielding part.
Composition of light-shielding part resin composition- Black pigment dispersion: 60 parts by weight-Photosensitive resin composition: 20 parts by weight-Diethylene glycol dimethyl ether: 30 parts by weight

  Then, the light shielding part resin composition was applied on a glass substrate having a thickness of 1.1 mm (AN material manufactured by Asahi Glass Co., Ltd.) with a spin coater, dried at 100 ° C. for 3 minutes, and a film thickness of about 1 μm. A light shielding part was formed. Next, the light-shielding part is exposed to a light-shielding pattern with an ultrahigh pressure mercury lamp, and then developed with a 0.05% by mass potassium hydroxide aqueous solution. The light-shielding part which has an opening part was formed.

The resin composition for red colored layer having the following composition is applied on the base material on which the light-shielding part is formed as described above by a spin coating method (coating thickness: 2.5 μm), and then in an oven at 70 ° C. for 3 minutes. Dried. Next, a photomask is arranged at a distance of 100 μm from the coating film of the red colored resin composition, and ultraviolet rays are applied only to the region corresponding to the red colored layer forming region using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Irradiated for 10 seconds. Subsequently, it was immersed in 0.05 mass% potassium hydroxide aqueous solution (liquid temperature 23 degreeC) for 1 minute, and alkali development was carried out, and only the uncured part of the coating film of a red colored resin composition was removed. Thereafter, the base material was left in an atmosphere of 180 ° C. for 30 minutes to form a red colored layer. Subsequently, in the same process as the formation of the red colored layer, a green colored layer was formed using the following resin composition for a green colored layer. Furthermore, in the same process as the formation of the red colored layer, a blue colored layer was formed using the following blue colored layer resin composition. In addition, a laminated column in which a red colored layer, a green colored layer, and a blue colored layer were laminated in this order was formed.
B. Composition of resin composition for red colored layer I. Pigment Red 177 (Chromofine Red 6605, manufactured by Dainichi Seika Co., Ltd.): 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, photosensitive resin composition: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight
C. Composition of resin composition for green colored layer I. Pigment Green 36 (manufactured by DIC Corporation): 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, photosensitive resin composition: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight
B. Composition of resin composition for blue colored layer I. Pigment Blue 15: 6 (EP-CF, manufactured by DIC Corporation): 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, photosensitive resin composition: 5 parts by weight, 3-methoxybutyl acetate: 82 parts by weight

Next, a binder resin used for preparing the thermosetting resin composition was prepared by the following method. In a 500 ml four-necked flask, 231 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-di-isobutylphenol, and 72.0 g of acrylic acid are mixed and mixed. It melt | dissolved by heating at 90-100 degreeC, blowing (25 ml / min). Subsequently, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. The solution gradually became transparent and was stirred as it was. The acid value of this solution was measured, and heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value 0.8). Then, it cooled to room temperature and obtained the colorless and transparent solid. Next, 2 kg of cellosolve acetate was added to 303 g of the bisphenol fluorene type epoxy acrylate resin obtained above to prepare a solution, and then 38 g of 1,2,3,6-tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride 80. 5 g and 1 g of tetraethylammonium bromide were added and mixed. The mixture was gradually warmed and reacted at 110 to 115 ° C. for 2 hours to obtain Compound A (m / n = 50/50). The acid anhydride reaction was confirmed by the disappearance of the 1780 cm @ -1 peak in the IR spectrum. Further, the inherent viscosity of the obtained compound A was 0.3 dl / g (ηinh = 0.3). The resulting compound A was designated as binder resin A. And the binder resin A, the polymerization initiator, and the solvent were mixed with the following composition, and the thermosetting resin composition 1 was prepared.
Composition of thermosetting resin composition 1 Binder resin A 20 parts by weight Perbutyl PV (polymerization initiator, main component: t-butyl peroxypivalate, manufactured by NOF Corporation) 0.7 part by weight propylene glycol 79.3 parts by weight of monomethyl ether acetate

  A thermosetting resin composition having the above composition is applied by spin coating (coating thickness: 2.5 μm) on the substrate on which the light-shielding portion, the colored layer, and the stacked pillars are formed as described above, and then 230 ° C. Was dried in an oven for 3 minutes to form a transparent protective layer on the laminated pillar. Thereby, the color filter which has the spacer which has a lamination pillar and a transparent protective layer was manufactured.

Example 2
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 2 Binder resin A 20 parts by weight Parroyl 355 (polymerization initiator, main component: di (3,5,5-trimethylhexanoyl) peroxide, manufactured by NOF Corporation) 0 .7 parts by weight / Propylene glycol monomethyl ether acetate 79.3 parts by weight

Example 3
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 3 Binder resin A 20 parts by weight Parroyl SA (polymerization initiator, main component: disuccinic acid peroxide, manufactured by NOF Corporation) 0.7 parts by weight propylene glycol monomethyl ether 79.3 parts by weight of acetate

Example 4
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 4 / resin component A (binder resin) 20 parts by weight / niper BW (polymerization initiator, main component: dibenzoyl peroxide, manufactured by NOF Corporation) 0.7 part by weight / propylene 79.3 parts by weight of glycol monomethyl ether acetate

Comparative Example 1
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 5 Binder resin A 20 parts by weight Perhexa HC (polymerization initiator, main component: 1,1-di (t-hexylperoxy) cyclohexane, manufactured by NOF Corporation) 0. 7 parts by weight ・ 79.3 parts by weight of propylene glycol monomethyl ether acetate

Comparative Example 2
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 6 Binder resin A 20 parts by weight Perhexyl Z (polymerization initiator, main component: t-hexyl peroxybenzoate, manufactured by NOF Corporation) 0.7 part by weight propylene glycol monomethyl 79.3 parts by weight of ether acetate

Comparative Example 3
A color filter was produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was as follows.
Composition of thermosetting resin composition 7 Binder resin A 20 parts by weight Park mill D (polymerization initiator, main component: dicumyl peroxide, manufactured by NOF Corporation)
0.7 parts by weight / propylene glycol monomethyl ether acetate 79.3 parts by weight

Measurement of thermosetting temperature Each of the thermosetting resin compositions 1 to 7 was held at 30 ° C for 5 minutes, and then heated to 230 ° C at a temperature rising rate of 10 ° C / min. It measured with the differential scanning calorimetry (DSC) apparatus (DSC-50, Shimadzu Corporation make), and obtained the DSC curve.

The DSC curves of the thermosetting resin compositions 1 to 7 obtained above are shown in FIG. The thermosetting temperature of each thermosetting resin composition calculated from the DSC curve is shown in Table 1 below. It turned out that the thermosetting temperature of the thermosetting resin compositions 1-4 used for Examples 1-4 is 80 degreeC or more and 135 degrees C or less.

Measurement of substrate temperature rise In the manufacturing process of the color filter, the temperature rise time of the substrate until reaching the thermosetting temperature of the thermosetting resin composition may vary depending on the location of the substrate. Therefore, as shown in FIG. 3, in the color filter manufacturing process in which eight patterning layers (shaded portions in FIG. 3) are provided on a glass substrate, a plurality of measurement points (1 to 12) are formed on the back surface of the substrate. : Immediately under the patterning layer, 13 to 15: Immediately under the raw glass layer), the temperature rise of the substrate is measured by a temperature measuring device (WINTFS WHTF-K-0.32-3-V, thermocouple) Measured using type K). As a result of the measurement, a temperature rise curve of the substrate was obtained.

  The temperature rise curve of the base material obtained above is shown in FIG. When the substrate temperature was 135 ° C., the variation in temperature increase (A in FIG. 4) was about 30 seconds, whereas when the substrate temperature was 150 ° C., the variation in temperature increase (B in FIG. 4) was about It was 50 seconds. Therefore, it was found that by reducing the thermosetting temperature of the thermosetting resin composition to 135 ° C., the variation in temperature rise can be greatly reduced and the entire in-plane curing can be made more uniform. Moreover, since time until hardening can be shortened, it turned out that fluidization of a thermosetting resin composition is prevented and shortening of a manufacturing process is realizable.

Measurement of film thickness of transparent protective layer About the color filter produced above, the film thickness of the transparent protective layer formed on the stacked pillars was measured using a film thickness measuring device (P-15, manufactured by KLA-Tencor). It calculated from the difference of the film thickness of the lamination | stacking column before application | coating of curable resin composition, and the film thickness of the lamination | stacking column after thermosetting resin composition application | coating. The results are shown in Table 2.

Measurement of spacer height variation For the color filter manufactured as described above, the height of the spacer is measured from the same colored single film arbitrarily determined using a measuring device (Super PSIS-6008, manufactured by SNU Precision). The spacer height variation 3σ was calculated from the equation (1). The number of measurements is n = 40.

  FIG. 5 shows the relationship between the variation in the height of the spacer and the thermosetting temperature of the thermosetting resin composition. The color filters manufactured in Examples 1 to 4 were found to have a spacer height variation 3σ of 0.09 or less.

DESCRIPTION OF SYMBOLS 10 Color filter 20 Base material 30 Light-shielding part 40 Colored layer 41 Red colored layer 42 Green colored layer 43 Blue colored layer 50 Laminated pillar 60 Transparent protective layer 70 Spacer 80 Spacer height

Claims (3)

A color filter for a liquid crystal display device driven by a horizontal electric field,
On the base material and the base material, the light-shielding portion, the colored layer, and the spacer,
The spacer has a stacked column in which colored layers of two or more colors are stacked, and a transparent protective layer formed on the stacked column,
The transparent protective layer is formed from a thermosetting resin composition containing a binder resin and a polymerization initiator,
The binder resin is a resin obtained by reacting at least an epoxy resin and acrylic acid,
The polymerization initiator is selected from the group consisting of t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, disuccinic acid peroxide, dibenzoyl peroxide, and mixtures thereof. ,
The color filter whose thermosetting temperature of the said thermosetting resin composition is 80 to 135 degreeC. The color filter according to claim 1, wherein the transparent protective layer formed on the laminated pillar has a film thickness of 0.35 μm or more. The spacer height variation 3σ is expressed by the following formula (1):
Formula 1
3σ = 3 × σ
σ = {Σ (x _i −x _A ) ² / (n−1)} ^1/2
In the formula, 3σ: variation in spacer height σ: standard deviation (positive square root of unbiased dispersion)
n: Number of measurements x _i : Each measured value (spacer height), (i: 1 to n)
x _A: when it is determined by the average value of the measurement is 0.09 or less, the color filter according to claim 1 or 2.

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