JP4983618B2 - Method for selecting resin member for color filter and method for producing color filter using the same - Google Patents

Description

  The present invention relates to a method for selecting a resin member for a color filter, and more particularly to a method for selecting a resin member used for a color filter that enables a liquid crystal display device having excellent display quality.

  In recent years, a color liquid crystal display device has attracted attention as a flat display. As an example of a color liquid crystal display device, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a common transparent electrode layer, and an alignment layer are provided. A transmissive liquid crystal in which a color filter and a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer face each other with a predetermined gap and a liquid crystal material is injected into the gap to form a liquid crystal layer. There is a display device. There is also a reflective liquid crystal display device in which a reflective layer is provided between the color filter substrate and the colored layer.

In such a color liquid crystal display device, when the alignment state of the liquid crystal changes due to a liquid crystal alignment failure, a voltage change applied to the liquid crystal, a voltage variation in the display surface, or the like, a display failure occurs. This display defect includes the following image sticking and white unevenness.
Image sticking occurs when the voltage is lowered or turned off after a voltage is applied to the same pixel for a certain period of time, so that the transmittance of this pixel differs from the transmittance of the surrounding pixels for which the voltage was not applied for a certain period of time. This is a phenomenon in which the uneven state is recognized, and the uneven state continues even after being left for a long time. In a burn-in phenomenon in a normally white panel, a pixel to which a voltage is applied for a certain time appears darker than surrounding pixels. Such seizure phenomenon is caused by the fact that the ionic substance adheres to the electrode during voltage application, and the ionic substance remains adsorbed on the electrode even if the voltage is released next, and the voltage due to this ionic substance is liquid crystal. It is thought that this is caused by continuing to act on

  Further, the white unevenness is a phenomenon in which the uneven state is recognized because a part of the display area does not become zero transmittance when a black screen is displayed by applying a voltage. This is because the voltage applied between the electrodes should be kept constant, but if there is an ionic substance in the liquid crystal, the ionic substance moves, that is, the current flows, so the voltage between the electrodes The cause is thought to be descending.

  It is considered that the ionic substance that causes the display defect phenomenon as described above does not stay on the electrode but easily moves in the liquid crystal layer. Various sources can be considered as the source of this ionic substance. In order to prevent display defects, impurities from chemicals, air, pure water, etc. used in the manufacturing process, management from equipment, human bodies, etc. Dust generation management and process conditions are optimized. Also, impurities such as residue are removed by cleaning the surface of the color filter and the counter electrode substrate, and by irradiating with ultraviolet rays and polishing the surface in the manufacturing process.

Although such a response makes it difficult for the display failure phenomenon to occur, there is a problem that the probability of the display failure is still high under long-time display conditions, particularly under severe display conditions such as high temperature and high humidity.
The present invention has been made in view of the circumstances as described above, and provides a method for selecting a resin member for use in a color filter in which mixing of an ionic substance into a liquid crystal layer is more reliably prevented. Objective.

  The present invention considers a resin member that is in contact with the liquid crystal layer of a liquid crystal display device as one of the sources of the ionic substance as described above, and has a correlation with a display defect due to the ionic substance transferred from the resin member into the liquid crystal layer. As a characteristic, the resin member in contact with the liquid crystal is subjected to a forced impurity extraction process, and attention is paid to the voltage holding ratio applied to the liquid crystal through the resin member.

That is, in order to achieve the above object, the present invention is a resin member that constitutes a color filter used in a liquid crystal display device, and is a resin-colored layer that can be located nearest to the liquid crystal, and the resin color In a method of selecting a resin protective layer for covering a layer and a resin member for forming a resin columnar convex portion, one ITO of a set of ITO substrates in which an electrode made of indium tin oxide (ITO) is provided on the surface of a glass substrate A resin member layer to be selected is formed on the ITO electrode of the substrate, and then both ITO substrates are opposed so that the distance between the ITO electrodes is in the range of 5 to 15 μm, and the peripheral portion is sealed with a sealing member, by sealing liquid crystal between two ITO substrates were fabricated liquid crystal cell for measurement, 105 ° C. in the measurement for each liquid crystal cell in an oven, the resin member is subjected to heat treatment by leaving 2.5 hours An impurity is forced extraction process on, then after returning to room temperature, in which the voltage holding ratio was measured by the following measuring conditions, the measured voltage holding ratio is selected as good a resin member made of a 90% In addition, the liquid crystal is configured to be a liquid crystal having a voltage holding ratio measured by the measurement liquid crystal cell of 95% or more in a state before the forced impurity extraction process.
(Measurement conditions of voltage holding ratio)
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec
In addition, the color filter manufacturing method of the present invention uses a resin member selected as a non-defective product by any of the selection methods described above to form a resin colored layer having a plurality of colors in a predetermined pattern on the substrate. The configuration.
In addition, the color filter manufacturing method of the present invention forms a colored layer having a plurality of colors on a substrate in a predetermined pattern, and then uses a resin member selected as a non-defective product by any of the above selection methods. A transparent resin protective layer is formed so as to cover at least the colored layer, and the resin member selected as a non-defective product by any one of the selection methods described above is used, and a plurality of components on the resin protective layer are formed. It was set as the structure which forms a transparent resin columnar convex part in a predetermined part.

  According to the present invention, a liquid crystal display device excellent in display quality can be obtained, in which display defects such as image sticking and white unevenness can be prevented even during long-time display under severe display conditions such as high temperature and high humidity. The resin member for the color filter that can be made can be selected reliably.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, exemplary embodiments of the invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a color filter to which the method for selecting a resin member for a color filter of the present invention is applied. In FIG. 1, a color filter 11 includes a substrate 12 and a resin colored layer 13 composed of a plurality of colors formed in a predetermined pattern on the substrate 12, and the resin colored layer 13 includes a black matrix 14, It is composed of a colored film 15 provided at a non-formed portion of the black matrix 14.

  The color filter 11 is used in a liquid crystal display device in a state where a common transparent electrode layer and an alignment layer are provided on the resin coloring layer 13. In this case, the resin coloring layer 13 is the closest to the liquid crystal as the resin member. It becomes the position. In the present invention, the resin member that is in contact with the liquid crystal layer of the liquid crystal display device is considered as one of the sources of impurities such as ionic substances, and as a characteristic that correlates with display defects due to impurities transferred from the resin member into the liquid crystal layer, The resin member in contact with the liquid crystal was subjected to a forced impurity extraction process, and attention was paid to the voltage holding ratio applied to the liquid crystal through the resin member.

  That is, in the present invention, in order to prevent display defects such as white unevenness and image sticking, the resin member in contact with the liquid crystal is subjected to a forced impurity extraction process, and the voltage applied to the liquid crystal through the resin member. A resin member that can maintain a retention rate of 90% or more is selected as a non-defective product. The color filter 11 in which the resin coloring layer 13 is formed using the resin member selected as described above, when used in a liquid crystal display device, impurities such as ionic substances are hardly eluted in the liquid crystal, and particularly at a high temperature. Even under severe display conditions such as long-term display under high humidity (for example, continuous image display for 200 hours under conditions of 50 ° C. and 60% RH), display defects such as burn-in and white unevenness occur. Is prevented, and a liquid crystal display device having excellent display quality is possible.

Here, the above-described impurity forced extraction process and voltage holding ratio measurement conditions will be described.
(Impurity extraction process)
As shown in FIG. 2, a set of ITO substrates 51 and 54 in which ITO (indium tin oxide) electrodes 53 and 56 are provided on the surfaces of glass substrates 52 and 55 are prepared. Next, a color filter resin member layer 57 (resin colored layer 13 in the case of the color filter 11) that is the nearest position to the liquid crystal is formed, and then the ITO electrode distance is in the range of 5 to 15 μm. The other ITO substrate 54 is made to face, the periphery is sealed with a seal member 59, and the liquid crystal 58 is sealed between the two ITO substrates to produce the measurement liquid crystal cell 50. The resin member layer 57 is formed under the same conditions as in the case of forming a color filter. When processing steps such as pre-baking and post-baking are necessary, the resin member layer 57 is processed under predetermined conditions. The liquid crystal 58 to be used is a liquid crystal having a voltage holding ratio of 95% or more measured under the following voltage holding ratio measurement conditions in the measurement liquid crystal cell 50 in the state before the forced impurity extraction process.

The resin member layer 57 is the resin colored layer 13 in the color filter 11 and may form the black matrix 14 and the colored film 15 at the same time, or the black matrix 14 alone, the colored film 15 alone, and further the colored film. The resin member layer 57 may be formed independently for each color of each of the colored patterns 15R, 15G, and 15B that constitutes 15. In the present invention, the resin member of the color filter that is the nearest position to the liquid crystal must satisfy the above-mentioned definition.
Next, the measurement liquid crystal cell 50 is subjected to heat treatment (in an oven, left at 105 ° C. for 2.5 hours) to perform impurity forced extraction processing on the resin member layer 57.

(Voltage holding ratio measurement conditions)
The liquid crystal cell for measurement 50 subjected to the forced impurity extraction treatment as described above is returned to room temperature, and the voltage holding ratio is measured under the following conditions.
・ Distance between ITO electrodes: 5 to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec

  When the color filter 11 is used in a liquid crystal display device, it is used in a state where a common transparent electrode layer or an alignment layer is provided on the resin colored layer 13 as described above. The thickness of the layer is usually as thin as 0.01 to 1 μm, and the effect of shielding impurities can hardly be expected. Therefore, it is necessary to make the resin colored layer 13 have the above characteristics.

  The substrate 12 constituting the color filter 11 has flexibility such as a transparent rigid material such as quartz glass, pyrex glass, and synthetic quartz plate, or a transparent resin film or an optical resin plate. A transparent flexible material can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices.

  Further, the black matrix 14 constituting the resin coloring layer 13 of the color filter 11 is provided between the display pixel portions formed of the coloring film 15 and outside the forming area of the coloring film 15. Such a black matrix 14 is formed by forming a resin layer containing light-shielding particles such as carbon fine particles and patterning the resin layer, and containing light-shielding particles such as carbon fine particles and metal oxides. Any of those formed by forming a photosensitive resin layer and patterning the photosensitive resin layer may be used.

  In order for the resin material for forming such a black matrix 14 to pass the selection method of the present invention, the amount of polymerization initiator used at the time of forming the black matrix 14, setting conditions for post-baking, patterning exposure It is preferable to increase the degree of crosslinking of the resin by adjusting the post-exposure amount after completion.

  In the present invention, the color filter 11 may not include the black matrix 14. In this case, the substrate 12 may be exposed at a portion where the colored film 15 is not formed, or the colored film 15 may be formed so as to cover the substrate 12.

  The colored film 15 constituting the resin coloring layer 13 of the color filter 11 is a photosensitive resin in which a red pattern 15R, a green pattern 15G, and a blue pattern 15B are arranged in a desired pattern shape and contains a desired colorant. Can be formed by a known method such as a printing method or a transfer method. In addition, for example, by increasing the thickness of the colored film 15 in the order of the red pattern 15R, the green pattern 15G, and the blue pattern 15B, an optimal liquid crystal layer thickness may be set for each color of the colored film 15. .

  In order for the resin material for forming such a colored film 15 to pass the selection method of the present invention, the amount of polymerization initiator used at the time of forming the colored film 15, post-bake setting conditions, patterning exposure It is preferable to increase the degree of crosslinking of the resin by adjusting the post-exposure amount after completion.

  In the case where a common transparent electrode layer is provided on the colored resin layer 13, a sputtering method or vacuum deposition is performed using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof. The film can be formed by a general film forming method such as a CVD method or a CVD method. The thickness of such an electrode layer is about 0.01 to 1 μm, and as described above, the effect of shielding impurities generated from the resin member located on the outside from moving to the liquid crystal layer can hardly be expected.

FIG. 3 is a schematic cross-sectional view showing another example of a color filter to which the method for selecting a resin member for a color filter of the present invention is applied. In FIG. 3, a color filter 11 'is a resin coloring composed of a substrate 12, a black matrix 14' formed on the substrate 12, and a plurality of colors formed in a predetermined pattern so as to cover the black matrix 14 '. Layer 15 'is provided.
The substrate 12 constituting the color filter 11 ′ can be the same as the substrate 12 constituting the color filter 11.

  The black matrix 14 ′ constituting the color filter 11 ′ is covered with a resin coloring layer 15 ′, and a metal thin film such as chromium having a thickness of about 1000 to 2000 mm is formed by a sputtering method, a vacuum deposition method, or the like. Formed by patterning, formed resin layer of polyimide resin, acrylic resin, epoxy resin, etc. containing light shielding particles such as carbon fine particles, and formed by patterning this resin layer, carbon fine particles, metal oxide It may be any one formed by forming a photosensitive resin layer containing light-shielding particles such as an object and patterning the photosensitive resin layer.

  When the resin colored layer 15 ′ constituting the color filter 11 ′ is used in a liquid crystal display device with a common transparent electrode layer or alignment layer provided on the resin colored layer 15 ′, the resin material nearest to the liquid crystal is used. It becomes the position. Therefore, similar to the colored film 15 of the resin colored layer 13 of the color filter 11 described above, the resin material for the resin colored layer 15 ′ is subjected to a forced impurity extraction process on the resin member in contact with the liquid crystal, A resin member capable of maintaining the holding ratio of the voltage applied to the liquid crystal through the resin member at 90% or more is selected as a non-defective product. The color filter 11 ′ in which the resin coloring layer 15 ′ is formed by using the resin member selected in this way is seized or white even under severe display conditions such as long-time display under high temperature and high humidity. Occurrence of display defects such as unevenness is prevented, and a liquid crystal display device having excellent display quality is possible.

  Such a resin colored layer 15 ′ is made of a photosensitive resin containing a desired colorant, in which a red pattern 15′R, a green pattern 15′G, and a blue pattern 15′B are arranged in a desired pattern shape. It can be formed by a known method such as a printing method or a transfer method. Further, by making the resin colored film 15 ', for example, the red pattern 15'R is the thinnest and the green pattern 15'G and the blue pattern 15'B are thickened in this order, the optimal liquid crystal for each color of the resin colored film 15'. The layer thickness may be set.

  In order for the resin material for forming the resin colored layer 15 ′ to pass the selection method of the present invention, the amount of polymerization initiator used at the time of forming the resin colored layer 15 ′, post-bake setting conditions, patterning It is preferable to increase the degree of cross-linking of the resin by adjusting the post-exposure amount after completion of the exposure.

  FIG. 4 is a schematic cross-sectional view showing another example of a color filter to which the method for selecting a resin member for a color filter of the present invention is applied. In FIG. 4, the color filter 21 includes a substrate 22 and a black matrix 24 and a colored layer 25 formed on the substrate 22, and a transparent resin protective layer 26 is formed so as to cover the black matrix 24 and the colored layer 25. Has been.

The color filter 21 is used in a liquid crystal display device in a state where a common transparent electrode layer and an alignment layer are provided on the resin protective layer 26. In this case, as the resin member, the resin protective layer 26 is closest to the liquid crystal. It becomes the position. Therefore, in the present invention, as the resin material for the resin protective layer 26, the resin member in contact with the liquid crystal is subjected to the impurity forced extraction process, and the holding ratio of the voltage applied to the liquid crystal through the resin member is reduced. A resin member that can be maintained at 90% or more is selected as a non-defective product. The color filter 21 in which the resin protective layer 26 is formed by using the resin member selected in this way has a seizing or white unevenness even under severe display conditions such as long-time display under high temperature and high humidity. Occurrence of display defects is prevented, and a liquid crystal display device having excellent display quality is possible.
The substrate 22 constituting the color filter 21 can be the same as the substrate 12 constituting the color filter 11 described above.

The black matrix 24 constituting the color filter 21 is formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by sputtering, vacuum deposition or the like, and patterning this thin film. Forming a resin layer made of polyimide resin, acrylic resin, epoxy resin or the like containing particles and patterning this resin layer, photosensitive resin containing light-shielding particles such as carbon fine particles or metal oxide It may be any one formed by forming a layer and patterning the photosensitive resin layer.
In the present invention, the color filter 21 may not include the black matrix 24.

  The colored layer 25 may be formed by a pigment dispersion method using a photosensitive resin containing a desired colorant in which a red pattern 25R, a green pattern 25G, and a blue pattern 25B are arranged in a desired pattern shape. Further, it can be formed by a known method such as a printing method, an electrodeposition method, or a transfer method. In addition, for example, by increasing the thickness of the colored layer 25 in the order of the red pattern 25R, the green pattern 25G, and the blue pattern 25B, an optimal liquid crystal layer thickness may be set for each color of the colored layer 25. .

  The resin protective layer 26 is provided to flatten the surface of the color filter 21 and to prevent the components contained in the colored layer 25 from eluting into the liquid crystal layer. The color filter 21 is a liquid crystal display device. The black matrix 24 and the colored layer 25 are formed to cover at least the black matrix 24 and the colored layer 25 so that the black matrix 24 and the colored layer 25 do not come into contact with the liquid crystal layer. Such a resin protective layer 26 can be formed using a resin material such as an acrylic copolymer. In order for the resin material for forming the resin protective layer 26 to pass the selection method of the present invention, the amount of the polymerization initiator used at the time of forming the resin protective layer 26, the post-bake setting conditions, and the completion of patterning exposure It is preferable to increase the degree of crosslinking of the resin by adjusting the amount of post-exposure later. The thickness of the resin protective layer 26 can be set in consideration of the light transmittance of the material used, the surface state of the color filter 21, etc., and can be set in the range of 0.1 to 3.0 μm, for example. .

  FIG. 5 is a schematic cross-sectional view showing another example of a color filter to which the method for selecting a resin member for a color filter of the present invention is applied. In FIG. 5, the color filter 31 includes a substrate 32, a black matrix 34 and a colored layer 35 formed on the substrate 32, and a transparent resin protective layer 36 is formed so as to cover the black matrix 34 and the colored layer 35. Furthermore, transparent resin columnar convex portions 37 are formed at predetermined locations on the black matrix 35 so as to protrude from the resin protective layer 36.

The color filter 31 is used in a liquid crystal display device in a state where a common transparent electrode layer and an alignment layer are provided on the resin protective layer 36. In this case, the resin member includes a resin protective layer 36 and a resin columnar convex portion 37. It is the closest position to the liquid crystal or a position in contact with the liquid crystal. Therefore, in the present invention, as the resin material for the resin protective layer 36 and the resin columnar convex portion 37, the resin member in contact with the liquid crystal is subjected to a forced impurity extraction process and applied to the liquid crystal through the resin member. A resin member capable of maintaining the retained voltage at 90% or more is selected as a non-defective product. The color filter 31 in which the resin protective layer 36 and the resin columnar convex portion 37 are formed using the resin member selected in this way, particularly under severe display conditions such as long-time display under high temperature and high humidity, Occurrence of display defects such as image sticking and white unevenness is prevented, and a liquid crystal display device having excellent display quality is possible.
The substrate 32 constituting the color filter 31 can be the same as the substrate 12 constituting the color filter 11 described above.

The black matrix 34 and the colored layer 35 constituting the color filter 31 can be the same as the black matrix 24 and the colored layer 25 constituting the color filter 21 described above. The color filter 31 may not include the black matrix 34.
The resin protective layer 36 constituting the color filter 31 can be the same as the resin protective layer 26 constituting the color filter 21 described above.

  The resin columnar convex portion 37 constituting the color filter 31 functions as a spacer when the color filter 31 is bonded to the counter electrode substrate. This resin columnar convex part 37 can be formed by, for example, applying a photosensitive resin paint, exposing, developing, and curing in a predetermined pattern. The resin columnar convex portion 37 has a certain height so as to protrude in the range of about 2 to 10 μm from the resin protective layer 36, and the protruding amount is a thickness required for the liquid crystal layer of the liquid crystal display device. It can set suitably from the above. Further, the formation density of the resin columnar protrusions 37 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape, material, and the like of the columnar protrusions 37. For example, the colored layer 35 is formed. Necessary and sufficient spacer functions are expressed at a ratio of one for each of the red pattern 35R, the green pattern 35G, and the blue pattern 35B. The shape of the resin columnar convex portion 37 is not particularly limited, and may be a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  Such resin columnar convex portions 37 can be formed using a resin material such as an acrylic copolymer. In order for the resin material for forming the resin columnar projections 37 to pass the selection method of the present invention, the amount of polymerization initiator used when forming the resin columnar projections 37, the post-bake setting conditions, patterning It is preferable to increase the degree of cross-linking of the resin by adjusting the post-exposure amount after completion of the exposure.

Next, an Example is shown and this invention is demonstrated further in detail.
<Preparation of resin material for color filter>
(1) Photosensitive paint for resin colored layer Photosensitive paints R1, R2, G1, G2, G3, B1, and B2 for resin colored layers of each color are dispersion compositions (pigments, dispersants, and solvents as necessary) Bead), dispersed with a disperser for 3 hours, and then mixed with a dispersion obtained by removing the beads and a clear resist composition (polymer, monomer, additive, disclosure agent and solvent), Its composition is shown below. A paint shaker was used as the disperser.

(Photosensitive paint R1 for red pattern)
・ Red pigment: 4.8 parts by weight (Ciba Specialty Chemicals Chromophthal Red A2B)
・ Yellow pigment: 1.2 parts by weight (PASFOL Yellow D1819 manufactured by BASF)
-Dispersant (Abyssia Solsperse 24000)-3.0 parts by weight-Monomer (Sartomer SR399)-4.0 parts by weight-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Ciba Specialty)・ Irgacure 907 from Chemicals)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Surfactant (Nonion HS-210, manufactured by NOF Corporation): 1.0 part by weight. Solvent: 79.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint R2 for red pattern)
・ Red pigment: 4.8 parts by weight (Ciba Specialty Chemicals Chromophthal Red A2B)
・ Yellow pigment: 1.2 parts by weight (PASFOL Yellow D1819 manufactured by BASF)
-Dispersant (Disperbic 161 manufactured by Big Chemie)-3.0 parts by weight-Monomer (SR399 manufactured by Sartomer)-4.0 parts by weight-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Ciba Specialty Chemicals Irgacure 907)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint G1 for green pattern)
Green pigment: 4.2 parts by weight (Avisia Monastral Green 6Y-CL)
・ Yellow pigment: 1.8 parts by weight (BASF Pariotol Yellow D1819)
-Dispersant (Abyssia Solsperse 24000)-3.0 parts by weight-Monomer (Sartomer SR399)-4.0 parts by weight-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Ciba Specialty)・ Irgacure 907 from Chemicals)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint G2 for green pattern)
Green pigment: 4.2 parts by weight (Avisia Monastral Green 9Y-C)
・ Yellow pigment: 1.8 parts by weight (BASF Pariotol Yellow D1819)
-Dispersant (Disperbic 161 manufactured by Big Chemie)-3.0 parts by weight-Monomer (SR399 manufactured by Sartomer)-4.0 parts by weight-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Ciba Specialty Chemicals Irgacure 907)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint G3 for green pattern)
Green pigment: 4.2 parts by weight (Avisia Monastral Green 6Y-CL)
・ Yellow pigment: 1.8 parts by weight (BASF Pariotol Yellow D1819)
-Dispersant (Abyssia Solsperse 24000)-3.0 parts by weight-Monomer (Sartomer SR399)-4.0 parts by weight-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Ciba Specialty)・ Irgacure 907 from Chemicals)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Surfactant (Nonion HS-210, manufactured by NOF Corporation): 1.0 part by weight. Solvent: 79.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint B1 for blue pattern)
・ Blue pigment: 6.0 parts by weight (BASF heliogen blue L6700F)
Pigment derivative (Abyssia Solsperse 12000) ... 0.6 parts by weight Dispersant (Abyssia Solsperse 24000) ... 2.4 parts by weight Monomer (Sartomer SR399) ... 4.0 parts by weight Polymer 1 ... 5.0 Part by weight ・ Initiator: 1.4 part by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

(Photosensitive paint B2 for blue pattern)
・ Blue pigment: 6.0 parts by weight (BASF heliogen blue L6700F)
Pigment derivative (Abyssia Solsperse 5000) ... 0.6 parts by weight Dispersant (Abyssia Solsperse 24000) ... 2.4 parts by weight Monomer (Sartomer SR399) ... 4.0 parts by weight Polymer 1 ... 5.0 Part by weight ・ Initiator: 1.4 part by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

  The polymer 1 is based on 100 mol% of a copolymer of benzyl methacrylate: styrene: acrylic acid: 2-hydroxyethyl methacrylate = 15.6: 37.0: 30.5: 16.9 (molar ratio). 2-methacryloyloxyethyl isocyanate was added at 16.9 mol%, and the weight average molecular weight was 42500. The same applies to the polymer 1 used in the following other paints.

(2) Coating for protective layer Three types of photosensitive coatings P1, P2, and P3 for resin protective layer having the following compositions were prepared.
(Photosensitive paint P1 for resin protective layer)
-Monomer (SR399 manufactured by Sartomer)-7.1 parts by weight-Polymer 1-8.8 parts by weight-Epoxy resin-9.7 parts by weight (Epicoat 180S70 made by oiled shell epoxy)
Initiator: 1.4 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Surfactant (Non-ion HS-210 made by NOF Corporation): 1.0 part by weight ・ Solvent (dimethyldiglycol): 37.0 parts by weight • Solvent (3-methoxybutyl acetate): 34.0 parts by weight

(Photosensitive paint P2 for resin protective layer)
-Monomer: 7.1 parts by weight (Nippon Kayaku Co., Ltd. KAYARAD DPHA)
-Polymer 1 ... 8.8 parts by weight-Epoxy resin ... 9.7 parts by weight (Epicoat 180S70 made of oil shell epoxy)
Initiator: 1.4 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent (dimethyldiglycol) 38.0 parts by weight Solvent (3-methoxybutyl acetate) 34.0 parts by weight

(Photosensitive paint P3 for resin protective layer)
-Monomer (SR399 manufactured by Sartomer)-7.1 parts by weight-Polymer 1-8.8 parts by weight-Epoxy resin-9.7 parts by weight (Epicoat 180S70 made by oiled shell epoxy)
Initiator: 1.4 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Surfactant (Non-ion HS-210, manufactured by NOF Corporation) 2.0 parts by weight Solvent (dimethyldiglycol) 36.0 parts by weight Solvent (3-methoxybutyl acetate) 34.0 parts by weight

(3) Photosensitive paint for columnar convex portions Three types of photosensitive paints S1, S2, and S3 for resin columnar convex portions having the following compositions were prepared.
(Photosensitive paint S1 for resin columnar protrusions)
-Monomer (SR399 manufactured by Sartomer) ... 8.7 parts by weight-Polymer 1 ... 10.9 parts by weight-Epoxy resin ... 12.1 parts by weight (Epicoat 180S70 made from oil-based shell epoxy)
・ Surfactant (Nonfax HS-210, manufactured by NOF Corporation): 1.0 part by weight ・ Initiator: 1.2 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 29.1 parts by weight (propylene glycol monomethyl ether acetate)
・ Solvent (3-methoxybutyl acetate) 36.1 parts by weight

(Photosensitive paint S2 for resin columnar protrusions)
-Monomer: 8.7 parts by weight (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
-Polymer 1 ... 10.9 parts by weight-Epoxy resin ... 12.1 parts by weight (Epicoat 180S70 made of oiled shell epoxy)
・ Initiator: 1.2 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 30.1 parts by weight (propylene glycol monomethyl ether acetate)
・ Solvent (3-methoxybutyl acetate) 36.0 parts by weight

(Photosensitive paint S3 for resin columnar protrusions)
-Monomer (SR399 manufactured by Sartomer) ... 8.7 parts by weight-Polymer 1 ... 10.9 parts by weight-Epoxy resin ... 12.1 parts by weight (Epicoat 180S70 made from oil-based shell epoxy)
・ Surfactant (Nonfax HS-210, manufactured by NOF Corporation): 2.0 parts by weight ・ Initiator: 1.2 parts by weight (Irgacure 907 manufactured by Ciba Specialty Chemicals)
Initiator: 1.0 part by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-
Tetraphenyl-1,2'-biimidazole)
・ Solvent: 28.1 parts by weight (propylene glycol monomethyl ether acetate)
・ Solvent (3-methoxybutyl acetate) 36.0 parts by weight

<Impurity forced extraction test of resin material for color filter>
(1) Preparation of liquid crystal cell for measurement A low expansion coefficient non-alkali glass substrate (7059 glass 100 mm × 100 mm, thickness 0.7 mm, manufactured by Corning) was prepared and washed according to a conventional method.

Next, on the ITO electrode of the glass substrate, the prepared photosensitive paints R1, R2, G1, G2, G3, B1, B2 for each color of the resin colored layer, photosensitive paints P1, P2, P3 for the resin protective layer, resin The columnar convex photosensitive paints S1, S2, and S3 were respectively applied by spin coating, pre-baked at 90 ° C. for 3 minutes, exposed with a frame-shaped photomask (100 mJ / cm ² ), 0.05% After spray development using a KOH aqueous solution for 60 seconds, a resin material layer having a film thickness of 1.5 μm was formed on the ITO electrode by performing post-baking at 200 ° C. for 30 minutes. In addition, the post-baking conditions of the photosensitive paints R2, G2, and B2 for the resin colored layer, the photosensitive paint P2 for the resin protective layer, and the photosensitive paint S3 for the resin columnar convex portion were set to 230 ° C. for 30 minutes.
On the other hand, a low expansion coefficient non-alkali glass substrate (Corning 7059 glass 100 mm × 100 mm, thickness 0.7 mm) on which an ITO electrode was formed was prepared as a counter electrode substrate and washed according to a conventional method.

Next, the glass substrate on which the resin material layer is formed as described above is opposed to the counter electrode substrate so that the distance between the ITO electrodes is in the range of 5 to 15 μm, and the peripheral portion is sealed with a sealing member. Liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected between the substrates, the inlet was sealed, and a liquid crystal cell for measurement was produced.
The liquid crystal used had a voltage holding ratio of 98% or more measured under the following voltage holding ratio measurement conditions in the measurement liquid crystal cell before the forced impurity extraction treatment.

(2) Impurity forced extraction treatment and measurement of voltage holding ratio The liquid crystal cell for measurement produced in (1) above is subjected to heat treatment (left in an oven at 105 ° C. for 2.5 hours) to the resin member layer Then, forced impurity extraction was performed.

Next, the liquid crystal cell for measurement subjected to the impurity forced extraction treatment as described above was returned to room temperature, the voltage holding ratio was measured under the following conditions, and the results are shown in Table 1 below.
(Voltage holding ratio measurement conditions)
・ Distance between ITO electrodes: 5 to 15 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec

<Production of color filter>
(1) Color filter sample 1
As a substrate for a color filter, a glass substrate (Corning 7059 glass) having a size of 100 mm × 100 mm and a thickness of 0.7 mm was prepared. After cleaning this substrate according to a standard method, a thin film of chromium (thickness 0.15 μm) is formed on the entire surface of one side of the substrate by sputtering, and a photosensitive resist is applied on the thin chromium film, mask exposure, development, and thin chromium film. Etching was performed to form a black matrix.

  Next, a colored layer was formed using the three types of photosensitive paints R1, G3, and B1 for the colored layer having the above composition. That is, a red pattern photosensitive paint R1 was applied to the entire surface of the substrate on which the black matrix was formed by spin coating to form a red photosensitive resin layer, and prebaked (90 ° C., 3 minutes). . Thereafter, the red photosensitive resin layer is alignment-exposed using a photomask for a predetermined colored pattern, developed with a developer (0.05% KOH aqueous solution), and then post-baked (200 ° C., 30 minutes). Then, a red pattern (thickness: 1.5 μm) was formed at a predetermined position with respect to the black matrix pattern.

Similarly, a green pattern (thickness: 1.5 μm) was formed at a predetermined position with respect to the black matrix pattern by using the photosensitive paint G3 for the green pattern. Further, a blue pattern (thickness: 1.5 μm) was formed at a predetermined position with respect to the black matrix pattern by using the photosensitive paint B1 for the blue pattern.
As a result, a color filter (sample 1) having a structure as shown in FIG. 1 was obtained. However, unlike the black matrix 14 of FIG. 1, the black matrix of this color filter is made of metallic chromium.

(2) Color filter sample 2
A color filter (Sample 2) was produced in the same manner as Sample 1 except that three types of photosensitive paints R1, G1, and B1 having the above compositions were used as the photosensitive paint for the colored layer.

(3) Color filter sample 3
A color filter (color filter) was prepared in the same manner as Sample 1 except that three types of photosensitive paints R2, G2, and B2 having the above-described composition were used as the photosensitive paint for the colored layer, and the post-baking conditions were set to 230 ° C. for 30 minutes. Sample 3) was prepared.

(4) Color filter sample 4
The resin protective layer coating material P1 having the above composition is applied by spin coating so as to cover the black matrix and the colored layer of the color filter (sample 1), dried and post-baked (200 ° C., 30 minutes). Thus, a protective layer having a thickness of 1.5 μm was formed to obtain a color filter (sample 4) having a structure as shown in FIG.

(5) Color filter sample 5
The resin protective layer coating material P2 having the above composition is applied by spin coating so as to cover the black matrix and the colored layer of the color filter (sample 1), dried, and post-baked (230 ° C., 30 minutes). Thus, a protective layer having a thickness of 1.5 μm was formed, and a color filter (sample 5) having a structure as shown in FIG. 4 was obtained.

(6) Color filter sample 6
The resin protective layer coating material P3 having the above composition is applied by spin coating so as to cover the black matrix and the colored layer of the color filter (sample 1), dried and post-baked (200 ° C., 30 minutes). Thus, a protective layer having a thickness of 1.5 μm was formed to obtain a color filter (sample 6) having a structure as shown in FIG.

(7) Color filter sample 7
The resin columnar convex photosensitive resin S1 having the above composition was applied by spin coating so as to cover the protective layer of the color filter (sample 5), and prebaked (100 ° C., 3 minutes). Thereafter, exposure is performed using a predetermined columnar convex photomask, development is performed with a developer (0.01% KOH aqueous solution), and then post-baking (200 ° C., 30 minutes) is performed, and the height is 5 μm. A plurality of columnar convex portions were formed to obtain a color filter (sample 7) having a structure as shown in FIG.

(8) Color filter sample 8
The color filter (sample 8) was the same as the sample 7 except that the resin photosensitive paint S2 having the above composition was used as the photosensitive paint for the resin columnar protrusions, and the post-baking conditions were 230 ° C. for 30 minutes. It was.

(9) Color filter sample 9
A color filter (sample 9) was prepared in the same manner as the sample 7 except that the resin photosensitive paint S3 having the above composition was used as the photosensitive paint for the resin columnar convex portions.

<Production of liquid crystal display device>
A transparent common electrode made of indium tin oxide (ITO) was formed on each of the color filters (samples 1 to 9).
Further, a glass substrate (Corning 7059 glass) having a size of 100 mm × 100 mm and a thickness of 0.7 mm was prepared as a transparent substrate. After this substrate is cleaned according to a standard method, thin film transistors (TFTs) are formed at a plurality of predetermined locations on the substrate, and transparent pixel electrodes are formed of indium tin oxide (ITO) so as to be connected to the drain electrodes of each TFT. Thus, a counter electrode substrate was produced.

Next, a polyimide resin paint was applied and dried to cover the transparent common electrode of the color filter and the transparent pixel electrode of the counter electrode substrate, and an alignment layer (thickness 0.07 μm) was provided to perform alignment treatment.
Next, liquid crystal display devices (Samples 1 to 9) were produced using these color filters and the counter electrode substrate. In addition, Merck Japan MLC-6846-000 was used as liquid crystal.

<Evaluation of liquid crystal display device>
About the produced nine types of liquid crystal display devices (samples 1 to 9), the following two types of display at high temperature and high humidity are performed for a long time, the display quality is evaluated according to the following criteria, and the results are shown in Table 2 below. It was.

(Image display conditions)
・ Continuous for 200 hours under conditions of 50 ° C. and 60% RH ・ Continuous for 500 hours under conditions of 80 ° C. and 60% RH

(Evaluation criteria for display quality)
○: Display quality is extremely good without image sticking and white unevenness ×: Image sticking and white unevenness are observed, and a display defect phenomenon is observed.

  As shown in Table 2, in each of the liquid crystal display devices of Samples 2 to 5, 7, and 8, the color filters constituting each of the liquid crystal display devices are in direct contact with the liquid crystal layer, or through an alignment layer or a transparent electrode. The resin member located in the vicinity of the liquid crystal layer is subjected to a forced impurity extraction process in contact with the liquid crystal, and the voltage applied to the liquid crystal through the resin member is maintained at 80% or more. Since it is a filter, even if image display is performed continuously for 200 hours under the conditions of 50 ° C. and 60% RH, a display defect phenomenon does not occur.

  In addition, each of the liquid crystal display devices of Samples 3, 5, and 8 is located at a position where the color filter constituting each is in direct contact with the liquid crystal layer, or in the vicinity of the liquid crystal layer via an alignment layer or a transparent electrode. Since the resin member is a color filter according to the present invention, which is subjected to a forced impurity extraction process in contact with the liquid crystal and maintains the holding ratio of the voltage applied to the liquid crystal through the resin member at 90% or more, more severe conditions Even when image display was performed at (80 ° C., 60% RH for 500 hours of continuous image display), display failure did not occur.

  In contrast, in the liquid crystal display device of sample 1, a green pattern having a voltage holding ratio of less than 80% is in direct contact with the liquid crystal layer. In the liquid crystal display device of sample 6, a resin having a voltage holding ratio of less than 80%. The protective layer is in direct contact with the liquid crystal layer. Further, in the liquid crystal display device of Sample 9, columnar protrusions having a voltage holding ratio of less than 80% are in direct contact with the liquid crystal layer. And a display failure phenomenon was observed.

  This is useful for manufacturing a liquid crystal display device excellent in display quality and a color filter used therefor.

It is a schematic sectional drawing which shows an example of the color filter used as the application object of the selection method of the resin member for color filters of this invention. It is a figure for demonstrating the structure of the liquid crystal cell for a measurement for performing an impurity forced extraction process and a voltage holding ratio measurement. It is a schematic sectional drawing which shows the other example of the color filter used as the application object of the selection method of the resin member for color filters of this invention. It is a schematic sectional drawing which shows the other example of the color filter used as the application object of the selection method of the resin member for color filters of this invention. It is a schematic sectional drawing which shows the other example of the color filter used as the application object of the selection method of the resin member for color filters of this invention.

Explanation of symbols

11, 11 ', 21, 21', 31 ... Color filter 12, 22, 32 ... Substrate 13 ... Resin colored layer 14, 14 ', 24, 34 ... Black matrix 15 ... Colored film 15' ... Resin colored layer 25, 35 ... Colored layer 26, 36 ... Transparent protective layer 37 ... Resin columnar convex part 50 ... Liquid crystal cell for measurement 53, 56 ... ITO electrode 57 ... Resin member layer 58 ... Liquid crystal

Claims (4)

A resin member constituting a color filter used in a liquid crystal display device, for forming a resin colored layer that can be the nearest position to the liquid crystal, a resin protective layer that covers the resin colored layer, and a resin columnar protrusion In the resin member selection method,
To form a resin member layer as a selection on the ITO electrode of one of the ITO substrate of a pair of ITO substrate having an electrode made of the surface of the glass substrate of indium tin oxide (ITO) target, then the distance between the ITO electrodes Both ITO substrates are made to face each other in a range of 5 to 15 μm , the periphery is sealed with a sealing member, and a liquid crystal cell for measurement is manufactured by enclosing liquid crystal between both ITO substrates. The resin member layer was subjected to a heat treatment by leaving it in an oven at 105 ° C. for 2.5 hours , and then returned to room temperature, and then the voltage holding ratio was measured under the following measurement conditions. A resin member having a measured voltage holding ratio of 90% or more is selected as a non-defective product, and the liquid crystal is a voltage measured by the measurement liquid crystal cell in a state before the forced impurity extraction treatment. Selection of the color filter resin member is characterized in that lifting rate is the liquid crystal is 95% or more.
(Measurement conditions of voltage holding ratio)
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec A method for producing a color filter, comprising: forming a resin coloring layer having a plurality of colors on a substrate in a predetermined pattern using a resin member selected as a non-defective product by the selection method according to claim 1 . A colored resin layer having a plurality of colors is formed on a substrate in a predetermined pattern, and then a transparent resin is used to cover at least the colored layer using a resin member selected as a non-defective product by the selection method according to claim 1. A method for producing a color filter, comprising forming a protective layer. The transparent resin columnar convex part is formed in a plurality of predetermined parts on the resin protective layer using the resin member selected as a non-defective product by the selection method according to claim 1. Manufacturing method of color filter.

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