JPH0629884B2 - Color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color filter, and more particularly to a color filter suitable as a fine color separation filter such as a color display, a color image pickup device and a color sensor. .

[Conventional technology]

As a conventional color filter, there is known a dye color filter in which a mordant layer made of a hydrophilic polymer such as gelatin, casein, glyu or polyvinyl alcohol is provided on a substrate, and the mordant layer is dyed with a dye to form a colored layer. Has been.

In such a dyeing method, there are many dyes that can be used, and it is relatively easy to respond to the spectral characteristics required of a filter, but in the dyeing step of the mordant layer, the mordant layer is formed in a dye bath in which the dye is dissolved. It employs a wet process that is difficult to control, such as dipping, and it has a drawback that the yield is poor because it has a complicated process such as providing an intermediate layer for dye protection for each color. The heat resistance of dyeable dyes is 15
It is relatively low at about 0 ° C. or less, and when the filter requires thermal treatment, it is difficult to use and also has a drawback that the dyeing film itself has poor reliability such as heat resistance and light resistance. ing.

As a color filter capable of eliminating the above-mentioned drawbacks, there has been proposed a color filter using a colored resin in which a certain kind of coloring material is dispersed in a transparent resin. This color filter is disclosed, for example, in JP-A-58-46325 and JP-A-6-46325.
0-78401, JP-A-60-184202, JP-A-60-
184203, JP-A-60-184204, JP-A-60-18
4205, JP 57-16407, JP 57-74707
JP-A No. 60-129707 and Japanese Unexamined Patent Publication No. 60-129707 have made it possible to provide a color filter having improved heat resistance and light resistance.

[Problems to be solved by the invention]

When the color filter formed by dispersing and containing the above-mentioned coloring material, particularly a pigment in a resin is applied as a fine color separation filter, the color filter is fine (eg, 10 ⁵ μm ² or less) on a glass substrate. The blue resin layer, the green resin layer and the red resin layer are arranged in a mosaic pattern or a stripe pattern.

When a color filter for color separation in which such a pigment is dispersed is applied to a color liquid crystal display screen, when the observer's viewing angle with respect to the display screen changes, the color balance of blue, green and red on the display screen changes. It has been found. In particular, it was found that as the viewing angle with respect to the vertical axis of the display screen was increased, the ratio of the green component and the red component was decreased in order, and the color tone was bluish as a whole.

Therefore, an object of the present invention is to provide a novel color filter that solves the above-mentioned problems, and in particular to provide a color separation filter applicable to a color liquid crystal display screen, a solid-state image sensor and an image sensor. is there.

[Means for Solving Problems] and [Function] The present invention includes a blue resin layer containing a blue coloring material dispersed therein, a green resin layer containing a green coloring material dispersed therein, and a red coloring material dispersedly contained on a substrate. In a color filter having a red resin layer, the average of the blue coloring material (particularly blue pigment), the green coloring material (particularly green pigment) and the red coloring material (particularly red pigment) is calculated. And when Between It is characterized by having the relationship of. That is, the present invention is To By so doing, the scattering efficiencies of the blue resin layer, the green resin layer, and the red resin layer with respect to the incident light can be made uniform. As a result, even when the viewing angle of the observer with respect to the display screen changes, the display screen can be changed. It is possible to prevent the fluctuation of the color balance of blue, green and red in, and it is possible to display a high quality color screen.

Further, the color filter of the present invention has mechanical properties, heat resistance,
Since it is formed of a resin system having good durability such as light resistance and solvent resistance and a colored resin layer using a pigment as a coloring material,
Since it has excellent characteristics of reliability, it is possible to easily design an excellent color filter, and it is possible to form a fine pattern by a simple method such as a general printing process or a photorin process. .

Blue (B), green (G), red (R) dispersed in the resin of the present invention
The average particle size (diameter) of the color pigment particles can be converted by the average volume of the pigment, and the average volume of the blue pigment can be calculated as The average volume of green pigment The average volume of the red pigment Then, The ratio of Is set to 1.0, (0.4 to 0.6): (0.6 to 0.8): 1.0 is preferable.

The average particle size of the pigment particles used in the present invention is, in terms of average volume, generally 1.0 × 10 ⁻⁶ μm ^{3 to} 1.0 × 10 ⁻² μm ³ , preferably 1.0 × 10 ⁻⁵ μm ^3. There is.

The size of the pigment particles here can be evaluated by an optical microscope or SEM analysis of the colored resin layer.

The simplest method is to observe under an optical microscope and evaluate the average value of about 100 particles of each color.

In the present invention, as a method for setting the size of the pigment particles in the resin to a predetermined size, a pigment having a surface treatment agent coated on the pigment is passed through a sieve, and a pigment having a desired size is prepared in a resin solution. After being mixed and sufficiently dispersed by ultrasonic waves or three rolls, a color filter is formed.

After the pigment is blended in the resin solution and sufficiently dispersed by ultrasonic waves or three rolls, it is filtered several times with a filter such as filter paper to obtain a colored resin of an appropriate size,
The resin is formed as a color filter.

There is a method such as.

In the present invention, blue means a color tone having a peak of transmitted light in the wavelength range of 400 to 500 μm, green means a tone having a peak of transmitted light amount in the wavelength range of 500 to 600 μm, and red means a wavelength of 600-7.
A color tone that has a peak of transmitted light in the range of 00 μm.

As the resin forming the colored resin layer constituting the color filter of the present invention, a cured film is obtained at 300 ° C. or lower,
For example, acrylic resin, polyamino resin (polyimide resin, polyamide resin), epoxy resin, urethane resin, polycarbonate resin, silicon resin, etc., which have specific light absorption characteristics especially in the visible light wavelength range (400 to 700 nm). Those that do not have (light transmittance of about 90% or more) are preferable.

Examples of the acrylic resin include JMC-25 manufactured by Japan Synthetic Rubber Co., Ltd. and RFG-10 manufactured by Sekisui Fine Chemical Co., Ltd.

To impart photosensitivity to the resin, a group having photosensitivity may be included in the molecule.

The photosensitive group in the present invention may be an aromatic chain having a photosensitive hydrocarbon unsaturated group as shown below, for example, (1) benzoic acid esters (In the formula, R ₁ is CHX = CY-COO-Z-, X is -H or -C ₆ H ₅ , Y is H or -CH ₃ , Z is-or an ethyl group or a glycidyl group.) (2) Benzyl Acrylates (Wherein Y represents -H or CH ₃ ) (3) Diphenyl ethers (In the formula, R ₂ is CHX = CY-CONH-, CH ₂ = CY.
-COO- _{(CH 2) 2} -OCO- or _CH 2 = CY-
COO-CH ₂ - which the containing 1 Ke or more, X, Y are synonymous. ) (4) Chalcones and other compound chains (In the formula, R ₃ represents H-, an alkyl group or an alkoxy group) Etc.

Specific examples of aromatic polyamide resins and polyimide resins having these groups in the molecule are lysocoat PA-10.
Examples include 00 (manufactured by Ube Industries, Ltd.) and Lithocoat PI-400 (manufactured by Ube Industries, Ltd.).

Generally, the photosensitive resins used in the photolithography process have excellent durability such as mechanical properties, heat resistance, light resistance, and solvent resistance, although there are differences depending on their chemical structures. On the other hand, the above-mentioned photosensitive polyamino resin of the present invention is a resin system having excellent durability in terms of chemical structure as well, and the color filter formed by using them also has very good durability. Becomes

The coloring material forming the colored resin layer of the color filter of the present invention is not particularly limited as long as it can obtain desired spectral characteristics among organic pigments, inorganic pigments, dyes and the like. In this case, each material can be used alone or as a mixture of some of them. However, when a dye is used, the performance of the color filter is governed by the durability of the dye itself.However, when the resin system of the present invention is used, a product having excellent performance is formed as compared with a normal dyed color filter. It is possible. Therefore, the organic pigment is most preferable as the coloring material in consideration of the color characteristics and various performances of the color filter. These pigments can be dispersed and contained in the resin in the range of 10% by weight to 70% by weight, preferably 30% by weight to 50% by weight.

The organic pigments include azo pigments such as soluble azo pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments,
And a condensed polycyclic pigment containing isodigo-based, anthraquinone-based, perylene-based, perinone-based, dioxazine-based, quinacridone-based, isoindolinone-based, phthalone-based, methine / azomethine-based, other metal complex-based pigments, or some of these A mixture of these is used. Further, in the present invention, a dye may be used as the colorant in addition to the above-mentioned pigment.

In the present invention, the coloring resin used to form the coloring resin layer is, for example, 10% by weight of the above-mentioned coloring material having the desired spectral characteristics in the photosensitive polyamino resin solution.
It is mixed at a ratio of about 50% by weight and sufficiently dispersed by ultrasonic waves or a three-roll mill, and then the one having a large particle size is removed by a filter to prepare.

The colored resin layer of the color filter of the present invention is formed by applying the colored resin on a substrate with a coating device such as a spinner or a roll coater, and forming it in a pattern by a photolithography process, the layer thickness of which has a desired spectral characteristic. However, it is usually about 0.5 to 5 μm, preferably 1 to 5 μm.
About 2 μm is desirable.

Although the colored resin layer of the color filter of the present invention is composed of a good material having sufficient durability itself, in particular, in order to protect the colored resin layer from various environmental conditions, On the surface of the colored resin layer, organic resin such as polyamide, polyimide, polyurethane, polycarbonate, silicon-based resin, Si ₃ N ₄ , SiO ₂ , Al ₂ O ₃ , Ta ₂ O ₃
Inorganic film such as spin coating, roll coating method,
Alternatively, it can be provided as a protective layer by a vapor deposition method. Further, after forming the protective layer, depending on the material, an alignment treatment may be performed to make it applicable to a device using liquid crystal. The thickness of this protective layer is generally 50
It is preferable to set it in the range of about 00Å to 2 μm.

The color filter having the colored resin layer as described above can be formed on an appropriate substrate. For example, a glass plate, a transparent resin plate, a resin film, or a cathode ray tube display surface, a light receiving surface of an image pickup tube, a wafer on which a solid-state image pickup device such as CCD, BBD, CID, or BASIS is formed, or a contact-type image sensor using a thin film semiconductor. , Liquid crystal display surfaces, color electrophotographic photoconductors, and the like.

If it is necessary to further increase the adhesion between the colored resin layer and the underlying substrate, either apply a thin coating of a silane coupling agent or the like on the substrate beforehand to form the colored resin pattern, or It is more effective to form a color filter by using a material to which a small amount of a silane coupling agent or the like is added.

Hereinafter, a typical method of forming a color filter of the present invention will be described with reference to the drawings.

FIG. 1 is a process diagram illustrating a method for forming a color filter using the photosensitive colored resin of the present invention. First, as shown in FIG. 1 (a), using a polyamino resin solution (NMP solution) in which a predetermined amount of a coloring material having desired spectral characteristics is blended,
The colored resin film 2 of the first color is applied and formed on a predetermined substrate 1 using a spinner so as to have a predetermined film thickness, and prebaked under appropriate temperature conditions. Then, as shown in FIG. 1 (b), light having the sensitivity of the photosensitive coloring resin (for example,
The colored resin film is exposed with a high-pressure mercury lamp or the like) through the photomask 3 having a predetermined pattern shape corresponding to the pattern to be formed, and the pattern portion is photocured.

Then, as shown in FIG. 1 (c), the colored resin film 2 having the photo-cured portion 2a is dissolved in a solution that dissolves only the unexposed portion (for example, one containing N-methyl-2-pyrrolidone-based solvent as a main component). ) Ultrasonic wave development, and then rinse treatment (for example,
1,1,1, trichloroethane, etc.). Then, post-baking treatment is performed to obtain the patterned colored resin layer 4 of the present invention as shown in FIG. 1 (d).

In the case of forming a color filter of the present invention having two or more colors, it is further necessary, that is, depending on the number of colors of the filter to be used, from FIG. 1 (a) to FIG.
The steps up to (d) are repeated by using the colored resin liquids in which the coloring materials corresponding to the respective colors are dispersed in the particle size according to the present invention, for example, different colors as shown in FIG. 1 (e). It is possible to form a color filter composed of three colors of the patterned colored resin layers 4, 5 and 6.

Further, the color filter of the present invention may have a protective layer 7 formed of the above-mentioned materials on the upper part of the filter as shown in FIG. 1 (f).

The color filter of the present invention can be applied to a substrate that constitutes a liquid crystal cell. FIG. 3 is a sectional view of a liquid crystal cell using the color filter of the present invention. The liquid crystal cell shown in FIG. 3 includes a pair of upper and lower substrates 31a and 31b arranged in parallel, and transparent electrodes 32a wired to the respective substrates.
It has 32b. A ferroelectric liquid crystal, preferably a non-helical ferroelectric liquid crystal 33 having at least two stable states, is arranged between the upper substrate 31a and the lower substrate 31b.

It is preferable that the transparent electrodes 32a and 32b described above are wired in stripes and are arranged such that the stripes intersect each other in order to drive the ferroelectric liquid crystal 33 by multiplexing.

In the liquid crystal cell shown in FIG. 3, orientation control films 34a and 34b are arranged on substrates 31a and 31b, respectively. This orientation control film 34
As a and 34b, a rubbing-treated polyimide film, polyvinyl alcohol film, polyamide film, or the like can be used, and also an oblique vapor deposition film of SiO or SiO ₂ can be used.

A color filter 35 formed by arranging the blue resin layer 35B, the green resin layer 35G and the red resin layer 35R in a stripe shape or a mosaic shape is provided on the lower substrate 31b. Above the color filter 35, a protective layer 36 similar to the above-mentioned protective layer 7 is provided.

In another preferred embodiment of the present invention, the transparent electrode 32b shown in FIG. 3 is formed in contact with the lower substrate 31b, and the color filter 35 and the alignment control film 34b described above may be sequentially laminated on the transparent electrode 32b. . At this time, the protective layer 36 may be omitted, but the ferroelectric liquid crystal 33 has a film thickness (for example, 0.5 μm to 10 μm) that eliminates the helical structure of the chiral smectic C liquid crystal when no electric field is applied. In the case of using the chiral smectic C liquid crystal set to, transparent electrodes 32a and 32b
The protective layer 36 is preferably used by functioning as an insulating layer in order to prevent short-circuiting.

A liquid crystal-electro-optical device having a matrix electrode structure using a ferroelectric liquid crystal of this kind has been proposed by Clark and Lagabal in US Pat. No. 4,367,924.

Ferroelectric liquid crystals that can be used in a liquid crystal device incorporating the color filter of the present invention include, for example, p-decyloxybenzylidene-p'-amino-2-methylbutylcinnamate (DOBAMBC), p-hexyloxybenzylidene- p'-amino-2-chloropropyl cinnamate (HOB
ACPC), p-decyloxybenzylidene-p'-amino-
2-methylbutyl-α-cyanocinnamate (DOBAMBCC),
p-tetradecyloxybenzylidene-p'amino-2-
Methylbutyl-d-cyanocinnamate (TDOBAMBCC),
p-octyloxybenzylidene-p'-amino-2-
Methylbutyl-α-chlorocinnamate (OOBAMBCC), p
-Octyloxybenzylidene-p'-amino-2-methylbutyl-α-methylcinnamate, 4,4'-azoxycinnamamide-bis (2-methylbutyl) ester, 4-o- (2-methyl) butyl Resorsilidene-4'-octylalinine, 4- (2'-methylbutyl) phenyl-4'-octylyloxybiphenyl-4
-Carboxylate, 4-hexyloxyphenyl-4
(2 "-methylbutyl) biphenyl-4'-carboxylate, 4-octyloxyphenyl-4- (2" -methylbutyl) biphenyl-4'-carboxylate, 4
-Heptylphenyl-4- (4 "-methylhexyl) biphenyl-4'-carboxylate, 4- (2" methylbutyl) phenyl-4- (4 "methylhexyl) biphenyl-4'-carboxylate and the like. These may be used alone or in combination of two or more, and may contain other cholesteric liquid crystals or smectic liquid crystals in a range showing ferroelectricity.

〔Example〕

 Examples of the present invention will be shown below.

Example 1 A blue colored resin material [Heliogen Blue L70] capable of obtaining desired spectral characteristics on a glass substrate.
80 (trade name, manufactured by BASF, CI No. 74160) is PA-1000 (trade name, manufactured by Ube Industries, polymer content 10%, solvent = N-methyl-2-pyrrolidone, pigment: polymer = 1: 2 blended) The photosensitive pigmented resin material prepared by dispersing the pigment in the solution was passed through a filter filter (Men Brown filter SM113, manufactured by Calz Ice Co., Ltd.) twice, and the particle diameter of the dispersed pigment was about 0.060 μm (diameter).
I chose the ones. In this selection, first, a filter having a size slightly larger than the desired particle size was passed through, and then a filter having a size smaller than the desired particle size was passed through to select particles having a predetermined size. The colored resin material in which the pigment was dispersed in this manner was applied to a film thickness of 2.0 μm by a spinner application method. Next, the colored resin layer was prebaked at 80 ° C. for 30 minutes, and then exposed with a high pressure mercury lamp through a pattern mask corresponding to the pattern shape to be formed. After completion of the exposure, development is carried out using ultrasonic waves with a dedicated developing solution (developing solution containing N-methyl-2-pyrrolidone as a main component) that dissolves only the unexposed portion of the colored resin film, and a dedicated rinsing solution ( After treatment with a rinse liquid containing 1,1,1, trichloroethane as a main component, post-baking was performed at 150 ° C. for 30 minutes to form a blue colored resin film having a pattern shape.

This blue colored resin film was randomly selected 100 with an optical microscope, and the average particle size was measured.The average volume of the blue pigment in the resin was about 1.1 × 10 ^-4 μm ³ . It was dispersed evenly.

Subsequently, a green colored resin material [Lionol Green 6YK (trade name, manufactured by Toyo Ink Co., C.
I.No.74265) was dispersed in PA-1000 (trade name, manufactured by Ube Industries, Ltd., polymer content 10%, solvent = N-methyl-2-pyrrolidone, pigment: polymer = 1: 2 blended) to make it photosensitive. [Coloring resin material] through a filter filter in the same manner as described above, and the particle diameter of the dispersed pigment is about 0.066 μm (diameter).
A green colored pattern was formed at a predetermined position on the substrate in the same manner as above except that the above-mentioned one was selected. When the average volume was measured by the same method as described above, in the green coloring resin thus formed, the green pigment was about 1.5 × 10 ⁻⁴ μm ³
Were evenly dispersed in the average volume of.

Furthermore, as a third color, a red colored resin material [Irgazin Red BPT (trade name, manufactured by Ciba-Geigy, CINo .71127) is dispersed in PA-1000 (trade name, manufactured by Ube Industries, Ltd., polymer content 10%, solvent = N-methyl-2-pyrrolidone, pigment: polymer = 1: 2 blend) to prepare a photosensitive colored resin. Material) through a filter filter in the same manner as above using a pigment having a particle size of about 0.076 μm (diameter), which was selected in the same manner as above except that a red colored pattern was formed on the substrate. Formed in position. When the average volume was measured by the same method as described above, the red pigment was uniformly dispersed in the red colored resin in a volume of about 2.3 × 10 ⁻⁴ μm ³ . R as described above
A colored pattern of three-color stripes of (red), G (green) and B (blue) was obtained.

The spectral characteristics of the two-color filter thus formed are shown in FIG.

The scattering light of the obtained color filter is integrated sphere (made by Hitachi
210-2101), the scattering rate for each color of blue, green and red was about 0.5%, which was about the same as the scattering rate (scattering rate is the amount of scattered light relative to the amount of incident light). Expressed as a percentage).

The viewing angle dependence of the color filter obtained above was measured by changing the observation angle with respect to the vertical axis of the color filter. As a result, the color balance when observed at a position where the observation angle to the vertical axis of the color filter is around 70 ° and the color balance when observed at the vertical axis position of the color filter are almost the same. found.

The obtained color filter has excellent heat resistance and can withstand a temperature of 250 ° C. or higher, which makes it possible to form ITO (indium-tein-oxide) used as a transparent electrode on the color filter with a spatula.

Further, the color filter of this example had high hardness and excellent mechanical properties, and even when the color filter was configured so as to be in contact with the spacer in the liquid crystal cell, the color filter was not damaged during pressure bonding. Furthermore, the color filter of this example has excellent solvent resistance, and is strong against each solvent after curing,
It did not change during each production process, and was also excellent in light resistance.

Comparative Example 1 Except that the average particle size of each of the blue pigment, green pigment and red pigment used in Example 1 was set to 1.5 × 10 ⁻⁴ μm ³ in terms of average volume, the same method as in Example 1 was used. A color filter was prepared. When the scattering rate of each color of blue, green and red in this comparative color filter was measured by the same method as in Example 1, blue light (400 to 500 nm) and green light (5
(00-600 nm) and red light (600-700 nm) have scattering rates of about
It was 1.0%, about 0.5% and about 0.3.

The viewing angle dependence of this comparative color filter was measured by the same method as in Example 1. As a result, the color filter gradually exhibited a bluish color tone from a position where the observation angle with respect to the vertical axis exceeded 30 °. It was

Example 2 Using a thin film transistor as a substrate, the color filter of the present invention was formed on the substrate to prepare a color liquid crystal display device as follows.

First, as shown in FIG. 4 (a), a glass substrate (product name: 705
9 Corning) 41 ITO pixel electrode with a layer thickness of 1000Å 42
After forming a desired pattern by the phototriso process,
Aluminum is further vacuum-deposited on this surface in a layer thickness of 1000Å, and this vapor-deposited layer is patterned into a desired shape by a photolithography process to form a gate electrode 43 as shown in FIG. 4 (b).
Was formed.

Next, photosensitive polyimide (trade name: semi-coffin,
Toray Co., Ltd.) is applied to the surface of the substrate 41 on which the electrodes 42 and 43 are provided to form an insulating layer 44, and a through hole that forms a contact portion between the drain electrode 45 and the pixel electrode 42 by pattern exposure and development processing. 46 was formed as shown in FIG. 4 (c).

Here, the substrate 41 is set at a predetermined position in the deposition tank, SiH ₄ diluted with H ₂ is introduced into the deposition tank, and the electrodes 42 and 43 and the insulating layer 44 are formed by a glow discharge method in vacuum. After depositing a photoconductive layer (intrinsic layer) 47 made of a-Si having a layer thickness of 2000 Å on the entire surface of the substrate 41 provided with, a 1000 Å layer is formed on the photoconductive layer 47 by the same operation. Thick n ⁺
Layer 48 was laminated as shown in Figure 4 (d). This board 41
Then, the n ⁺ layer 48 and the photoconductive layer 47 were patterned in this order into a desired shape by a dry etching method as shown in FIG. 4 (e).

Next, Al is vacuum-deposited on the surface of the substrate 41 on which the photoconductive layer 47 and the n ⁺ layer 48 are provided in this manner with a layer thickness of 1000 Å, and this Al vapor deposition layer is patterned into a desired shape by a photolithography process. Then, the source electrode 49 and the drain electrode 45 as shown in FIG. 4 (f) were formed.

Finally, a color filter 35 is formed corresponding to each of the pixel electrodes 42 in the same manner as in Embodiment 1 as shown in FIG. 4 (g), and then, as shown in FIG. 4 (h), the substrate 41 surface is formed. A polyimide resin as an insulating film 40 having an orientation function applied to the entire surface is applied to a layer thickness of 1200 Å, and the resin is cured by heat treatment at 250 ° C. for 1 hour to manufacture a thin film transistor in which a color filter 35 is integrated. .

A liquid crystal display element for an arm was further formed by using the thin film transistor with the color filter 35 thus produced.

That is, a glass substrate (trade name: 7059, manufactured by Corning) is attached to one side of the ITO of 1000 Å in the same manner as the above method.
An electrode layer is formed, and an insulating layer having a layer thickness of 1200 Å made of a polyimide resin having an orientation function is further formed on the electrode layer,
Twisted nematic liquid crystal (ZLI123; product name, manufactured by Merck & Co., Inc.) was sealed between the substrate and the thin film transistor with a color filter formed previously, and the whole was fixed to obtain a liquid crystal display device for color.

The color liquid crystal display element formed in this manner had a function of good display quality.

Example 3 Instead of providing a three-color filter on the pixel electrode,
A color liquid crystal display device having the color filter of the present invention was obtained in the same manner as in Example 2 except that it was provided on the counter electrode.

The color liquid crystal display element formed in this manner has a function of good display quality.

Example 4 A color liquid crystal display device having a color filter of the present invention was obtained in the same manner as in Example 2 except that a three-color filter was first formed on a counter substrate and then a counter electrode was provided.

The color liquid crystal display element formed in this manner had a function of good display quality.

Example 5 A wafer on which a CCD (charge, coupled, device) is formed is used as a substrate, and three-color stripe color is arranged so that each colored pattern of the color filter is arranged corresponding to each light receiving cell of the CCD. A color solid-state image sensor having the color filter of the present invention was formed in the same manner as in Example 1 except that the filter was formed.

The color solid-state image pickup element formed in this manner had no flare and had a good function of the color characteristics of the sensor.

Example 6 The color filter formed in Example 1 is arranged on a wafer on which a CCD (charge, coupled, device) is formed, and each colored pattern of the color filter is arranged in correspondence with each light receiving cell of the CCD. The color solid-state imaging device was formed by aligning and sticking as described above.

The Kerr solid-state image pickup device thus formed had no flare and had a good function of the color characteristics of the sensor.

Example 7 A color photosensor array having a color filter of the present invention as shown in the partial plan schematic view of FIG. 5 was formed according to the steps shown in FIG. 6 as follows.

First, glass substrate (Product name: 7059, Corning) 61
A photoconductive layer (intrinsic layer) 62 consisting of an a-Si (amorphous silicon) layer was provided on the above by a glow discharge method as shown in FIG. 6 (a).

That is, SiH ₄ diluted with H ₂ to 10% by volume is used for gas pressure 0.50.
Torr, RF (Radio Frequency) power 10W, substrate temperature 250 ℃
The photoconductive layer 62 having a thickness of 0.7 μm was obtained by depositing it on the substrate for 2 hours.

Then, on the photoconductive layer 62, as shown in FIG.
An n ⁺ layer 63 was provided as shown in (b).

That is, SiH ₄ diluted to 10% by volume with H ₂ and 100 p with H ₂ .
A gas of 1:10 mixed with PH ₃ diluted to pm is used as a raw material, and the other conditions are the same as the deposition conditions of the photoconductive layer 62 above. Thick n ⁺ layer 63
Was set up.

Next, as shown in FIG. 6 (c), Al is formed by electron beam evaporation.
Was deposited on the n ⁺ layer 63 with a layer thickness of 0.3 μm to deposit the conductive layer 64. Subsequently, as shown in FIG. 6 (d), a portion of the conductive layer 64 corresponding to the portion to be the light conversion portion was removed.

That is, after forming a photoresist pattern in a desired shape using a positive-type microposit 1300-27 (trade name, manufactured by Shipley) photoresist, phosphoric acid (85% by volume aqueous solution), nitric acid (60% by volume) Aqueous solution), glacial acetic acid and water in a ratio of 16: 1: 2: 1 to remove the conductive layer 64 on the exposed portion (the portion where the resist pattern is not provided) from the substrate by using an etching solution to form a common electrode. 65 and individual electrodes 66 are formed.

Next, as shown in FIG. 6 (e), the n ⁺ layer 63 in the portion to be the light conversion portion was removed.

That is, after peeling off the microposite 1300-27 photoresist from the substrate, a parallel plate type plasma etching apparatus DEM-451 (manufactured by Nichiden Anerva Co., Ltd.) was used with a plasma etching method) at RF power 120 W and gas pressure 0.1 Torr. CF ₄
Dry etching with gas is performed for 5 minutes, and n ⁺
Part of the surface layers of layer 63 and photoconductive layer 64 were removed from the substrate.

In this embodiment, in order to prevent the implantation of the cathode material of the etching apparatus, a polysilicon target for the sputtering (8 inches, purity) is formed on the cathode.
99.999%), the sample was placed on it, and the part of the cathode material where SUS was exposed was covered with a Teflon sheet cut out in a donut shape, and etching was performed while the SUS surface was hardly exposed to plasma. Then add 3 nitrogen
Heat treatment was carried out at 20 ° C. for 60 minutes in an oven that was flowed at a speed of / min.

Next, a protective layer 67 was formed on the surface of the photosensor array thus prepared as follows.

That is, a silicon nitride layer as the protective layer 67 was formed on the photo sensor array by the glow discharge method.

That is, using a mixed gas in which SiH ₄ diluted with H ₂ at 10% by volume and 100% NH ₃ were mixed at a flow rate ratio of 1: 4, other than the same as in forming the a-Si layer. , A protective layer 67 made of a silicon nitride (a-SiNH) layer having a layer thickness of 0.5 μm
Was formed as shown in FIG. 6 (f).

Further, using this protective layer 67 as a substrate, a color filter 35 consisting of three colored patterns of blue, green and red is formed in the same manner as in Example 1, and as shown in FIG. A color photosensor array was formed in which colored filters were arranged on the respective surfaces.

The color photosensor array formed in this example also had no flare and had a good color characteristic.

Example 8 The color filter formed in Example 1 was attached to the photosensor array formed in Example 7 with an adhesive to form a color photosensor array.

The color photo sensor formed in this example also had a good function as in the case formed in Example 7.

〔The invention's effect〕

According to the present invention, a colored resin material obtained by dispersing a pigment in a resin having a photosensitive group in the molecule or having no photosensitive group is used, and the pigment particles in the dispersion are dispersed in the resin. Since the blue pigment, the green pigment, and the red pigment are formed in the order of magnitude of the average value to have the patterned colored resin layer, the following effects can be obtained.

That is, since the scattering intensity scattered from the color filter has almost the same value for each color of blue, green, and red, it is possible to eliminate the viewing angle dependence of the color balance, and the display quality of the display element is significantly improved. It will improve. Also in the sensor element, the color characteristics are improved for the same reason.

Further, according to the present invention, the mechanical strength is excellent, and the heat resistance,
The color filter having a fine pattern excellent in various properties such as light resistance and solvent resistance can be easily manufactured by using a colored resin material and a simple manufacturing process.

Therefore, it is possible to apply to a wide variety of devices that require a color filter with good performance, and it is possible to produce a color device with excellent characteristics.

Further, according to the present invention, it is possible to easily design desired spectral characteristics by controlling the concentration of the colorant in the colored resin and the thickness of the colored resin layer.

[Brief description of drawings]

1 (a) to 1 (f) are process drawings for explaining a method for forming a color filter of the present invention, and FIG. 2 is a colored resin layer of the color filter of the present invention obtained in Example 1. FIG. 3 is a cross-sectional view of a liquid crystal cell using the color filter of the present invention, and FIGS. 4 (a) to 4 (h) are liquid crystal display devices for color having the color filter of the present invention. FIG. 5 is a schematic plan partial view of a color photo sensor array having a color filter of the present invention.
FIGS. 6A to 6G are process diagrams of forming the color photo sensor array shown in FIG.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tatsuo Murata 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Miki Tamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. (56) References JP-A-60-129738 (JP, A)

Claims (17)

[Claims] 1. A color filter having a blue resin layer containing a dispersed blue colorant, a green resin layer containing a dispersed green colorant, and a red resin layer containing a red colorant dispersed on a substrate, wherein the blue The average volume of coloring material, green coloring material and red coloring material, respectively And when A color filter characterized by having the following relationship. 2. The color filter according to claim 1, wherein the resin layer is a layer obtained by forming a film from a resin having a photosensitive group in the molecule. 3. The above Between The color filter according to claim 1, which has the following relationship. 4. The above Are 1.0 × 10 ⁻⁶ μm ^{3 to} 1.0 × 10 ⁻² μm ^{3 respectively} , and the color filter according to claim 1. 5. The above Are 1.0 × 10 ⁻⁵ μm ^{3 to} 1.0 × 10 ⁻³ μm ^{3 respectively} , and the color filter according to claim 1. 6. The colorant in the resin is 10% by weight to 70% by weight.
The color filter according to claim 1, wherein the color filter is dispersed and contained in the following ratio. 7. The coloring material is 30% by weight to 50% by weight in the resin.
The color filter according to claim 1, wherein the color filter is dispersed and contained in the following ratio. 8. The color filter according to claim 1, wherein the coloring material is an organic pigment. 9. The color filter according to claim 1 or 2, wherein the resin layer is a layer formed of a photosensitive polyamino resin. 10. The color filter according to claim 1, wherein a protective layer is provided on the blue resin layer, the green resin layer and the red resin layer. 11. The color filter according to claim 10, wherein a transparent electrode is provided on the protective layer. 12. A transparent electrode is provided on the blue resin layer, the green resin layer and the red resin layer.
The color filter described in the item. 13. The color filter according to claim 1, wherein a transparent electrode is provided between the blue resin layer, the green resin layer, the red resin layer and the substrate. 14. The color filter according to claim 1, wherein an alignment control film in contact with the liquid crystal is provided above the blue resin layer, the green resin layer and the red resin layer. 15. The color filter according to claim 14, wherein the liquid crystal is a ferroelectric liquid crystal. 16. The color filter according to claim 15, wherein the ferroelectric liquid crystal is a chiral smectic liquid crystal. 17. The color filter according to claim 14, wherein the liquid crystal is a twisted nematic liquid crystal.