JPS6042706A - Color filter - Google Patents

Abstract

PURPOSE:To complement the spectral characteristics of phthalocyanine type dye and to obtain a color filter having a superior green dye layer and superior in resistances to light, solvents, etc. by using a combination of the phthalocyanine type dye and an isoindolinone type dye to form a green dye layer. CONSTITUTION:A green dye layer is formed by vapor depositing a combination of a phthalocyanine type green dye and a yellow dye of isoindolinones represented by the formula shown here in which R is a divalent org. group, such as phenylene. For instance, a resist pattern 2 is formed on a transparent base plate 1 by using a positive type resist, then a Pb phthlocyanine dye film is formed by vacuum evaporation, and an isoindolinone dye film is likewise laminated to form the green dye film 3. The green dye film pattern 4 is formed by removing the resist pattern 2 together with the dye film 3 overlaid on it. Then, necessary other dye films 5, 6 are successively formed likewise, and a protective layer is formed by using a proper resin 7. The filter thus obtained has superior green spectral characteristics and superior durability, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color filter, and particularly to a color filter for fine color separation in color image pickup devices, color sensors, color displays, and the like.

As a color filter, a dyed color filter is known, in which a mordant layer made of a hydrophilic polymer material such as gelatin, casein, grue, or polyvinyl alcohol is provided on a substrate, and the mordant layer is dyed with a dye to form a colored layer. ing. With this type of dyeing method, many dyes can be used, and it is relatively easy to meet the spectral characteristics required for filters. Moreover, because it involves a complicated process of providing an interlayer for resist dyeing for each color, the yield is poor and there is always a point. Furthermore, it has a relatively low heat resistance of about 150 to 16 Q'00, making it difficult to use in processes that require thermal treatment.

On the other hand, a vapor deposition method is known in which a thin film of dye or pigment is formed by a vapor deposition method such as vapor deposition (Special Japanese Patent No. 55-14
6406 etc.). According to this method, a colored layer can be formed on the dye, so it can be made thinner than the dyeing method, and it is a non-aqueous process and can be easily controlled. It also has the feature of good heat resistance. However, it has not been widely used until now because it is not easy to select a usable dye suitable for vapor deposition.

When looking at color filters from the perspective of dyes, dyes for color filters are required to have the following properties. First of all, it must have appropriate spectral characteristics as a filter.

On the other hand, from a manufacturing method point of view, even if the spectral characteristics are good, there is a lack of manufacturing stability, and dyes that require special processing steps lead to a decrease in yield, making them unsuitable for color filters. Put it away.

Therefore, as a dye for color filters, the spectral characteristics and
! ! ! You must choose the best one that is well-balanced from both aspects of your legacy.

In particular, the vapor deposition method has many advantages over the dyeing method because it is heat resistant, can be easily evaporated, and can withstand solvent treatment for about 700 ml. However, vapor-deposited color filters were not widespread.

By the way, the characteristics required for the dye used in vapor-deposited filters are those that can be vapor-deposited and that are determined by the resist after vapor-deposition.
The 7-thalocyanine dyes can be cited as dyes that relatively satisfies these characteristics, as they are resistant to solvent and heat treatment in the Otolithic process and have well-balanced spectral characteristics as a filter. Phthalocyanine dyes have excellent vapor deposition properties and solvent resistance because the basic phthalocyanine ring is chemically and thermally stable.

However, in terms of spectral characteristics, phthalocyanine dyes range from blue to green, and many exhibit blue or cyan characteristics. Depending on the central metal or substituent, it may exhibit characteristics close to green, but it is generally on the blue side, so it is not sufficient to be viewed strictly as green.

Therefore, the main object of the present invention is to provide a vapor-deposited color filter that takes advantage of the excellent vapor deposition properties and solvent resistance of these seven talocyanines and compensates for their disadvantageous spectral properties. be.

The color filter according to the present invention is characterized by having a green pigment layer formed by vapor-depositing a heptalocyanine pigment and an isoindolinone pigment. That is, in the present invention, by using an isoindolinone-based yellow dye in addition to a phthalocyanine-based dye as a green dye layer, the blue spectral component of the phthalocyanine dye is cut, and a colored layer having excellent green spectral characteristics is created. It is something that forms.

The dye used for color correction of the phthalocyanine dye must be a yellow dye with sharp rise characteristics.

Furthermore, since it is formed by a vapor deposition method, it must have vapor deposition properties and solvent resistance comparable to phthalocyanine dyes, and the isoindolinone yellow dye used in the present invention satisfies all of these properties. In combination with a phthalocyanine dye, it is possible to form an excellent vapor-deposited green colored layer.

The yellow isoindolinone dye used in the present invention has an aromatic condensed polycyclic structure containing a petro atom, and can basically be represented by the following formula.

Those in which the 4.5 and 6.7 positions are not substituted with chlorine can also be included, but substituted types are preferred in terms of light resistance and solvent resistance.

The color varies from yellow to orange to red depending on the structure of R (divalent organic group) in the formula, but it is particularly excellent as a yellow pigment due to its versatility and sharp spectral characteristics.

In addition, the basic skeleton of isoindolinone pigments, which is an aromatic condensed polycyclic structure, is extremely stable thermally, and it does not decompose even when heated, but it has the property of easily evaporating with stones above a certain temperature. It is extremely suitable for forming a dye thin film by vapor deposition. The thin film of isoindolinone dye formed by MW is not a loose film as is often seen in organic films, but is extremely dense and adheres strongly to the surface of inorganic materials such as this glass, making it an excellent 5N film. It has certain physical properties.

On the other hand, this deposited film has excellent resistance to organic solvents. That is, it hardly dissolves in good solvents such as ketones, esters, ether alcohols, and halogen solvents as well as poor solvents such as alcohols, and does not cause any change in spectral characteristics. Therefore, there is no problem at all when applying a resist or applying a phenomenon to the dye layer, and the dye layer can be easily microfabricated, making it extremely suitable for manufacturing fine color filters, etc. be.

Examples of typical isoindolinone dyes include R in the above formula.
The following can be mentioned.

CH However, the present invention is not necessarily limited to these. Commercially available isoindolinone pigments (trade names) include Irgazine Yellow 2GLT, 2GLTg, and 2GLT.
N (manufactured by Ciba Geigy) Lionogen Yellow 50X (manufactured by Toyo Ink) First Gen Super Yellow GRoGRO, GROH (manufactured by Dainippon Ink) Irgazine Yellow 2RLT, 3RLT,! IRLTN (manufactured by Ciba Geigy) Lionogen Yellow RX (manufactured by Toyo Ink → Resol Fast Yellow 1840' (manufactured by BASF) Kayaset Yellow E 2RL, Ni-3RL176 (Japanese bodywork) Cromophthal Orange 2G (manufactured by Ciba Geigy) Irgajin Red 2 BLT (manufactured by Ciba Geigy) and the like.

Examples of typical phthalocyanine dyes include metal-free phthalocyanine, copper phthalocyanine, and phthalocyanine.
Um phthalocyanine, magnesium lp thalocyanine% zinc phthalocyanine, titanium phthalocyanine, tin phthalocyanine, lead phthalocyanine, vanadium 7 thalocyanine, chromium phthalocyanine, molybdenum phthalocyanine, manganese 7 thalocyanine, iron phthalocyanine, cobalt 7 thalocyanine, nickel phthalocyanine, palladium 7 thalocyanine, platinum 7 talocyanine.

In order to form a green pigment layer in combination with an isoindolinone dye, a phthalocyanine having a high transmittance on the green side is desirable, and lead-7 thalocyanine is particularly suitable.

The green pigment layer is generally formed by sequentially depositing a 7-thalocyanine pigment and an isoindolinone pigment by vapor deposition.
Simultaneous vapor deposition may also be used.

The respective film thickness or steam fermentation is controlled depending on the desired spectral characteristics. Normally, the film thickness is 500 to 100
oi is appropriate.

Next, a method for forming these patterned dye layers will be described. Patterning techniques for vapor-deposited dye layers include a dry etching method and a 7-off method. In the dry etching method, a resist pattern is created on a dye layer, and using this as a mask, a dye pattern is formed by plasma or ion etching. (Unexamined Japanese Patent Publication No. 58-34961, etc.)
. This method does not require the formation of an intermediate layer as in the dyeing method, but instead a resist mask remains on the dye pattern. However, since it is extremely difficult to remove this mask without damaging the dye layer, a resist mask that is essentially optically unnecessary is eventually layered on top of the dye layer2. It becomes a layered structure.

In addition, the patterned green layer formed by the lift-off method is formed by forming a pattern at the bottom of the dye layer to be removed using a soluble substance, mainly a resist, and then depositing a vapor-deposited dye layer on top of the pattern.
Thereafter, the resist pattern is dissolved or peeled off, without any direct effect on the dye layer.
The dye layer thereon can be physically removed.

The resist used in the dye layer lift-off method may be either negative or positive type as long as it can be dissolved later. However, in the case of a negative type, crosslinking generally progresses when exposed to radiation, and a solvent with strong dissolving power is required to dissolve it. Therefore, it is not preferable because it tends to damage or dissolve the dye layer.

In this regard, positive resists become soluble if the entire surface is irradiated with radiation after the resist pattern is formed, so it is possible to select a solvent that dissolves the dye less easily than with negative resists, making it suitable for 7 to 7. . Furthermore, positive resists have a wide variety of resin components, and various solvents are used for coating and developing them. It is desirable to select a positive resist that contains a solvent that has less action on the dye, and a positive resist that is mainly composed of a fluorine-containing methacrylate shown in the structure shown below as a polymerized unit is a preferred example. It will be done. This resist contains esters,
It dissolves well not only in good solvents with high solubility such as aromatics and halogenated hydrocarbons, but also in poor solvents with low solubility such as alcohols, allowing the use of solvents that have little effect on the pigment film. It is.

As such a resist, FPM210. FBM
Examples include llo and FBM120 (both trade names manufactured by Daikin Industries).

3 where R1 and R1 are hydrogen or an alkyl group, and R3 is an alkyl group with at least one fluorine bonded to each carbon.

Typical examples include the following:

As other resists, various types of resists commercially available under the following trade names can be used as appropriate.

Az series: 111, 119A, 120, 340.
1?150B, 1350J.

1570.1375, 1450, 1450. T, 147
0,1475,2400,2415°430 (all manufactured by Sibley) WaayCoat Po5itive LST Re5
1st (195, 295, 395) Waycoat H
PRPo5itive Re5ist (104,104
) (manufactured by Hunt) Kodalc Micro Po5itive Re5
ist (= made by r Duck) Isofine Po5it
ive Re5ist (made by Micro Image Chikunolji) PC129, 129SF (made by Polychrome) OFPR
■ 77.78,800 0EBR1000,1010,10300DUR100
0, 1001, 1010', 1013, 1014 (manufactured by Tokyo Ohka) KBRl, 9 (manufactured by Toshi) FMRgloo, glol (manufactured by Fuji Pharmaceutical Co., Ltd.) A patterned colored layer was formed by the above patterning process. Afterwards, it is desirable to provide a protective film on the colored layer. The purpose of kneading is to prevent defects such as dust and scratches, and to protect the colored layer from each 8i environmental condition.

Various commonly known methods can be used to form a protective film.

Organic resins such as polyurethane, polycarbonate, silicone, acrylic polyparasililene, Si, N,
810. ．． 810. Az, O, Ta, 0. An inorganic film such as the above can be formed by a coating method such as a spin cord, tipping, or roll coater, or by vapor deposition.

It is also possible to use various photosensitive resins, such as various resists.

The substrate used in the present invention is not particularly limited as long as dye deposition is possible. For example, the following can be specifically used. Glass plates, optical resin plates, resin films such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, methyl methacrylate, polyester, butyral, polyamide, etc., and patterned colored layers can also be formed integrally with those applied as color filters. It is. Examples of substrates in this case include cathode ray tube display surfaces, image pickup tube light receiving surfaces, wafers on which solid-state image elements such as COD, BBD, and O2 are formed, contact type image sensors using thin film semiconductors-liquid crystal display surfaces, Examples include photoreceptors for color electrophotography.

If it is necessary to increase the adhesion between the vapor-deposited dye layer and the underlying substrate, such as glass, apply a thin layer of polyurethane resin, polycarbonate resin, silane coupling agent, etc. to the glass substrate in advance before applying the vapor-deposited film. It is effective when formed.

Hereinafter, one typical pattern forming process of the present invention will be explained with reference to the drawings.

A positive resist is spin-coated onto a desired substrate using a spinner. After drying, prebaking is performed under appropriate temperature conditions.

Then, it is exposed to light or electron beam having resist sensitivity in a predetermined pattern shape and developed. If necessary, pretreatment is performed for the purpose of alleviating strain on the resist film before development, and rinsing treatment is performed after development for the purpose of suppressing swelling of the resist film.

If the remaining resist film and residue, so-called scum, cannot be removed even after development, they can be removed by plasma ashing.

Through the above steps, the resist pattern 2 shown in FIG. 1 is formed on the substrate 1. Next, as shown in FIG. 2, the entire surface is irradiated with light or an electron beam having resist sensitivity.

This is to facilitate the subsequent dissolution and removal of the resist pattern by cutting and decomposing the main chain of the resist, but it can be omitted. If it is omitted, it is necessary to use a solvent with stronger solubility.

Next, as shown in FIG. 5, a dye layer 3 is formed on the resist pattern by vacuum vapor deposition. When forming a frt layer of phthalocyanine dye and isondolinone dye, the vapor deposition is repeated. The thickness of the dye layer is determined depending on the desired spectral characteristics, but is usually about 500 to 10,000 A.

Next, in order to remove the resist pattern under the dye layer, the resist pattern is immersed in a solvent that dissolves or peels only the resist pattern from the substrate without dissolving the dye and without damaging the spectral characteristics.

Removal of the resist pattern simultaneously removes the dye layer on it, and to assist this,
It is also effective to apply ultrasonic energy during immersion.

In this way, a patterned colored layer 4 is formed as shown in FIG. When forming dyes on the same substrate, the above steps may be repeated while shifting the position of the resist pattern according to different patterns.

By repeating these steps as many times as there are different colors, it is possible to produce a patterned colored layer 4, 5, and 6 having three colors, as shown in FIG. 5, for example.

Next, a desired resin layer 7 is applied as a protective layer on the patterned coloring 1J to complete a color filter (Fig. 6).
FPM210 (Product name: Daikin Industries 1!! Riwo 0
．． It was applied to a film thickness of 6 μm. After prebaking at 180° for 30 minutes, stripe-shaped exposure was performed with deep ultraviolet light, and a resist pattern was formed by processing with a dedicated pretreatment solution, developer, and rinse solution. Next, the entire surface of this pattern is irradiated with deep ultraviolet light to make it soluble in developer.

The glass substrate on which a resist pattern was formed and the pb phthalocyanine packed in a molybdenum deposition boat were placed in a vacuum deposition machine and evacuated. 1- to 1(r't
The pb phthalocyanine was deposited to about 2000X thickness by heating the deposition boat to 450-550'O at the orr.

In a similar manner, First Gen Super Yellow GROE (trade name, manufactured by Nidai Nippon Ink) as an isoindolinone pigment was vapor-deposited to a thickness of about 400 OA. Subsequently, the glass substrate on which the vapor deposition was completed was immersed and stirred in the above-mentioned special developer to dissolve the resist pattern and remove unnecessary portions of the vapor deposited film, thereby making it possible to obtain a colored layer of green stripes.

The spectral characteristics of the obtained green colored layer are shown in curve 10 of FIG. pb phthalocyanine alone (7) W property (curve 8)
Compared to First Gen Super Yellow () ROH (
It was observed that by correcting using curve 9), the dorsal side had improved and superior green characteristics.

Examples 2 to 4 A green colored layer was formed in the same manner as in Example 1, except that the isoindolinone yellow pigment was changed to the following.

In each case, patterned green colored layers with improved spectral characteristics were obtained as in Example 1.

Kayaset Yellow 1-2RL (Nippon Kayaku)... Example 2 Kayaset Yellow 1ii-5RL176C Nippon Kayaku)... I3 (A/Gajin Yellow 3R-LTN
(Ciba Geigy)...I4

[Brief explanation of the drawing]

1 to 6 show color fill graphs according to the present invention. 1...Substrate 2...Tresist pattern 3...Dye layers 4.5 and 6...Patterned dye layer 7...
・Resin too fθ0 θ0θ 7σθ

Claims (3)

[Claims] (1) A color filter characterized by having a green pigment layer formed by vapor-depositing a phthalocyanine pigment and an isoindoline pigment. (2) Claims in which the green pigment layer is a patterned green pigment layer formed by depositing a phthalocyanine dye and an isoindolinone pigment on a substrate having a resist pattern and then removing turns from the resist. Force 2-filter according to paragraph 1. (3) The color filter according to claim 2, wherein the resist pattern is formed of a positive resist.