JPS6042707A - Color filter - Google Patents

Abstract

PURPOSE:To complement the spectral characteristics of phthalocyanine type dye and to obtain a color filter having a superior blue dye layer and superior in resistance to light, heat, solvents, etc. by using a combination of the phthalocyanine type dye and a quinacridone type magenta dye. CONSTITUTION:A blue dye layer is formed by using a combination of a phthalocyanine type dye and a quinacridone type magenta dye, e.g., represented by formula I or II. A resist pattern 2 is formed on a base plate 1 of glass or the like, and all this plate 1 is irradiated with far UV rays to solubilize the resist pattern 2 in a developer. Cu phthalocyanine is vapor deposited on all the plate 1, and next, a quinacridone type dye is deposited to form the blue dye layer 3. The blue pattern 4 is formed on the plate 1 by developing the layer 3. Then, necessary other dye films 5, 6 are formed likewise, and a protective layer 7 is formed to cover the dye layer. The color filter thus obtained has superior durability, etc., too.

Description

[Detailed Description of the Invention] The invention is related to color filters, especially color?
The present invention relates to a color filter for fine color separation with an R image element, a color sensor, and a color display.

As a color filter, a dyed color filter is known, in which a mordant layer made of a hydrophilic polymer material such as zeftin, casein, gryu, or polyvinyl alcohol is provided on a substrate, and the mordant layer is dyed with a dye to form a colored layer. ing. In this dyeing method, many dyes can be used, and it is relatively easy to meet the spectral characteristics required for the filter. It also has the drawback of poor yields due to the complicated process of installing an intermediate layer for resist dyeing for each color. In addition, the heat resistance is about 150 to 160℃ IAf,
is relatively low, 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 (Japanese Unexamined Patent Publication No. 55-14
6406) With this method, a colored layer can be formed using the dye itself, so it can be made thinner than the dyeing method, and it is easy to control as it is a non-aqueous process. It is also characterized by 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 the viewpoint of the manufacturing method, even if the spectral characteristics are good, dyes that lack manufacturing stability or require special processing steps will lead to a decrease in yield, making them unsuitable for color filters. Therefore, as a dye for color filters, it is necessary to select an optimal dye that is well-balanced in terms of both spectral characteristics and manufacturing.

In particular, the vapor deposition method has strong manufacturing constraints such as being heat resistant, easily evaporated, and resistant to solvent treatment in the photolithography process, so although it has various advantages over the dyeing method, it It wasn't.

By the way, it can withstand the pigmentation used in vapor-deposited filters,
It also has well-balanced spectral characteristics as a filter, and phthalocyanine dyes are examples of dyes that relatively satisfies these characteristics.

The basic phthalocyanine ring of phthalocyanine dyes is extremely stable both chemically and thermally, so they have excellent vapor deposition and solvent resistance. However, in terms of spectral characteristics, 7-thalocyanine pigments range from blue to green, and many exhibit blue or cyan characteristics. Although it may exhibit properties close to blue depending on the central metal or substituents, it generally contains a green component, and is not sufficient when viewed strictly as blue.

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 7 talocyanines and compensates for their disadvantageous spectral properties. .

The color filter according to the present invention is characterized by having a blue dye layer formed by vapor-depositing a heptalocyanine dye and a quinacridone dye. That is, in the present invention, by using a quinacridone-based magenta dye in addition to a 7-thalocyanine-based dye as a blue dye layer, the green spectral component of the 7-thalocyanine dye is cut, thereby creating a colored layer having excellent blue spectral characteristics. It forms the

The dye used for color correction of the phthalocyanine dye must be a magenta dye with sharp rising characteristics. Furthermore, since it is formed by a vapor deposition method, it needs to have vapor deposition properties and solvent resistance comparable to phthalocyanine dyes, but the quinacridone magenta dye used in the present invention satisfies all of these properties. In combination with a 7-thalocyanine dye, it is possible to form a vapor-deposited blue-colored layer.

The quinacridone dye used in the present invention has a basic skeleton represented by the m formula, and includes derivatives derived therefrom.

(I) Derivatives and examples are etc. There may also be a mixture of these.

In terms of spectral characteristics, both have a rising transmittance on the back side, and are suitable for the green component of the phthalocyanine color (g).

In addition, quinacridone dyes are extremely stable thermally,
It does not decompose even when heated, and it evaporates easily when the temperature exceeds a certain temperature. 7 is extremely suitable for forming a dye thin film by vapor deposition. The thin film of quinacridone dye formed by vapor deposition 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 glass, and has excellent physical properties as a vapor-deposited film. On the other hand, this vapor-deposited film has excellent resistance to organic solvents. That is, it is hardly soluble in good solvents such as ketones, esters, ether alcohols, and halogen solvents as well as poor solvents such as alcohols, and there is no change in the spectral characteristics. Therefore, applying resist to the dye layer,
Since there is no problem at all even when development is performed, the dye layer can be easily finely processed, and is extremely suitable for manufacturing fine color filters and the like.

Examples of internal pigments include Lionogen Magenta R (Toyo Ink), First Gen Super Magenta R0RE (Dainippon Ink), Syncasia Red BRT, ¥, RT, (7'Yuhon) Syncasia Violet BRT (Devon), etc. .

An example of a typical phthalocyanine is Metal Free 7.
Talocyanine, steel phthalocyanine.

Beryllium phthalocyanine, magnesium 7-thalocyanine, zinc phthalocyanine, z-umphthalocyanine,
Tin phthalocyanine, lead phthalocyanine, vanadium phthalocyanine, chromium phthalocyanine, molybdenum phthalocyanine.

Manganese phthalocyanine, iron phthalocyanine.

Examples include cobalt phthalocyanine, nickel phthalocyanine, palladium phthalocyanine, and platinum 7-thalocyanine.

The blue dye layer is generally formed by sequentially depositing and laminating a phthalocyanine dye and a quinacridone dye, but simultaneous vapor deposition may also be used. Each film thickness or deposition amount is controlled according to desired spectral characteristics. Usually, a film thickness of 500 to 10,000 A is appropriate for each film.

Next, a method for forming a patterned dye layer will be described. Patterning techniques for vapor-deposited dye layers include dry etching and lift-off. In the dry etching method, a resist pattern is created entirely on the dye layer, and the pattern is used as a mask to form dye turns by plasma or ion etching. The formation of the layer is unnecessary, but instead a resist mask remains on the dye pattern.Moreover, it is extremely difficult to remove this mask without causing any damage to the dye layer, and in the end it is virtually impossible to optically remove it. In general, it becomes a two-layer structure in which an unnecessary resist mask is laminated on the dye layer.

In addition, the pattern supporting dye layer 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.
It can be formed by physically removing the dye layer thereon.

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

In this respect, positive resists become soluble when the entire surface is irradiated with radiation after forming a resist pattern, so a solvent that dissolves the dye less easily can be selected compared to negative resists, making it suitable for lift-off. Furthermore, positive resists also 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 can be used with lip agents that have less action against pigments, and a positive resist that is mainly composed of a fluorine-containing methacrylate having the structure shown below as a polymerized unit is a suitable example. I get kicked. This resist dissolves well not only in good solvents that have a high dissolving power such as esters, aromatics, and halogenated hydrocarbons, but also in poor solvents that have a low dissolving power such as alcohols. This is because a solvent with less impact can be used.

As such a resist, FPM210. FBML
lo and FBM120 (both trade names manufactured by Daikin Industries).

R, -C-R.

s Here, R1 and H are hydrogen or an alkyl group, and R8 is an alkyl group in which at least one fluorine is bonded to each carbon.

Typical examples include:

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

AZ Shi IJ-s: 111,119A, 120,340
, 1350B, 1350.71370.1375.14
50.1450J, 1470,1475°2400.2
415,2450° (manufactured by Shipley) WMuycoat Po5itive L day X Re5
1st (195, 295, 395) Waycoat H
PRPo5itive Re5ist (104,10
6) (manufactured by Hunt) Kodak Micro Po5itine Re5i
st 809 (= made by r duck) Teofine Po
eitlJe Re5ist (made by Micro Image Technology) PC129, 129SF (made by Polychrome) OFPR
177,78,800 0KBR1000,1010,10300DUR100
0, 1001, 1010, 1015, 1014 (manufactured by Tokyo Ohka), ICBRl, 9 (manufactured by Toshi), FMRgloo, 1o1 (manufactured by X±Yakuhin Kogyo) or above.A patterned colored layer is formed by a patterning process such as After that, it is desirable to provide a protective film on the colored layer. This is to prevent defects such as dust and scratches, and to protect the colored layer from various environmental conditions.

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

Organic resins such as polyurethane, polycarbonate, silicone, acrylic, polyparaxylylene, 81BN4
, 5i02, 810, A40g+''2oB, etc. can be formed by coating methods such as lath spin coating, tipping, roll coater, etc., or 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 used:

It is also possible to integrally form a glass plate, an optical resin plate, a resin film such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, methyl methacrylate, polyester, butyral, polyamide, etc., and a colored pattern with a book that is applied as a color filter. . Examples of substrates in this case include a cathode ray tube display surface, a light receiving surface of an image pickup tube, a wafer on which a solid-state image sensor such as a COD, BBD, or OID is formed, a liquid crystal display surface of a contact type image sensor using a thin film semiconductor, Force 2 - Photoreceptor for electrophotography, etc.

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 isobaric polyurethane resin, polycarbonate resin, silane coupling agent, etc. to the glass substrate before applying the vapor-deposited film. It is effective when formed.

A typical pattern forming process of the present invention will be explained below 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 for the purpose of alleviating strain on the resist film is performed before development, and rinsing treatment is performed for the purpose of suppressing swelling of the resist film after development.

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

Through the above steps, the resist pattern 2 shown in FIG. 1 is formed on the substrate 1. Then, as shown in FIG. 2, the entire surface is irradiated with a resist-sensitive light or electron beam.

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.

Then, as shown in FIG. 3, the coating is combed over the resist pattern. The thickness of the dye layer is determined depending on the desired spectral characteristics, but is usually about 500 to 100X.

Next, in order to remove the resist pattern under the dye layer, the dye is not dissolved, and the spectral characteristics are changed to assist the removal of the resist pattern, which simultaneously removes the dye layer above it. 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 depending on the type of color, for example, a patterned M color layer 4, 5 and 6 having three colors as shown in FIG. 5 can be manufactured.

Then, a desired resin layer 7 is maintained on the patterned colored layer.
A color filter is completed by coating as J (Figure 6).
FPM 210 (product name: Daikin Industries) to 0.
It was applied to a film thickness of 6 μm. After prebaking for 180υ3o minutes, mask exposure was performed using 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 was irradiated with deep ultraviolet light to make it soluble in a developer. Subsequently, the glass substrate on which the resist pattern was formed and the Cu phthalocyanine packed in the molybdenum vapor deposition boat were placed in a vacuum vapor deposition machine and evacuated. Vacuum level 1
1~1 (Deposition port at r'torr 450~
Heating to 550'O and Cu phthalocyanine to about 200O
It was deposited to a thickness of A.

Lionogen Magenta R (trade name: Toyo Ink Co., Ltd.) as a quinacridone dye was vapor-deposited to a thickness of about 400 OA using a similar method. Next, the glass substrate on which 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 with blue stripes.

The spectral characteristics of the obtained blue colored layer are shown in curve 8 in FIG. It was observed that the tL7j had superior blue characteristics with improved edges compared to the characteristic 1 curve 9 of Ou phthalocyanine alone.

Examples 2 to 4 A blue colored layer was formed in the same manner as in Example 1 except that the phthalocyanine dye was changed to the following. In each case, patterned blue colored layers with improved spectral characteristics were obtained as in Example 1.

Meta/I/7 leaf thalocyanine... Example 2 Lead phthalocyanine... 13 Nickel 7 thalocyanine... #4

[Brief explanation of drawings]

Figures 1 to 6 show the process of forming a color fill protective layer according to the present invention. FIG. 7 shows a graph of spectral transmittance. 1...Substrate 2...Resist pattern 3...Dye layers 4.5 and 6...Patterned dye layer 7...Resin 56 4θ05θ06θθ 7σ0 Saka liquid Table

Claims (3)

[Claims] (1) A color filter characterized by having a blue dye layer formed by vapor-depositing a phthalocyanine dye and a KINAC IJtone dye. (2) A 17 dye layer is formed by depositing a 7 talocyanine dye and a quinac 1 nodone dye on a substrate with turns (a turn-shaped blue dye layer), and then removing the turns. Claim 8g1 A ridged color filter. (3) The color filter according to claim 2, wherein the resist pattern is formed of a positive type resist.