JPH04505635A - Orange filter dye and filter components for color filter arrays - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Invention of orange filter dye and filter member for color filter array field of The present invention is a color solid state imager (color 5 solid state imager). ate imager), more specifically, the imagers used in these imagers. For organic color filter arrays concerning orange azo dyes and color filter components containing such dyes. do.

Background of the invention A solid-state imager has a color filter array on the photosensitive part of the device. - (CFAs) are made so that colors can be distinguished. general In addition, CFAs absorb organic dyes into layers patterned into appropriate filter patterns. Manufactured by accommodating

Among the applications of solid-state imaging is mounting! is the tone correlation coefficient (colo rmatching function, spectrum close to CM Fs It is sometimes desirable to have sensitivity. Common red, green and blue colors color filters provide sufficient color information for most images, but In some applications where quality color reconstruction is required, CMFs can make the perceived color more accurate. This is preferable because it reconfigures accurately.

(For more information about CMFa, see “The Theory of Photographic Processes.” heoryof the Photographic Process)” , T. H., James M., 4th edition, Macmillan Publishing, 1977]. figure 1 is the 1931 CIE color harmonics function plotted as relative intensity 1 versus wavelength. i: These CMFs are internationally adopted standards. y and ECMF The curves corresponding to s are usually approximated by green and blue color filters, respectively. can be done. However, with a common red color filter, the ECMF Can't get close enough and this can be done by a dye that has an orange color It is better. In order to manufacture a filter that approaches deCMF, the spectral curve It is necessary to contain a CFA dye of suitable shape, structure and stability. That's below The following criteria are considered to be sufficient. Please refer to Figure 2. Figure 2 shows the xCMF Compare the curve with the transmittance versus wavelength curve of a material containing a dye that meets the criteria of the present invention. This is what I did.

1. The bathochromic absorption edge of the iCMF curve is determined by installing an appropriate infrared blocking filter in front of the sensor. The hypsochromic edge can be created by placing a filter dye in CFA. must be limited by fees. Therefore, the spectral requirements for dyes transmits less than 5% of the light at 500 nm, determined by the characteristics of its absorption edge. (optical density or OD>1.3), at least 50 nm at 570 nm. % (OD<0.3) and at least 80% COD<0.1) at 600 nm. have to pass. The color of this dye is best described as orange However, those familiar with this technical field know that the color varies between orange and pink depending on dye concentration. It should be understood that it varies between .

2. The dye is a matrix used to bind the dye into the color filter. must be compatible with the Commercially available CFAs are cationic mordants. is made using a photopatternable composition containing. fully bound to this mordant. The filter dye must be anionic in order to Also, other In order to be compatible with the CFA process, the dye should be kept at a suitable pH that does not attack other CFAs. It must be soluble in (between 3 and 10) solvents or aqueous solutions.

3. The dye must be obtained by a simple and high-yield synthetic route. do not have.

4. The dye must have good photostability. For the purposes of the present invention: Good photostability means that the peak of the dye after exposure to light at 150 kilolux for one hour is defined as a case where the decrease in absorption of is less than 10%. Photostability is due to oxygen in the dye. Improved by using overcoats, additives or equipment packaging methods that prevent can be done.

5. The dye must have good thermal stability. solid state toy The various processes used in the packaging of magers require the use of small amounts of dye (both at 150°C It has been found that at least one hour at the temperature is required.

Summary of the invention [・EF”1 or L is found to be particularly suitable for meeting all the criteria. ga-] 2 (In the formula, R', -R' are hydrogen, alkyl having 1-8 carbon atoms, and halogen (The dye is metallized with a metal such as nickel).

The dyes encompassed by the present invention are soluble in aqueous solutions and are also compatible with CMF (Figure 2). The vectors fit well and exhibit acceptable stability. In some cases (specific dye binding specific tAII) in the matrix, without the need to exclude oxygen from the layer. It provides excellent photostability. In other cases, oxygen may be used to obtain acceptable photostability. need to be eliminated.

In addition to using these dyes in a single layer, a layer containing one of the dyes can be used in another layer. Estuary in combination with a layer (on top or bottom of the layer) containing a dye (e.g. yellow) 1 is a traditional typical tone correlation coefficient plotted as relative intensity versus wavelength; do FIG. 2 is a graph of transmittance versus wavelength for representative dyes of the present invention with tonal correlation coefficients or The inventive metallizable ab dye includes: 3-biricinol moiety whose 2-position is substituted with a methyl group, and biricinol moiety is bonded to the 6-position by an azo bond, and the ortho position to such a bond is Includes aryl rings substituted with syl groups.

In particular, we evaluated three dyes with direct substituents of the F series and found that these were acceptable. I found out that R', R' ・ R' lR' 4 R' 6 R' etc. Compound 1) HHHH HH Compound 2) I(I(HCI HH Compound 3) H) I Hn-Bu HH dye is 2f! l photopatternable (photopatternbLe) evaluated in a mordant system. These mordants The system L is based on McGukin's I [acGukin] and Cohen's Photosensitive diazo resins (formula I) and and a cationic mordant (formula ■), and the other is a mixture of photocrosslinkable cinnamate groups and as described in US Pat. No. 4,808,510 of Bi cation l13! It is a polymer containing a dye (formula ■).

Formula I formula n (In the formula, R7 and R2 may be the same or different and have from 6 to about 20 carbon atoms. aryl, arylalkyl or alkaryl group, or a carbon atom is an alkyl of number 1 to about 10; R3 is alkyl having 1 to about 3 carbon atoms, and n is 0.1 or 2;

R1 and R1 are hydrogen or together with the carbon atom to which they are bonded. Therefore, carbon atoms such as noclohexyl, cyclopentyl, phenyl and naphthyl Forms saturated, unsaturated or aromatic ring systems with 5-10 members.

X (9 is an a anion).

Expression■ (In the formula, R and R1 are lower alkyl groups R1 is a divalent bonding group.

R1, R5 and RII are hydrocarbon groups having 1-16 carbon atoms.

X is a photocrosslinkable group, and Z is a counterion that balances the charge).

Compound 1 Diazonium salt B was prepared by dissolving NaOH (4 g: 0.1 mol) in 100 ml of water. and then by adding anotranilic acid (13.71 g: 0.1 mol). Manufactured by Stir sodium nitrite (6.9 g:O, 1 mol) until dissolved. I added while doing so. Then, while stirring this solution, add 200 g of crushed water and 30 I was added to a beaker containing 1 ml of 'aHc1.

Compound A (10.9 g: o.

1 mol) and Na2CO1' R20 (95 g; 0.766 mol). was added dropwise to the cold stirring solution. Stir the dye solution for [h], then add the dye (compound 1) While stirring at T, carefully add concentrated HCI (120 ml; 1.44 mol). It was 11 years ago. This mixture was stirred for 1 hour, then i! ! passed. The dye was washed with water and dried. 24.0g (93.3%) A yellow-orange solid was obtained.

2. Manufacturing a filter component containing Compound 1 The dye solution contains 2 g of Compound 1. Niyotte was prepared by adding to 1 liter of standard pH 10 borate buffer. Formula I II (where y=40.z=60.R1''R1=R4=R6-CHl, R, -- CH2CH2-1Rs -CH2CH2CH20H and X--CHICH,〇- Polymer of Co CH=CHC5Hs) and sensitizer 3-(7-medquino 3-bear 8 containing linoyl)-1-methylpyridinium p-4 luenesulfonate , 0% solid aqueous solution was spin-coated onto a glass wafer at 300 rpm. 1♀ was produced by The polymer to sensitizer ratio was 121.

Using a Canon PLA501F aligner, expose the layer to UV light for 22 seconds and Color was developed with a mixture of 20% methanol and 80% iso-butanol for 0 seconds.

Soak the dried product in the dye solution for 1 minute, rinse, dry, and add 2 weights of nickel acetate. % aqueous solution for 30 seconds, rinsed and dried. The final colored coating has the following transmittance had: 500nm: L, 4%T, 570nm: 63%T, 600nm :87%T0 The dye obtained in the filter layer is thought to have the following structure Dyes suitable for color filter arrays encompassed by the present invention are soluble in aqueous solution. icMF (Fig. 2), and has an acceptable safety profile. Indicates qualitative. In some cases (specific dyes in specific dye-binding matrices), the layer Sufficient photostability can be obtained without the need to exclude oxygen from. in another case Exclusion of oxygen is necessary to obtain acceptable photostability.

FIG. 1 abstract Concerning metallizable olene-azo dyes for color filter arrays. . This dye has... 3-bilinol moiety substituted with a methyl group at the 2-position, and bilinnol moiety It binds to the 6-position of Includes aryl rings substituted with syl groups.

A layer containing this metallizable dye is used to form a color filter member. I can do it.

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Claims (4)

[Claims] 1. Structure below: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R'1-R'6 are hydrogen, alkyl having 1-8 carbon atoms, and halogen. and the dye is metallized with a metal such as nickel). A metallizable azo dye for color filter arrays, characterized in that it comprises: 2. R'1=R'2=R'3=R'5=R'6=H, and R'4 is Cl, n- The dye of claim 1 selected from the group consisting of Bu and H. 3. A support, a photosensitive diazo resin and a cationic mordant on the support, and claims. A color for image sensors, etc., characterized by comprising a layer containing a dye of 1. - Filter components. 4. a support, and a photocrosslinkable cinnamate group and a cationic mordant on the support. comprising a layer containing a polymer containing the orange dye according to claim 1 and the orange dye according to claim 1. , color filter components for image sensors, etc.