JPS5946609A - Production of multicolor optical filter - Google Patents

Abstract

PURPOSE:To perform the resist printing treatment effectively with one process and to prevent the occurrence of reticulation and side etching, by processing a polymer relief, which is dyed in the preceding proces, with an aq. acidic solution of a condensation high molecular compound of an aromatic sulfonic acid after heating the polymer relief at 150-180 deg.C for 30min. CONSTITUTION:A mosaic-shaped or stripe-shaped relief 4 is formed on a substrate 1 consisting of a transparent glass, a silicon wafer, or the like. The relief is processed with a solution containing, for example, a yellow dye, and a relief 5 is dyed by the yellow dye. The dyed relief 5 is processed with the aq. acidic solution of a condensation high molecular compound of an aromatic solfonic acid to obtain a dyed relief 6 subjected to the mixing preventing treatment. In this case, it is desirable that the aq. solution of acetic acid having pH<=5.5, especially, pH<=5.5 is used as the aq. acidic solution. Since there are occasions when reticulation or side etching phenomena occur on the relief surface after the resist printing treatment, the dyed relief is subjected to the heat treatment at 150-180 deg.C for 30min before the resist printing treatment. Next, said process is repeated.

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing a polychromatic optical filter.

117, the present invention relates to color image pickup tubes and color solid-state image sensors''
The method for manufacturing a polychromatic optical filter with λ used for τ is described below.

Color image pickup tube or color charge-coupled device (COD)
, Kashi-1 (, I; Pa' Injection!) Kan-solid fat i'l represented by Kuko (CID): (-A9 uses polychromatic optical filters in the form of mosaics and stripes. .

Normally, a polychromatic optical filter has one red, green, color or cyan, green, yellow, white color in a regular stripe pattern! ;) Ruiha・T: They are arranged in a zaic pattern, but the color 4'i゛・1 is 1 in these! There are also 2 colors, 4 colors, 11) ℃ and more.

In order to manufacture a color solid-state image pickup device having a polychromatic optical film, the laminating method and the onueno i4j method are generally known. The f3fJ person takes a solid-state image on a transparent support such as glass (y, , ;
t>("j:<by putting p stone non'TJ≦ on the child board? j, 1. On the other hand, rJ expert] 1,
A polychromatic optical filter is formed directly on the 11ζ element: iy;E.

No matter which IA) line is on these boards! - In order to form an optical filter, a photosensitive layer 1'' and a rim layer are provided on a substrate, and then a solid layer 1'' is formed by mask path light and a wash/off process (development). I
(3(, '4+ (<Child drawing 7-() Form a mosaic or striped relief corresponding to 3, and apply this to each!
1 Te constant σ dyeing 5゛ (The process of coloring 1 eye with 1 is done and the 1 force method is performed 4 times. This method has relatively f7f operations)
Although this is an advantageous method for funerals, it has the following drawbacks.

Zubuyo 1) [), repeat the above steps for l and k, j4.3 In case, during processing, the dye comes out iYJ from the colored relief at the previous upper value. Dyeing the second relief may cause color mixture in the next dyeing process, or dyeing not only the relief of 2) but also the stained relief of IJ. There were problems such as color mixing.

To prevent this, after forming the 513-color relief, if! E&, I'tari? 1(
J9 is known as a method of treating the dyed relief with tannin C.1, an aqueous solution of acetic acid, and andemonyl potassium tartrate water-IDK (Unexamined Japanese Patent Publication No. Publication No. 55-25067 has been proposed.

Of these methods, the latter method is simpler than the method of providing an intermediate layer, but since it requires sequential processing in two baths, the processing method is complicated and control is difficult.
There is a point at 1llL.

The present inventor conducted a study on alternative resisting treatment, and found that -
We discovered that prevention≦(18 treatments) can be effectively performed in one treatment, and completed the present invention.

It has a resisting effect, but in some cases after resisting treatment,
Phenomena such as reticleation or night etching of 1/IJ-F may occur on the relief surface (1), but this phenomenon can be prevented (2) Before performing the treatment, heat the relief at 150C to 180T. This can be completely prevented by heating for at least 30 minutes.

Therefore, in the first aspect of the present invention, after forming a mosaic or stripe relief on a substrate, this is dyed with a dye 11 that has a constant spectral 11 characteristic. A method for producing a polychromatic optical filter comprising repeating the step at least twice, in which the polymer relief prepared in the previous step (°C) is treated with an acidic aqueous solution of a condensed polymer compound of sulfone 11. That'1!I
- There is a method for manufacturing a polychromatic optical filter, which has the following characteristics.
After forming the upper stripe shape, this is subjected to a predetermined spectroscopy! 1′
In a method for manufacturing a polychromatic optical filter, which comprises repeating the step of dyeing with a dye having r properties at least twice, the polymer relief dyed in the previous step is dyed with 150 U
A method for manufacturing a polychromatic optical filter, which comprises heating at 180C for 60 minutes or more, and then treating with a solution of an acid ↑L water of an aromatic sulfonic acid (IZ compound). So, (7ru.

Hereinafter, the present invention will be explained with reference to 1j sink 1=1 shown in the accompanying drawings.

FIGS. 1(a) to (g) are explanations showing the steps of manufacturing a polychromatic optical filter according to the present invention. As shown in FIG. 1(0), a substrate such as transparent glass or silicone 1, a photosensitive resin film 2 made of a photoresist such as dichromium dark gelatin is coated to a thickness of about 2000×~
15,0OOA. .

This resin 1] (\) is coated with a mask (not shown) having a predetermined mosaic or stripe pattern.
i4 exposure, :! By doing so, a mosaic or striped relief 4 as shown in FIG. 1 (1)) is formed. Next flJ
For example, the relief 5 is treated with a solution containing a yellow dye, and the relief 5 is dyed with the yellow dye as shown in (c).

Then, in accordance with the present invention, for example, Bayer AG has the product name 1 &
To an acidic aqueous solution of a condensed polymer compound of aromatic sulfonic acid sold as 5itol NBS 1iquid (1 color), treat the mixed relief 5;
c]) Shown in 3-(・112! The power of the color mixture prevention treatment is applied), - the dyed relief 6 is shown as 1゛i). The acidic aqueous solution of this J:'J combination is p)l 5,5 or less, Q! ] Ni/
4.5 or less (7) Acetic acid water i'i'i 'l+V, t]
'7. + Koto is I:j4. 4 [As mentioned above, "1. ) In case of (1(-yotsu)C, retigulation or two-edge phenomenon may occur on the relief surface after resist dyeing treatment, so before resist dyeing treatment,
It is preferable to heat-treat the dyed relief at 15[)C to 113[JC] for 0 minutes or more. By doing so in this way, it is possible to prevent the occurrence of "retching noises" or "sound bites".

Next, the above process is cut out as follows. A relief 6 of 11 squares and 11 squares with color A and color mixture prevention is placed on the base plate 1 using a photosensitive material such as gelatin, as shown in FIG. +-
, 14'+J'' mask 7 is provided, and a second layer 7 is exposed to ultraviolet light through a mask having a striped or striped pattern and developed.
) -7-;j Form a second roof 8 adjacent to the dyed relief B as in Nissho (r). The development process for the upper ML is carried out in warm water or 1 part weak acid in 1.0 warm water. If the resist dyeing treatment such as [;] is not done,
- Some of the dyed 11 from the 1
[It dissolves into the liquid and reduces the color effect.
・Ride) I: <, this lj4 'I'l newly formed relief 4・staining t2, next o)] γj-colored in other Mulberry family in two culms 14.1. l, c may cause color mixture when
reactor. However, 1-Ki θ) l11 ward anti-leaf treatment was carried out, and in Nariai, it is as shown in 2-Ki!・[Prevent elution of Go4i.

The relief 8 formed with l~ as described above was then dyed with another dye, such as cyan 7/IJ, and 1.
1;151/! shown in Figure (g). I+ <Cyan ((-
・Place the colored relief 9. above! (! Color number,
If Jt filter carried out in an aqueous solution of cyan dye is not treated with relief dyeing dyed with Yer r1- (Itl F,
The cyan dye was dyed yellow, and the elm relief was also dyed? (l, coloring, causing color mixture, and yellow dyeing, However, the occurrence of such color mixing can be prevented by carrying out the above-mentioned prevention process. In order to carry out the treatment, ``About Relief 9-Jl f
tl: Perform the same resist dyeing treatment and proceed to the next dyeing process (fal
magenta). In this case, the relief 6 should be subjected to resist dyeing treatment once.1.The final dyed relief should also be subjected to resist dyeing treatment in order to stabilize the dyeing in Tsugutoshi's treatment.1. 'f sho ■7.

Figure 2 shows fQI34J of fll+ of the relief pattern formed by the present invention.
After forming the relief 12, a cyan resin layer 13 is formed so that a part 14 of the relief layer 13 overlaps, and is dyed twice: yellow and cyan (the middle part is dyed twice). ) can be formed. Furthermore, by creating a portion 15 where no relief is present, a portion corresponding to white can be formed. This "7↓h match also, AiT
It is also possible to perform the anti-iiQ treatment on the cyan-dyed relief formed in the second step as described above (σ), and then perform the next dyeing process (for example, magenta).

The substrate used in the present invention may be a transparent glass or a solid-state imaging device wafer such as a silicon urchin on which pixels have already been formed.

Photosensitive, 1',' IJ moms used in the present invention include gelatin, casein, fish manure, and 1'. Livinyl alcohol or the like to which dichromium salt or chromate is used is used. Such a single layer of photosensitive polymer can be applied, for example, by spin-coating or the like.

1) In light, the above photosensitivity, I? Dyes used to dye the relief pattern formed by the +)mer include acidic g4v $-), direct dyes, and reactive dyes. Specifically, for example, rf'? Kayanol Yellow NGS (C, 1, A
c1dye1.1otv 110r Nipponka pi 1 old (
Strain 1), iji,'7), Suminol 7/-su1
--I x Low G (G, I Jcl<3 yellow
, ow 61゜Made by Sumitomo Chemical Co., Ltd.), Suminol・
First let 1.゛e (C, I , Ac1(i
Ra (l l 18. Manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Milling Red R0S (G, I, Ac1d
Red, 114. (manufactured by Nippon Kajuku Co., Ltd.), Diazid・
First Red 3BL (C0I.

Acj, d RO+] i 58. Mitsubishi Chemical Industries (
), / ') Pudding Green (C0I, Ac
1d Green 9. Tokyo Kasei, Tsuke(ka)ψso),
Brilliant India Blue 5 G (GJ, A
c1d Blue 105+ Hoechst tL? Ni'ri, Kayanor Zianin 6 B (C0I, Ac1
(113], ue 83° [1 Mokuka, I, j5 Co., Ltd.
(manufactured by Acid), Acid Nuanin 78 FH (CJ, Ac
”, rT L3. Lue 100r Tokotsuchigayaka Ii Jokogyo (Match) (N), etc. are used as direct dyes, but as direct dyes, Lue 100r is used as a direct dye.
, Dirt>ct, Yel, 1ow 85° 11 pieces;~manufactured by Co., Ltd.), Sumiraitoretsu l-゛4 B (C
.

1, DJ rer t, 11p, +381. Manufactured by Sumitomo Chemical Co., Ltd.), Chikara Y Las Spun Blue BWL
(C01, Direct, Blue257, F1 version 2j, ; made by 1'(,)), Eisen Green G
X (C, 1, Di, racl; Grpen 8+
4J”, Yuka Doba (manufactured by IIO), 3;;;
In addition, reactive dyes such as I'-1 and Prozine Brilliant Let'CD (C, 1, ii (, ya, ct-j,
vol, (ecl, 6ro.

(Manufactured by Nisubishi Fhi Narudogyo Co., Ltd.), Mandarin Green 2B
S (C,jI(active Green 7.
Nippon Kayaku Co., Ltd.), Sumifix Navy Blue R (U, I.

Rractive Blue 20. (manufactured by Sumitomo Chemical Industries, Ltd.), /, and C. These may be used in 7]X Germany or in combinations V of 21 or more.

In this book, I-Ming.
? Jt sulfonic acid condensation polymer compound '147 acidic water (i\liquid)? Kozoku Sulho 71'2 is If
:F L, -(&;'t, has 1 to 4 sulfones, -73 groups in the molecule -F, ::In combination, C is li, 7. substituent) (b) Benzene, - is preferably derived from naphthalene. Favorable aroma? ? The condensation polymer compound of group sulfonic acid '+'=I is the following general formula (% formula %) where R is a benzenide or naphthalene group, and X is water [1, 1, 1, 1, ; ;Halogen, +, b
c Argyl of 1 to C; (diOOH; alkoxy of C, to C4; alkyl of C1 to C4 or phenoxy substituted with halogen and -C also preceded by 1'; alkyl of C1 to C4 or... Triazinylamino, which may be substituted with 11-11 chloride (this triazinyl group is mono- or di-01-C6 alkylamino, mono- or di-1-80 xyethylamino, phenylamino, or sulfonylamino). Place 1 in 1 [・Susete C is also good); Y Y 1 (MO3S)r, -11-SO2-; ! Meko+:
I (1・AO3S) ,, -R---C1l-G
ll-, where Y is water;: 80) I, nitroono, -(yoC1-C4 alkyl')゛mino Table 1)
Z), M is water-4, alkali gold 1, a, FIC natriuno, kaliuno, ), ammonium i, fiq
J, shi, m are [], 14:ta('', 2 in Table-1) shi(
The river is 2, 1 par, 1 go, XG, 1 round -, but (7+, 7.
Even if it is J:L), 11ba1~/l;, ]:4
J) -j-1゛HIKiwa3\Rei) Fewer compounds, c <
1 and lower aliphatic aldehyde A.1 (IF'F
at least one of the products or compounds of the following general formula, 1, and 3 compounds q of the above-mentioned -tubular formula-Q n;
)σ) At least one small office (Iσ1, In is 2 Te,,
x ) One is O)], X (1)ljl (+) One is Y-F(-8O2- 1. It is a condensation product of dihydrogen (dihydroyl)-dihydroyl (phenylsulfone, etc.) and lower 1ji rib group (anol 1-7).

Formaldehyde is the best for eyebrow aldehyde.

At 1℃' for the sulfone 612 component, naphthalene-
1゜4-disulfone fi': , naphthalene-1,5-
Disulfone rI9. ．． Naphthalene-1,6-disulfonic acid, naphthalene-2,6-disulfone 1ya, naphthalene-1,3,6-1 risulfone t, '2.2-no-ibiloxynafcrene-6-sulfone 1'3 '? ,')−
-f l゛roquinaphthalene 6,8-disulfone I
Y's, 2-no-ite80xinaphthalene-A, 6-disulfonic acid, /I-chloro-2-toluenesulfone/'
it, ";'-Amino-4-sulfobenzoic acid, dinoenyl ether sulfone f'i'!!, cyt-ruyl ether sulfone l'l' (, noenyl ether sulfone ri:y
-, naphthalenesulfonelf'2.2.4-)sulfobenzaldehy)',4.4'-sini)Llsalpene-2,2'-disulfonic acid, 4.4'-)methylaminostilbene-2,2 '-disulfonic acid, bis-triazinylamino-methyl R-disulfonic acid, and the like.

A preferred condensation polymer compound is diphenyl ether-sulfone 1 wave. 71 Norsulfone "ib i or naphthalenesulfonic acid and pormaldehyde (plus +, L, i
+,;i combination oil r/. The condensation product ゛i・′ (in addition to 4,4′-cybaitroxidineenylsulfone) is compatible with (I′j4 of 1・ε). In particular, a suitable 4i'6 polymerization f1' direction is l
'When it was released in Italy''No. 1,9 6 0,6 1 6 was 1112・i, +5 4) Yono I, 4.4
'-Civite 90 xydino-enzyme sulfone 1 mol, naphthalene sulfone j't2 i 'r. =(condensation product of 0.2 to 0.7 mol of phenolsulfonic acid and 0.7 to 1.1 mol of porno, alphydride or its J4
(!I'rK /I-7 enol sulfone (
+1. 0.2 5~[J. 5-1' = condensation product of
, 111 bow is 11 years old), C4.4'-
Dihi 1, SrJ condensation product 'I' of 17 sulfonic acid of diphenyl sulfone and 0.5 to 1 mole of forno-N aldehibi! /I can (listen to the salt one by one) in a nice manner.

This compound C) has a known order of -i'. l(
There are nine products available.

'l! 1'-Q'v Modern condensation polymer compounds of aromatic sulfonic acids, such as NBS from Bayer AG,
1,'J,. , 51 It is possible to use a condensation polymer compound of sulfonic acid, and a).

1Jk Example 1.

Thickness 0. 5 rqrs on a Pyrex substrate with a thickness of 0.7 μm,
8), and after performing line exposure using the photomask of Jh')j, it was developed with warm water, the unbleached edge was eluted and removed, and the edge of the process was removed. This was dyed with yellow pigment (Sminol Milling Yellow MR: Sumitomo Chemical Co., Ltd., Tai) to form a yellow relief of the shape NojLcL.

Next, this is the product name: Mesit,ol NBS
Liquid (manufactured by T3AYAR) was diluted 40 times with warm water, adjusted to 40% with acetic acid, heated for 4 minutes in a resist dyeing room heated to 40'C, washed with water, and washed. After that, I dried it in a 150U oven for 30 minutes.

A cyan relief was further formed on the yellow relief which had been resist-dyed in this manner by a method similar to the method for forming the yellow relief. Here, the dye for dyeing cyan is Kayanor Milling Turkers Blue 6G (
Japaneseization; lid;

Colors formed as above)・17 Kazy filter G↑1, cyan, yellow, clean (height of cyan and yellow, edge part), white (non-relief part)
Ka Jr, regular, (Jlij'i order arranged i)
I'm standing there. Famous color spectroscopy! Multi υ of 11r items
1 light ν; 1 micro 4) μ・expansion\4 S 1) (manufactured by NJ Linnos Co., Ltd.) TE3 p m Heemson I? Tsul
In ancient times, cyan and yellow il, '+ colors were not used at all.

Comparison amount 1 Fruit/1i except for excluding the resisting treatment described in Example 1
As a result of forming a °C color separation color filter according to LifMell 1 and measuring the spectral '1v property, it was found that cyan and yellow were clearly mixed with each other.

From this, by carrying out the resist dyeing process described by the main brother, during the fan dyeing of the second color, the yellow relief of the first color moon will not be dyed with cyan nakate-1 (resist dyeing 1 cow) and the first color will not be dyed. The yellow color of the color is not dyed.
It was found that it has an effect of +>.

[Brief explanation of the drawing]

Figure 1 (a) - 0□) is a tree, C'; i, ll l; rfQ.
! Figure 2 is a book! t, 'It') fl mouth fruit t1'11
In the cross section 11■1 figure showing 1/1], -6゜15 (1, 1, 11 are), (2 plates, 2,7 are /i'g)Y; gender f'' J +i'l'lj j・:)
, 4 and 8 are reliefs, and 5.6.9.12.13 are dyed reliefs. Agent: Patent attorney (8107) Kiyoshi Takashi Viaki (and 6 others)
Name) Figure 1 @ Figure 2 Procedure Supplementary City Book It”fi4157 '11 [Mon/3119 Temple, i'1
1jl-4'Iha] in 1+-A phase Daidono ('l'111111"il'? 1no111・-,-
! , (u)Y; How to manufacture a filter θ, 3, r+
1M ishij 'J'''-J, °j in 1'l and (
For sol I, i Post '1. i',, 1st 1st [1 person 1'l
“IJ・(ri2U) Hatashi FFJ Shin Film Co., Ltd. 1
1. Agent〒1110 11 1'li width! +4: fli'-r daill 1 ward if noka gate 3 'J'l l 2if; 5 bow j, 1
No is L'+'j Hill 321"1r)・I is inside IILIlljJjI-i 'tIA1':"IN'
T! 491. +7, Supplementary i [father of] CS and Akii, lI1;'s review of 1 invention; 1; 1's 4Mf
i8, Contents of Sodeyama 1) Mei IY (llft No. 6 Tei 8 Yume's "・Government" of course "
... Koru +1)?'' he asked. 2) [...“1・l',
L-+1 points or 1,'' is changed to ``...there are points that I know.''
and h, il-no 4) 3.3) 1JLI'1llj
ll 8 Di 10th line nor 2t) Doλ-is
, oooXJ is ``[200U 1-I5 OU 00 people'' and 7+i eyes 1-J. 4) Bright + Fll eyes! i-;:I P4167-11'' 1...Kuri I4 Ezu. ” as “...Kuriga$zu.” and F111tun-J 2. .

Claims (5)

[Claims] (1)ノ+',=11 on the board? F'
Manufacture of polychromatic optical filter consisting of v-reflection;:'i
In the final method, the polymer relief dyed in the previous step is treated with an acidic aqueous solution of a condensed polymer compound of aromatic sulfonic acid.
A method for manufacturing a polychromatic optical filter, characterized in that it is treated with T(7t,;i). (2) Substrate” second yl? After forming the relief into a mosaic or stripe shape, this is divided into a predetermined portion)C3)
Production of polychromatic optical filter comprising repeating the dyeing process with a dye having T7 property at least twice - J
In the J method, the polymer relief dyed in the previous step is treated with an acidic aqueous solution of a condensed polymer compound of aromatic sulfonic acid after heating and cooling at 150 to 180 C. A method of manufacturing a color optical filter. (3) r of 1111 polymer compound of aromatic sulfonic acid
The rR aqueous solution is characterized by being an rR aqueous solution with a pH of 5.5 or less! 1. Effect''Claim81'!:
(Term 11 or (21, ILT!:L: I:1.'
'i:'i method for manufacturing a polychromatic optical filter. (4) The condensation polymer compound of aromatic sulfonic acid has the following general formula (% formula %) where H represents a benzene or naphthalene group,
X is water rl? 2 groups: no-rogen; C1-C4 alkyl; coort; ciio; c1-C4 alkoxy; CL, <4 alkyl or halogen; 1i
'i4j'% to the phenomenon that may be done;C1~C
4 alkyl or halogen-substituted triazinylamino (this triazinyl group is mono-positive, C1-C6 algylamino, mono- or di-oxyethylamino, phenylamino or sulfonylamino, etc.) further f:r;, may be replaced); y Y ■ (), 10 a S) IJ-to5o2-; or (M
O3S)r]-B-C1(=CH-, where Y
represents water, H1-011, 2) Ross 1=, 01 to C4 alkylamino), M is hydrogen, alkali metal,
45 is ammoniumuno wo (I, m represents 0.1 or 2, and n is 2 (audience/, X is 1 or II' amount - or 1'j-), 11 represents 1 to 4, a product consisting of at least one of the compounds represented by [Claim 1'lll'S] The poly(Δ
Method of manufacturing optical filters. (5) A condensation polymer compound of aromatic sulfonic acid is a condensation product of sulfonic acid of aromatic sulfonic acid and formaldehyde S, or a salt thereof, or phenol sulfo/acid or naphthalene sulfone ri
A condensation product of 2 and 4.4'-I 90-oxydiphenyl sulfone and formaldehyde or a salt thereof! A method for producing a polychromatic optical filter according to claim (1) or (2), characterized in that the filter is white.