JPS6225171A - Blue dye composition - Google Patents

Abstract

PURPOSE:The titled composition especially suitable for dyeing a resin relief such as gelatin relief, etc., to give a blue colored resin film, containing triphenylmethane blue dye and phthalocyanine blue bye in a specific ratio. CONSTITUTION:The aimed dye composition consisting of (A) 1pt.wt. tripheylmethane blue dye (preferably CI Acid Blue 83, 90, 93, 100, 103 or 104) and (B) 0.2-5pts.wt. phthalocyanine blue dye (preferably CI direct blue 86, 90, 95, CI Active Blue 7, 9, 13, 14, 40, 38 or 41).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to blue dye compositions. More specifically, the present invention relates to a blue dye composition particularly suitable for dyeing a resin relief such as a gelatin relief to form a blue resin layer in the production of a micro color filter for a color imaging device.

[Background of the Invention] In VTR cameras and the like, micro color filters installed in the light receiving section of the imaging device to extract color signals corresponding to color images are made of gelatin, casein,
Alternatively, a resin relief (cured resin film formed as a pattern) prepared from a water-soluble synthetic polymer compound or the like is colored with a dye, and several layers of colored resin films are superposed one on top of the other. That is, when using the additive color method, blue, green, and red dyes are used, and when using the subtractive color method, the three colors cyan, yellow, and magenta are used.

Until now, when a resin relief is dyed blue to obtain a blue-colored resin film for a microcolor filter, a triphenylmethane-based blue dye, which has excellent spectral properties as a blue dye, has generally been used. However, according to studies conducted by the present inventors, triphenylmethane-based blue dyes tend to dye other than the desired resin relief, and as a result, the spectral characteristics of colored resin films in other colors, such as green and red, are degraded. It turns out that there are some drawbacks.

The resin relief is manufactured by a series of methods including formation of a photocurable resin film, exposure through a photomask having a light-transmitting part, and development. In this case, ideally the cured resin film remains only on the exposed area (relief pattern area),
It is desirable that no cured resin film remains in other areas, but in reality, a small amount of cured resin film (so-called residual 11!2) often forms in areas other than the exposed areas.
The figure shows the generated relief patterns (1a, lb, lc)
FIG. 3 is a diagram schematically showing the remaining films (2a, 2b, 2c).

According to research by the present inventor, when the cured resin film obtained as described above is dyed blue using triphenylmethane-based blue dye 1, relief patterns (la, la,
It was found that not only the remaining films (lb, lc) but also the remaining films (2a, 2b, 2c) tended to be colored blue. Next, a green colored resin film, a red colored resin film, etc. are formed on top of this remaining film. It clearly deteriorates the spectral characteristics of colored resin films, etc. Therefore, a problem arises in that the resolution of the resulting microcolor filter is reduced.

On the other hand, dyes of other colors used for dyeing colored resin films have a low tendency to stain the remaining film. In order to reduce the influence of the residual colored film on the resolution of the micro color filter, the order is usually to first form a blue colored resin film, and then to form a green colored resin film, a red colored resin film, etc. as an upper layer. was forced to take. However, even with these measures, the adverse effect of the blue dyed residual film on the resolution of the microcolor filter could not be sufficiently avoided.

In order to prevent the formation of residual films, methods for suppressing the dark reaction of the photocurable resin film (coated film), methods for reducing exposure to light for curing, adjustment of development conditions, or conditions for rinsing after dyeing are used. However, it is extremely difficult to reliably prevent the formation of residual film using these methods.

[Object of the invention] The present invention provides a blue dye composition particularly suitable for dyeing a resin relief such as a gelatin relief to form a nine-color colored resin film in the production of a micro color filter for a color imaging device. The purpose is to

An object of the present invention is to provide a blue dye composition that is less likely to stain residual films, particularly when dyeing resin reliefs such as gelatin reliefs.

[Summary of the Invention] The present invention provides a blue dye composition comprising 1 part by weight of a triphenylmethane blue dye and 0.2 to 5 parts by weight (preferably 0.5 to 3 parts by weight) of a phthalocyanine blue dye. It is what it is.

[Effects of the Invention] The blue dye composition of the present invention easily dyes resin reliefs such as gelatin reliefs in the same way as ordinary triphenylmethane blue dyes, and is dyed in the same manner as ordinary triphenylmethane blue dyes. While it exhibits almost the same spectral characteristics as the micro color filter, it also exhibits behavior that makes it difficult to stain the residual film that is generated along with it.Therefore, the resolution of the resulting micro color filter is maintained at a high level.

In addition, the blue dye composition of the present invention has the advantage that it is difficult to dye the residual film, so it can be used as a blue colored resin layer, which has been forced to be the first layer in the conventional micro color filter manufacturing process. The formation can be performed after the formation of other colored resin layers. Therefore, there is an advantage that the degree of freedom in the manufacturing process of micro color filters is dramatically increased.

[Detailed Description of the Invention] According to the present invention, a blue dye composition containing a triphenylmethane blue dye and a phthalocyanine blue dye in an amount within a specific range is used as a blue dye for manufacturing micro color filters. By using this method, a blue colored resin film can be prepared without impairing the excellent spectral properties of the triphenylmethane blue dye as described above, and the spectral properties of other colored resin films will not be degraded. .

Triphenylmethane-based buffer used in the present invention
□Rue dyes can be selected arbitrarily from known ones.
:Jru. Examples include the following triphenylmethane blue dyes.

222l Yuiejeni'' Kayanor Rei Cyanine 6B [Kyaku] Solar Cyanine 6B Conch [Resident] Sumitomo Brilliant Indocyanine 6Bh/c [Resident Kingdom] Coomassie Brilliant) - Blue R [ICI]
l Supranol Cyanine 6B [FBy]・Soluble Blue 〇BB [One five more than Oriento] "22 Ridan" Supranor Cyanine 78F [FBy] 2222 above Enni""" Sumitomo Brilliant Blue 5G [Inhabitant Kingdom] Brilliant India Blue 5G [FH] Men L Nishi 2 E Ki 2”” Ashiran Φ Brilliant Blue F F R [FByl
In addition, the display in square brackets at the end of the above-mentioned compound examples means the name of the supplier, and is as shown in t and d, respectively.

[Kayaku]: Nippon Kayaku ■ [Resident]: Residence Chemical Industry ■ [Resident Kingdom]: Residence Sanda Chemical Industry ■ [ICI]: Imperial Chemical Industry [FByl: Falpen Fabriken I (Inil [S] :Sand [+1)↑Soto] ・Narient Chemical T Industry■ [FH]
: Farb Berghöchst Next, the phthalocyanine blue dye used in the present invention can be arbitrarily selected from known dyes. Examples include the following phthalocyanine blue dyes.

CI Direct Blue 86 Eisen Brimuraken Turkey's Blue-GLH [Hodogaya] Cupro Cyanine Blue GL [Toyo] Guibogensha Turkey's Blue S [Dainippon] Direct 7 Ast Cyanine-Blue L [Takaoka] Kayaras・Turkey's Blue 〇L [Kayaku] Kiwa Turkey's Blue GL [Kiwa] Nankai Redirect
Fast Cyanine □Blue GL [Nanga] Phthalocyanine Blue G Conch [Usu] Sanyo
Turkey's Blue BLR [Mountain Area] 'Sanyo Cyanin Blue SBR Conch-B [Sanyo] Sumilite Shupra Turkeys Blue G Conch [Resident] Sumilight Shupra Turkeys Competition Blue FB Conch [Resident] Area Mina Contest Kai Turkeys G [Acna] Sirius Shubra Turkeys Blue 〇L [FBy
l Solar Turkeys Blue 〇LL [S] Sirius, Shupra Turkeys Blue FBLT, [FBV
] CI Direct Blue 90 Kayaras Shupra e Blue FGL-Conch "Kayaku" Sumilite Shupra Blue FGL [Resident] Solar Blue FGL [S] CI Direct Blue-98 Sumilite Kai Shupra Number Blue FBGL [Resident] Sirius Shupra・Blue FBGL [FByl Sorophenyl ・Blue AGL [Gy] CI Reacti
Buburu-7 Prussian Book Turkeys H-G [(IIF Cipacron-Turkeys Competition Blue G -E [CIBA] Prussian Competition Turkeys H-G [ICI] CI Reactibu Blue 9 Mikasian Navy Fist Blue 3R3 [Kyaku] Mikasian φ Ney B Blue 3R3 [=ICI Reactive Blue 13 Prussian Blue H-5R [Kayaku] Cibacron Blue 2 RA [CIBA] Prussian Blue H-5R [ICI] cr Reactive Blue 14 Cibacron φ Brilliant Blue F C4G - P [CrBA] CI Reactive Blue-40 Prussian Navy Blue H-4R [Kayaku] Cibachron Fist Navy ◆ Blue F R-E [CIBA
l Prussian fist navy blue H-4R [ICI] C
I Reactive Blue 38 Diamira Brilliant Competition Green 6B [Mitsubishi] Leman' Le Brilliant Competition Green 6 B [F Old 9 Area Active Blue 41 Cibachron Turkey Blue 2G -E [CIB
In the examples of the compound A]-1-, the display in square brackets at the end means the name of the supplier as in the above case, and the other display is as follows.

[Hodogaya]: Hodogaya Chemical Co., Ltd. ■ Toyo 1: Toyo Ink ■ [Dainippon]: Dainippon Ink Chemical Industry ■ [Takaoka]: Takaoka Chemical Co., Ltd. [Kiwa]: Kiwa Chemical Industry ■ [Sankai]: Sankai Dye Manufacturing ■ [Usu] : Usu Chemical Industry ■ [Yamakawa] : Depth dye ■ [Acna] : Azinde Color Pear, Naru [G
y] :Geigy [Mitsubishi] :Mitsubishi Chemical Industries, Ltd. [CIBA] :Chipasai Limited In the blue dye composition of the present invention, 0.2 to 0.2 to 100% of phthalocyanine blue dye is added to 1 part by weight of triphenylmethane blue dye. 5 parts by volume (preferably 0.5 to 3 parts by volume) is blended.

If the amount of phthalocyanine blue dye blended is too small,
The main objective of the present invention, which is to prevent staining of residual film, may not be achieved sufficiently, and if the amount of phthalocyanine blue dye blended is too large, the composition contains triphenylmethane blue dye. is relatively small, making it difficult for the triphenylmethane-based blue dye to exhibit its preferable spectral characteristics.

Note that the blue dye composition of the present invention may also contain dyes other than the triphenylmethane blue dye and the phthalocyanine blue dye, as long as it does not contradict the above aspect of the present invention. Additionally, there are two similar types of triphenylmethane blue dyes and phthalocyanine blue dyes.
1- It goes without saying that they may be used in combination.

When using the blue dye composition of the present invention as a blue dye for manufacturing microcolor filters, the same operations and conditions as for dyeing operations using ordinary triphenylmethane blue dyes can be used.

Next, Examples and Comparative Examples of the present invention will be shown.

[Example 1] A dichromate gelatin photocurable resin film with a thickness of 0.71 Lm was provided on a transparent glass substrate, a mask (exposure pattern) consisting of a mosaic pattern was placed on top of this, and contact exposure was performed. Next, the exposed resin layer is washed with hot water,
The uncured resin portion was eluted and removed (developed), leaving a cured resin layer consisting of mosaic-like convex portions.

The above cured resin layer was dyed blue using a blue dyeing solution with the following formulation.Triphenylmethane blue dye (CI Acid Blue 83) 0.012% by weight
Phthalocyanine blue dye (CI Reactive Blue 14) 0.025% by weight
Water (pH 3.3) After the remaining dyed resin film was sufficiently rinsed with a pH 3.3 rinse solution, it was dried to obtain a blue colored resin film.

The spectral transmittance of the unstained part (the part where the blue colored convex resin film is not present) of the transparent glass substrate on which the blue colored resin film was formed by the above method was measured using a micro spectrometer (MMSP, Olympus The measurement was carried out using an optical instrument (manufactured by Kogaku ■).

The measurement results are shown as spectrum A in Figure 2.As is clear from this figure, the visible wavelength range (400 to 70
The transmittance of the unstained area at 0 nm) was approximately 100%.

[Comparative Example 1] The same treatment as in Example 1 was carried out, except that the blue dyeing treatment of the cured resin layer was carried out using a blue dyeing solution consisting only of triphenylmethane blue dye of the following formulation, and a blue colored resin film was obtained. A transparent glass substrate formed on the surface was obtained.

LfL Immunization A] Triphenylmethane blue dye (CI Acid Blue 83) 0.02% by weight Water - (pH 3,3) Balance The spectral transmittance of the undyed area of the transparent glass substrate obtained by the above method was Measurement was carried out in the same manner as in Example 1 using a spectrometer.

The measurement results are shown as spectrum B in Figure 2.As is clear from this figure, within the visible wavelength range, 510~
A maximum decrease in transmittance of 15% was observed in the 670 nm region. This is due to residual film staining in the unstained area.

[Example 2] A transparent glass substrate on which the blue colored resin film obtained in Example 1 was formed was treated with an acetic acid tannic acid aqueous solution (containing 0.3% by weight of tannic acid and 1% by weight of acetic acid) at 40°C. After 2 minutes of immersion in an aqueous solution of antimonylic acid and 0.25% of acetic acid, the solution was immersed in an aqueous solution of 1.0% by weight and 0.25% of acetic acid.
The blue colored resin film was subjected to resist dyeing treatment by being immersed in an aqueous solution (containing 5 parts by weight) for 2 minutes.

Next, a green colored resin film was formed on top of the resist-dyed blue colored resin film by adjusting the alignment by a conventional method. The green colored resin film was formed by the same method as the method for producing the blue colored resin film, except that a green dyeing solution having the following formulation was used.

W Blood ﾾ Hill Wataru A' CR Acid Green 16 0.7% by weight CI Direct Ie O-10, 088% by weight, li% 'Water (pH 4,4) The remainder Green colored resin film on transparent glass substrate obtained by the above method The spectral transmittance of the region was measured in the same manner as in Example 1 using a micro spectrometer. The measurement results are shown as spectrum C in FIG.

[Comparative Example 2] The blue colored resin film obtained in Comparative Example 1 was
Resistant treatment and green colored resin film form similar to Example 2 except that a transparent glass substrate formed on the □ surface was used.
A transparent glass substrate on which blue and green colored resin films were formed was obtained by acid treatment.

The spectral transmittance of the green colored resin film region of the transparent glass substrate obtained by the above method was measured in the same manner as in Example 1 using a micro spectrometer. The measurement results are shown as spectrum D in FIG.

As is clear from this figure, the spectral transmittance in the green wavelength region is higher than that of Example 2 in Comparative Example 2 (spectrum D).
(spectrum C). In other words, the decrease in spectral transmittance of the non-dyed area that appeared in Comparative Example 1 caused the decrease in the spectral transmittance of the green colored resin film (formed on the above-mentioned non-dyed area) obtained in Comparative Example 2. You can clearly see what it brings.

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing a relief pattern and a residual film generated in the manufacturing process of a micro color filter. FIG. 2 is a spectrum showing the spectral transmittance of the undyed portion of the transparent glass substrate on which a blue colored resin film was formed on the surface obtained in Example 1 and Comparative Example 1. FIG. 3 is a spectrum showing the spectral transmittance of the green colored resin film region on the surface obtained in Example 2 and Comparative Example 2. la, lb, lc Ni relief patterns 2a, 2b, 2c: Remaining film A: Spectrum B showing the spectral transmittance of the undyed part of the transparent glass substrate of Example 1: Spectrum of the undyed part of the transparent glass substrate of Comparative Example 1 Spectrum C showing the spectral transmittance: Spectrum D showing the spectral transmittance of the green colored resin film region of Example 2: Spectrum showing the spectral transmittance of the green colored resin film region of Comparative Example 2 Patent applicant: Fuji Photo Film Co., Ltd. Agent Patent Attorney Yasushi Yanagawa (Figure 1, Figure 2) (Tnm)

Claims (1)

[Scope of Claims] 1. A blue dye composition comprising 1 part by weight of a triphenylmethane blue dye and 0.2 to 5 parts by weight of a phthalocyanine blue dye. 2. The blue dye composition according to claim 1, wherein the phthalocyanine blue dye is contained in an amount of 0.5 to 3 parts by weight per 1 part by weight of the triphenylmethane blue dye. 3. The triphenylmethane blue dye belongs to any of CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 93, CI Acid Blue 100, CI Acid Blue 103, and CI Acid Blue 104. The blue dye composition according to claim 1 or 2, characterized in that: 4. Phthalocyanine blue dyes include CI Direct Blue 86, CI Direct Blue 90, CI Direct Blue 98, CI Reactive Blue 7, CI Reactive Blue 9, CI Reactive Blue 13, CI Reactive Blue 14, and CI Reactive. Blue 40, C
3. The blue dye composition according to claim 1 or 2, which is a phthalocyanine blue dye belonging to either I Reactive Blue 38 or CI Reactive Blue 41. 5. The blue dye composition according to claim 1 or 2, which is used for blue dyeing micro color filters.