CN110819134A - Metal complex organic dye, color photoresist composition and application thereof - Google Patents

Metal complex organic dye, color photoresist composition and application thereof Download PDF

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CN110819134A
CN110819134A CN201911144470.4A CN201911144470A CN110819134A CN 110819134 A CN110819134 A CN 110819134A CN 201911144470 A CN201911144470 A CN 201911144470A CN 110819134 A CN110819134 A CN 110819134A
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color
organic dye
metal complex
complex organic
resin
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李颖
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TCL Huaxing Photoelectric Technology Co Ltd
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TCL Huaxing Photoelectric Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B6/00Anthracene dyes not provided for above
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00Complex metal compounds of azo dyes
    • C09B45/01Complex metal compounds of azo dyes characterised by the method of metallisation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00Complex metal compounds of azo dyes
    • C09B45/02Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14Monoazo compounds
    • C09B45/22Monoazo compounds containing other metals
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The invention provides a metal complex organic dye, a color photoresist composition and application thereof. The molecular structure of the metal complex organic Dye provided by the invention contains a calcium sulfonate group, a barium sulfonate group or a magnesium sulfonate group with poor water solubility, so that a metal slightly soluble salt complex is formed, the metal slightly soluble salt complex has better solvent resistance and water resistance, a small molecular compound is still formed although the solubility is reduced, a crystal structure cannot be formed or solid particles cannot be precipitated in a color photoresist composition, the metal slightly soluble salt complex still has high penetration and high coloring capability of a common small molecular Dye, and meanwhile, the heat resistance stability is improved.

Description

Metal complex organic dye, color photoresist composition and application thereof
Technical Field
The invention relates to the technical field of display, in particular to a metal complex organic dye, a color photoresist composition and application thereof.
Background
A Thin Film Transistor Liquid Crystal Display (TFT-LCD) has many advantages such as a Thin body, power saving, and no radiation, and is widely used. Most of the existing liquid crystal display devices in the market are backlight liquid crystal display devices, which include a liquid crystal display panel and a backlight module (backlight module). Generally, a Liquid Crystal display panel is composed of a Color Filter (CF) substrate, a TFT array substrate, a Liquid Crystal (LC) and a Sealant (Sealant) sandwiched between the Color Filter substrate and the TFT array substrate; the molding process generally comprises: front Array (Array) process, CF process (film, yellow light, etching and stripping), middle Cell (TFT Array substrate and CF substrate bonding), and back Module assembly (Module) process (driving IC and printed circuit board bonding); wherein, the front-stage Array process mainly forms a TFT substrate to control the movement of liquid crystal molecules; the front CF process mainly forms a CF substrate; the middle Cell process is mainly to add liquid crystal between the TFT substrate and the CF substrate; the back module assembly process mainly drives the integration of IC pressing and printed circuit board, and further drives the liquid crystal molecules to rotate and display images.
The CF substrate is a main device used by the LCD to realize color display, and its basic constitution generally includes: a glass substrate, a Black Matrix (BM), a color filter layer, etc. The color filter layer achieves a color display effect mainly through the color photoresist, light emitted by the backlight source is modulated by liquid crystal molecules and enters the CF substrate, red (R) photoresist, green (G) photoresist and blue (B) photoresist of the color filter layer on the CF substrate are used for filtering, red, green and blue light rays are respectively displayed, and the photoresists of different colors respectively transmit light of corresponding color wave bands, so that the color display of the display is realized.
In the color filter layer, the main components of a general color resist include a colorant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and the like, wherein the colorant plays a role of dyeing in the color resist, and is generally an organic pigment (pigment) or a novel organic Dye (Dye). The organic pigment is the most widely applied color photoresist material in the TFT-LCD industry at present due to the characteristics of excellent sun resistance, water immersion resistance, acid resistance, alkali resistance, organic solvent resistance, heat resistance, stable crystal form, dispersibility, covering power and the like. However, in recent years, with the development of high-penetration high-contrast technology in the TFT-LCD industry, pigment-based color photoresist materials have not been able to meet the needs of the industry. Due to the small molecular structure of Dye, light scattering is not easy to occur in the photoresist material, so that the influence on the transmittance and the contrast can be reduced, and the Dye becomes a research hotspot in recent years. However, due to the small molecular structure of Dye and its high solubility in organic solvents and water, the solvent resistance and water resistance of Dye are poor, so that after exposure of a color photoresist material, Dye is easily washed away by a developing solution in a subsequent developing process; in addition, Dye may enter into the protective film in a more subsequent process of coating the protective film. Both of the above two situations can cause significant color floating, color shift and even pollution problems to the pixel unit.
Disclosure of Invention
The invention aims to provide a metal complex organic Dye, which belongs to a metal slightly soluble salt complex, has high water resistance and solvent resistance, can effectively solve the problems of color film flooding made of a photoresist containing Dye components and color cast in the subsequent process, and improves the display quality of a display device.
The invention also aims to provide a color photoresist composition, wherein the colorant comprises the metal complex organic Dye, so that the problems of color film flooding and color deviation in the subsequent process, which are produced by using the photoresist containing Dye components, can be effectively solved, and the display quality of a display device is improved.
The invention also aims to provide a color photoresist which is prepared by adopting the color photoresist composition, can effectively solve the problems of color flooding of a color film prepared by using the photoresist containing Dye components and color deviation in the subsequent process, and improves the display quality of a display device.
The invention also aims to provide a color film substrate which comprises the color photoresist, can effectively solve the problems of color film flooding made of the photoresist containing Dye components and color cast in the post-processing process, and improves the display quality of a display device.
The invention also aims to provide a display device which comprises the color film substrate, can effectively solve the problems of color film flooding made of the photoresist containing Dye components and color cast in the post-processing process, and improves the display quality of the display device.
In order to achieve the above object, the present invention provides a metal complex organic dye, which is applied to a color photoresist and has a molecular structure containing a calcium sulfonate group, a barium sulfonate group, or a magnesium sulfonate group.
Alternatively, the metal complex organic dye has a general molecular structure formula as shown in formula I:
wherein R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2+Or Mg2+
Alternatively, the metal complex organic dye has a general molecular structure formula as shown in formula II:
wherein R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure BDA0002281792290000033
2<n2<12, R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2Or Mg2+
Alternatively, the metal complex organic dye has a general molecular structure formula as shown in formula III:
Figure BDA0002281792290000034
wherein R2 is- (CH)2)n3CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、
-NHR、-SO3Na、-SO2NH2、-NO2
Figure BDA0002281792290000041
0<n3<12, R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure BDA0002281792290000043
2<n2<12, R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2Or Mg2+
Alternatively, the metal complex organic dye has a general molecular structure formula as shown in formula IV below:
Figure BDA0002281792290000044
wherein R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure BDA0002281792290000045
2<n2<12, R is CH3(CH2)n1,n1<6;
R2 is- (CH)2)n3CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2
Figure BDA0002281792290000046
Figure BDA0002281792290000047
0<n3<12;
R3 is R1, R2,
Figure BDA0002281792290000051
Figure BDA0002281792290000052
A is Ca2+、Ba2Or Mg2+
The invention also provides a color photoresist composition, which comprises a coloring agent, resin, an initiator, a monomer and a dispersing agent;
wherein the colorant comprises a metal complex organic dye as described above.
The resin comprises one or more of acrylic resin, epoxy resin, polyolefin resin, polyester resin, phenolic resin and urea resin.
The invention also provides a color photoresist which is obtained by adopting the color photoresist composition.
The invention also provides a color film substrate which comprises a substrate base plate and the color light resistor positioned on the substrate base plate.
The invention also provides a display device which comprises the color film substrate.
The invention has the beneficial effects that: the molecular structure of the metal complex organic Dye provided by the invention contains a calcium sulfonate group, a barium sulfonate group or a magnesium sulfonate group with poor water solubility, so that a metal slightly soluble salt complex is formed, the metal slightly soluble salt complex has better solvent resistance and water resistance, a small molecular compound is still formed although the solubility is reduced, a crystal structure cannot be formed or solid particles cannot be precipitated in a color photoresist composition, the metal slightly soluble salt complex still has high penetration and high coloring capability of a common small molecular Dye, and meanwhile, the heat resistance stability is improved. According to the color photoresist composition provided by the invention, the colorant comprises the metal complex organic Dye, so that the problems of color film flooding made of the photoresist containing Dye components and color cast in the later process can be effectively solved, and the display quality of a display device is improved. The color photoresist provided by the invention is obtained by adopting the color photoresist composition, can effectively solve the problems of color film flooding made of the photoresist containing Dye components and color cast in the post-processing process, and improves the display quality of a display device. The color film substrate provided by the invention comprises the color photoresist, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of a display device is improved. The display device comprises the color film substrate, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of the display device is improved.
Detailed Description
To further illustrate the technical means adopted by the present invention and the effects thereof, the following detailed description is given with reference to the preferred embodiments of the present invention.
The invention firstly provides a metal complex organic dye which is applied to a color photoresist and has a molecular structure containing a calcium sulfonate group, a barium sulfonate group or a magnesium sulfonate group.
The molecular structure of the metal complex organic dye contains a calcium sulfonate group, a barium sulfonate group or a magnesium sulfonate group with poor water solubility, thereby forming a metal slightly soluble salt complex, having better solvent resistance and water resistance, and being a small molecular compound although the solubility is reduced, does not form a crystal structure or precipitate to form solid particles in the color photoresist composition, thereby having better solvent resistance and water resistance of the pigment, high penetration and high coloring capability of common micromolecule dye, simultaneously improving the heat resistance stability, in the developing process of the color film process of the display device and the film forming process of the post-process, the color film is difficult to be brought out from the color photoresist by water and other organic solvents, the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-process can be effectively solved, and the display quality of the display device is improved.
Specifically, the solubility of the metal complex organic dye of the present invention can be adjusted by adjusting the contents of the calcium (Ca), magnesium (Mg), barium (Ba) salt functional groups of the sulfonic acid group.
In addition, the metal complex organic dye of the invention is prepared by introducing calcium ions (Ca) into the molecular structure of common small molecular dye2+) Magnesium ion (Mg)2+) Or barium ion (Ba)2+) The structure of the metal micro-soluble salt complex does not change the conjugation degree of the primary dye molecules, so that the absorption wavelength of the molecules does not change greatly, the chromatic light and the transmission spectrum are still determined by the structure of the coupling components in the primary dye molecules, the influence of metal ions is not obvious, and the chromatic light is deepened only by a certain color-assisting effect.
Example 1
The molecular structure general formula of the metal complex organic dye is shown as the following formula I:
Figure BDA0002281792290000071
wherein R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2+Or Mg2+
Example 2
The molecular structure general formula of the metal complex organic dye is shown as the following formula II:
Figure BDA0002281792290000072
wherein R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure BDA0002281792290000073
2<n2<12, R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2Or Mg2+
Example 3
The molecular structure general formula of the metal complex organic dye is shown as the following formula III:
Figure BDA0002281792290000074
wherein R2 is- (CH)2)n3CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2
Figure BDA0002281792290000081
Figure BDA0002281792290000082
0<n3<12, R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure BDA0002281792290000083
2<n2<12, R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2Or Mg2+
Example 4
The molecular structure general formula of the metal complex organic dye is shown as the following formula IV:
Figure BDA0002281792290000084
wherein R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、2<n2<12, R is CH3(CH2)n1,n1<6;
R2 is- (CH)2)n3CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2
Figure BDA0002281792290000092
0<n3<12;
R3 is R1, R2,
Figure BDA0002281792290000093
Figure BDA0002281792290000094
A is Ca2+、Ba2Or Mg2+
Based on the metal complex organic dye, the invention also provides a color photoresist composition which comprises colorant resin, an initiator, a monomer, a dispersant, other additives and the like.
Wherein the colorant comprises a metal complex organic dye as described above.
Specifically, the resin includes one or more of acrylic resin, epoxy resin, polyolefin resin, polyester resin, phenol resin, and urea resin.
According to the color photoresist composition, the colorant comprises the metal complex organic Dye, so that the problems of color film flooding made of the photoresist containing Dye components and color cast in the later process can be effectively solved, and the display quality of a display device is improved.
Based on the color photoresist composition, the invention also provides a color photoresist which is obtained by adopting the color photoresist composition.
The color photoresist provided by the invention is obtained by adopting the color photoresist composition, can effectively solve the problems of color film flooding made of the photoresist containing Dye components and color cast in the post-processing process, and improves the display quality of a display device.
Based on the color photoresist, the invention also provides a color film substrate which comprises a substrate and the color photoresist positioned on the substrate.
The color film substrate provided by the invention comprises the color photoresist, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of a display device is improved.
Based on the color film substrate, the invention also provides a display device, which comprises the color film substrate.
The display device comprises the color film substrate, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of the display device is improved.
In summary, the molecular structure of the metal complex organic Dye provided by the invention contains a calcium sulfonate group, a barium sulfonate group, or a magnesium sulfonate group with poor water solubility, thereby forming a metal slightly soluble salt complex, which has better solvent resistance and water resistance, and although the solubility is reduced, the metal slightly soluble salt complex is still a small molecular compound, a crystal structure cannot be formed or solid particles cannot be precipitated in a color photoresist composition, the metal slightly soluble salt complex still has high penetration and high coloring capability of common Dye small molecules, and meanwhile, the heat resistance stability is improved, the metal slightly soluble salt organic Dye is difficult to be brought out from color photoresists by water and other organic solvents in the developing process and the film forming process of a color film process of a display device, the problems of color flooding of the color film made of the Dye component photoresist and color deviation in the post-process can be effectively improved, and the display quality of the display device is improved. According to the color photoresist composition provided by the invention, the colorant comprises the metal complex organic Dye, so that the problems of color film flooding made of the photoresist containing Dye components and color cast in the later process can be effectively solved, and the display quality of a display device is improved. The color photoresist provided by the invention is obtained by adopting the color photoresist composition, can effectively solve the problems of color film flooding made of the photoresist containing Dye components and color cast in the post-processing process, and improves the display quality of a display device. The color film substrate provided by the invention comprises the color photoresist, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of a display device is improved. The display device comprises the color film substrate, so that the problems of color film flooding made of the photoresist containing Dye components and color deviation in the post-processing process can be effectively solved, and the display quality of the display device is improved.
As described above, it will be apparent to those skilled in the art that various other changes and modifications can be made based on the technical solution and the technical idea of the present invention, and all such changes and modifications should fall within the protective scope of the appended claims.

Claims (6)

1. The metal complex organic dye is characterized in that the metal complex organic dye is applied to a color photoresist, and the molecular structure of the metal complex organic dye contains a calcium sulfonate group, a barium sulfonate group or a magnesium sulfonate group;
the general formula of the molecular structure is shown as the following formula III:
Figure FDA0002281792280000011
wherein R2 is- (CH)2)n3CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2
Figure FDA0002281792280000012
Figure FDA0002281792280000013
0<n3<12, R1 is- (CH)2)n2CH3、-H、-F、-Cl、-Br、-OH、-NH2、-COOR、-NHR、-SO3Na、-SO2NH2、-NO2、-Ph、
Figure FDA0002281792280000014
2<n2<12, R is CH3(CH2)n1,n1<6;
A is Ca2+、Ba2Or Mg2+
2. A color photoresist composition is characterized by comprising a coloring agent, a resin, an initiator, a monomer and a dispersing agent;
wherein the colorant comprises the metal complex organic dye of claim 1.
3. The color resist composition according to claim 2, wherein the resin comprises one or more of an acrylic resin, an epoxy resin, a polyolefin resin, a polyester resin, a phenol resin, and a urea resin.
4. A color resist obtained by using the color resist composition according to claim 2 or 3.
5. A color filter substrate, comprising a substrate base plate and the color photoresist according to claim 4 on the substrate base plate.
6. A display device comprising the color filter substrate according to claim 5.
CN201911144470.4A 2017-07-07 2017-07-07 Metal complex organic dye, color photoresist composition and application thereof Pending CN110819134A (en)

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