CN108178839A - A kind of reflectance coating - Google Patents
A kind of reflectance coating Download PDFInfo
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- CN108178839A CN108178839A CN201810017687.8A CN201810017687A CN108178839A CN 108178839 A CN108178839 A CN 108178839A CN 201810017687 A CN201810017687 A CN 201810017687A CN 108178839 A CN108178839 A CN 108178839A
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- reflectance coating
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- black
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 241000251468 Actinopterygii Species 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000002310 reflectometry Methods 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
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- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- -1 photoinitiator Substances 0.000 claims description 4
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- 238000002360 preparation method Methods 0.000 claims description 4
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 43
- 239000004332 silver Substances 0.000 abstract description 43
- 229910052709 silver Inorganic materials 0.000 abstract description 43
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 abstract description 23
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 12
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- GMMAPXRGRVJYJY-UHFFFAOYSA-J tetrasodium 4-acetamido-5-hydroxy-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].OC1=C2C(NC(=O)C)=CC=C(S([O-])(=O)=O)C2=CC(S([O-])(=O)=O)=C1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 GMMAPXRGRVJYJY-UHFFFAOYSA-J 0.000 description 5
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- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
It the present invention relates to the reflective film material technical field of backlight LCD, while is also covered by needing the field of similar reflectance coating, specifically, is related to a kind of black reflectance coating of the slim anti-dirty high brightness silver of finger of high reliability.In order to solve the problems, such as that warpage is serious after the black reflectance coating reliability of existing high silver lustre, the present invention provides a kind of reflectance coating.The reflectance coating successively include hardening coat, priming coat, oxygen fish tail and waterproof layer, Ag layers, substrate layer, Al layers and ink layer.The surface of reflectance coating provided by the invention has high rigidity, excellent wearability, excellent soil resistance, solves the existing black reflectance coating of high silver lustre and is easily scratched by light guide plate, silver layer is caused to be aoxidized, so as to which backlight briliancy be caused to reduce the problem of even completely black；Reflectance coating provided by the invention is prepared using individual base material simultaneously, and warpage is serious after solving the problems, such as finished product reliability.
Description
Technical field
The present invention relates to the reflective film material technical field of backlight LCD, while it is also covered by needing the neck of similar reflectance coating
Domain specifically, is related to a kind of black reflectance coating of the slim anti-dirty high brightness silver of finger of high reliability.
Background technology
LCD is non-luminescent property display technology device, it is necessary to could show image using backlight.Therefore, backlight module
Development plays the role of the development of display vital.With present liquid crystal display towards ultrathin mode into
Row development, backlight module similarly towards light, thin, low-power consumption, high brightness, low cost on developed.
Backlight module is mainly by assemblings such as LED light source, lampshade, reflectance coating, light guide plate, diffusion barrier, brightness enhancement film and outline borders
It forms.The main function of reflectance coating is will to leak out the light high efficiency of light guide plate bottom and reflect without loss, so as to reduce light
Consume reduces electricity consumption, improves the light saturation degree of liquid crystal display.Therefore, the thickness of reflectance coating is reduced, reflectance coating is reduced and trusts
Property after warpage, improve reflectance coating assembling yield become important research topic.
The black reflectance coating of silver used at present, is belonged to and is prepared using compound technique, the shrinking percentage of two layers of substrate layer
Difference will largely influence the warpage after the black reflectance coating reliability of silver.Meanwhile as following machine is towards slim hair
Exhibition, existing thickness is 80 or 75 μm on the market, subsequently will be unable to meet the needs of client.Therefore, a kind of high reliability is prepared
There are its necessity for the slim dirty high black reflectance coating of silver lustre of anti-finger.
Invention content
In order to solve the problems, such as that warpage is serious after the black reflectance coating reliability of existing high silver lustre, the present invention provides a kind of reflection
Film.The surface of reflectance coating provided by the invention has high rigidity, excellent wearability, excellent soil resistance, solves existing
The high black reflectance coating of silver lustre is easily scratched by light guide plate, and silver layer is caused to be aoxidized, so as to which backlight briliancy be caused to reduce even completely black ask
Topic；Reflectance coating provided by the invention is prepared using individual base material simultaneously, and warpage is serious after solving the problems, such as finished product reliability.
In order to solve the above technical problem, the present invention provides following technical solutions：
The present invention provides a kind of reflectance coating, and the reflectance coating includes hardening coat, priming coat, oxygen fish tail and waterproof layer successively
(coating layers of Over), Ag layers, substrate layer, Al layers and ink layer.
The reflectance coating only includes one layer of substrate layer.
The reflectance coating is also known as the slim anti-dirty high black reflectance coating of silver lustre of finger of high reliability.
The reflectance coating is by hardening coat, priming coat, oxygen fish tail and waterproof layer (coating layers of Over), Ag layers, base material
Layer, Al layers and ink layer composition.
The hardening coat is also known as the dirty hardening coat of anti-finger, the dirty hardened layer of anti-finger, and it is black that ink layer is also known as anti-finger sump oil
Layer.
Compared to other compound silver reflectance coatings, reflectance coating provided by the invention belongs to individual silver-colored reflectance coating.
Further, in preparation process, the hardening coat is first configured to coating fluid.
The coating fluid is also known as hardening bath.
Further, the coating fluid of the hardening coat includes acrylic ester prepolymer, and acrylate monomer is light-initiated
Agent, fluorine element additive and organic solvent.
Fluorine element additive is also referred to as fluorine auxiliary agent.
Under UV lamp irradiation rapid polymerization occurs for the coating fluid of the anti-finger dirt hardening coat so that fluoride (fluorine element
Additive) matrix resin surface is floated on, so as to provide the anti-smoothness and soil resistance for referring to dirty hardening coat surface, acrylate is pre-
Functional group content can have a major impact the hardness of coating surface in polymers and monomer, and then influence the resistance to of the dirty hardening coat of anti-finger
Grind characteristic.
Further, the group of the one kind or the two of the material of the priming coat in acrylic resin or polyurethane
It closes.
Further, the material of the priming coat in aqueous polyurethane, solvent borne polyurethane, acrylic system one
Kind or at least two combination.
Further, the material of the oxygen fish tail and waterproof layer is selected from acrylate polymer.
Further, the one kind of the material of the oxygen fish tail and waterproof layer in acrylic system.
Further, it is prepared by the way of physical vapour deposition (PVD) for described Ag layers.
Further, the material of the substrate layer is selected from makrolon (PC), polyethylene terephthalate (PET)
One kind or combination of the two.
Further, the preferred polyethylene terephthalate of the material of the substrate layer (PET).
Further, the PET base material, using low-shrinkage transparent base.
Further, the ink layer, is prepared by the way of silk-screen.
Further, Ag layers of thickness is 30-80nm, and the thickness of substrate layer is 25-75 μm, and Al layers of thickness is 0-
60nm, the thickness of ink layer is 0.5-1.5 μm.
The thickness of hardening coat is 4 μm, and the thickness of priming coat is 0.1 μm, and the thickness of oxygen fish tail and waterproof layer is 0.2 μm.
By it is above-mentioned it is anti-refer to dirty hardening coat, priming coat, oxygen fish tail and waterproof layer, Ag layers, pet layer, Al layers and ink layer
Thickness limit within the above range, to after the final black reflectance coating reliability of high silver lustre warpage, assembling yield have it is more excellent
Management and control property.
Further, Ag layers of thickness is preferably 40-60nm.
Further, Ag layers of thickness is preferably 50nm.
Further, the thickness of PET base material layer is preferably 50-75 μm.
Further, Al layers of thickness is preferably 20-30nm.
Further, Al layers of thickness is preferably 30nm.
Further, the thickness of ink layer is preferably 0.7-1 μm.
Further, angularity when reflectance coating production is offline is 0-1mm, and the angularity after reliability is 0-3mm,
Reflectivity ＞ 96.0%.
The reflectivity refers to reflectivity when reflectance coating production is offline.
Further, the anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resins of 30 parts by weight
Prepolymer, 18 parts by weight, three official's polyurethane acrylic resin prepolymer, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight
Photoinitiator (photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is second
Acetoacetic ester.
The present invention also provides a kind of methods for preparing reflectance coating, the described method comprises the following steps：
(1) it is first pre-processed using high transparency base material, is then deposited Ag layers in the one side of base material；
(2) it is coated with oxygen fish tail and waterproof layer in Ag layer surfaces；
(3) one layer of priming coat is coated in oxygen waterproofing protection layer surface, for the coating of subsequent curing liquid；
(4) hardening bath is coated on priming coat, hardening coat is obtained after curing；
(5) in the another side evaporating Al layer of PET；
(6) it carries out covering protective film on hardening coat surface；
(7) by the way of silk-screen printing ink is printed at Al layers；
(8) slitting is carried out, packs shipment.
Further, the silk-screen number of the ink is 2-6 times.
Further, the silk-screen number of the ink is 3-4 times.
The ink is also known as anti-finger sump oil ink.
Compared with the existing high black reflectance coating of silver lustre, the surface of reflectance coating provided by the invention has high rigidity, excellent
Wearability, excellent soil resistance, simultaneously because this product is non-composite film, angularity≤3mm after material reliability, reflectivity
＞ 96.0%.
Reflectance coating provided by the invention realizes following technique effect：
1st, the coating of silver layer face is anti-refer to dirty hardened layer after, the characteristics of can realizing high-wearing feature, high rigidity, can avoid leading
Scuffing, scratch of the tabula rasa to reflector plate surface, play the role of the silver-colored reflectance coating of protection, while also do not scratch, scratch light guide plate, have
There is high reliability；
2nd, the anti-mode for referring to sump oil ink is republished after aluminium layer is deposited in PET base material layer, with high soil resistance, GOOD TASTE
Feature can reduce the influence for material yield such as finger pollution in assembling process；
3rd, the method that reflectance coating is prepared using individual base material is reduced the offline warpage with after reliability of material production, kept away
Exempted from present on the market the difficult to govern control of composite material warpage the problem of, so as to further improve the yield of complete machine assembling.
Description of the drawings
Fig. 1 is a kind of structure diagram of reflectance coating provided by the invention；
Fig. 2 is the structure diagram of the existing common black reflectance coating of high silver lustre of aluminizing；
Fig. 3 is the structure diagram of the black reflectance coating of high silver lustre of existing common tunica albuginea coating；
Fig. 4 is a kind of structure diagram of reflectance coating semi-finished product provided by the invention.
Wherein：
10：It is anti-to refer to dirty hardening coat, play wear-resisting, anti scuffing,
20：Priming coat,
30：Oxygen fish tail and waterproof layer,
40：Ag layers,
50：PET base material layer,
60：Al layers,
70：Ink layer,
80：PET base material layer or the tunica albuginea base material containing barium sulfate,
90：Hot dry glue composite layer.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combine.The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
In order to which the personnel for making correlative technology field are better understood from patent of the present invention, below in conjunction with the embodiment of the present invention and
Attached drawing carries out the technical solution in the embodiment of the present invention clear, complete description, it is clear that described is only the present invention
The embodiment rather than whole embodiments of a part.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
All other embodiments obtained under the premise of creative work are made, should all belong to the scope of protection of the invention.
It should be noted that in description and claims of this specification and above-mentioned attached drawing term " first ", "
Two " etc. be the object for distinguishing similar, and specific sequence or precedence are described without being used for.It should be appreciated that it uses in this way
Data can be interchanged in the appropriate case, so as to the embodiment of the present invention described herein.In addition term " comprising " and " having "
And their any deformation, it is intended that cover it is non-exclusive include, for example, containing series of steps or the mistake of unit
Journey, method, system, product or equipment are not necessarily limited to those steps or unit clearly listed, but may include unclear
It is that ground is listed or for other intrinsic steps of these processes, method, system, product or equipment or unit.
The reflectance coating of offer is be provided below in conjunction with embodiment.
The preparation method of reflectance coating provided by the invention includes the following steps：
(1) it is first pre-processed using high transparency base material, is then deposited Ag layers in the one side of base material；
(2) it is coated with oxygen fish tail and waterproof layer in Ag layer surfaces；
(3) one layer of priming coat is coated in oxygen waterproofing protection layer surface, for the coating of subsequent curing liquid；
(4) hardening bath is coated on priming coat, hardening coat is obtained after curing；
(5) in the another side evaporating Al layer of PET；
(6) it carries out covering protective film on hardening coat surface；
(7) by the way of silk-screen printing ink is printed at Al layers；
(8) slitting is carried out, packs shipment.
Further, the silk-screen number of the ink is 2-6 times.
Reflectance coating provided by the invention is tested for the property in accordance with the following methods：
Silver-colored face reflectivity：According to the standard of NIST 2054, light is divided using Agilent Cary5000 UV, visible lights near-infrared
Reflectivity of each silver-colored reflectance coating of degree measurement examination at 550nm.Silver face reflectivity refers to that surface layer refers to dirt firmly to be anti-in reflectance coating
Change laminated reflectivity.
Adhesive force：According to GB 1720-1979《Paint film adhesion measuring method》Standard, the adhesive force of test oil layer of ink,
In 100/100 represent not demoulding, 90/100 represents and comes off 10%.
Wearability：According to HG/T 4303-2012《Surface hardened layer polyester film wearability assay method》Test each hardened layer
It is wear-resisting lossy, using 0000# steel wool, 1000gf/cm2It bears a heavy burden, by detecting abrasion resistance of the membrane surface without scuffing
The limit, to judge the abrasion resistant effect of film.
Water contact angle：According to GB/T 30693-2014《The measurement of plastic film and water contact angle》Standard, test anti-finger
The surface water contact angle of dirty hardened layer, ink layer.Water contact angle is bigger, and the anti-dirty ability of finger is stronger.
Warpage is tested after reliability：In temperature it is 70 DEG C by reflectance coating, the high temperature and humidity condition of humidity 95% places 500h
After tested, the specification of warpage test for 10cm × 10cm, using feeler gauge tested by depth of camber test.
Black flour reflectivity：According to the standard of NIST 2054, light is divided using Agilent Cary5000 UV, visible lights near-infrared
Degree measurement tries its reflectivity at 550nm.Black film face reflectivity refers to anti-laminated for ink in surface layer in reflectance coating
Penetrate rate.
Black flour is sampled：It is observed by the naked eye using reflected light, judgment criteria is black for superbright, and brilliant black is mute black, super mute black.
Process complexity：Mainly on material machine flattening etc. factors consider, judgment criteria be high ＞ higher ＞ in ＞ compared with
Low ＞ is low, wherein high represent difficulty of processing height, but does not represent and cannot produce product.
Assemble yield：The non-defective unit that the black reflectance coating of silver for being 5.5 cun according to 1000 specifications is assembled into backlight is accounted in total quantity
Ratio.
Pencil hardness：According to GB 1720-1979《Paint film adhesion measuring method》Standard.
Warpage is tested：The specification of test is 10cm × 10cm, and depth of camber is tested using feeler gauge.
Embodiment 1
As shown in figure 4, the present embodiment provides a kind of reflectance coating semi-finished product, the semi-finished product include hardening coat, priming coat,
Oxygen fish tail and waterproof layer, Ag layers and substrate layer.
The thickness that its moderate resistance refers to dirty hardened layer 10 is 4 μm, and the thickness of priming coat 20 is 0.1 μm, oxygen fish tail and waterproof layer 30
Thickness for 0.2 μm, the thickness of Ag layers 40 is 30nm, and the thickness of PET base material layer 50 is 50 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of the priming coat is acrylic.
The material of the oxygen fish tail and waterproof layer is acrylic.
Embodiment 2
Such as the reflectance coating semi-finished product that embodiment 1 provides, the thickness difference lies in Ag layers 40 is 40nm.
Embodiment 3
Such as the reflectance coating semi-finished product that embodiment 1 provides, the thickness difference lies in Ag layers 40 is 50nm.
Embodiment 4
Such as the reflectance coating semi-finished product that embodiment 1 provides, the thickness difference lies in Ag layers 40 is 60nm.
Embodiment 5
Such as the reflectance coating semi-finished product that embodiment 1 provides, the thickness difference lies in Ag layers 40 is 80nm.
Embodiment 6
The present invention provides a kind of reflectance coating, and the reflectance coating includes hardening coat, priming coat, oxygen waterproofing protection successively
Layer, Ag layers, substrate layer, Al layers and ink layer.
The thickness that its moderate resistance refers to dirty hardened layer 10 is 4 μm, and the thickness of priming coat 20 is 0.1 μm, oxygen fish tail and waterproof layer 30
Thickness for 0.2 μm, the thickness of Ag layers 40 is 50nm, and the thickness of PET base material layer 50 is 50 μm, and the thickness of Al layers 60 is 0nm, i.e.,
Without Al layers, the print pass of ink layer 70 is 2 times, and thickness is 0.5 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of the priming coat is acrylic.
The material of the oxygen fish tail and waterproof layer is acrylic.
Embodiment 7
Such as the reflectance coating that embodiment 6 provides, the thickness difference lies in Al layers 60 is 20nm.
Embodiment 8
Such as the reflectance coating that embodiment 6 provides, the thickness difference lies in Al layers 60 is 30nm.
Embodiment 9
Such as the reflectance coating that embodiment 6 provides, the thickness difference lies in Al layers 60 is 60nm.
Embodiment 10
Such as the reflectance coating that embodiment 6 provides, it is 4 μm that moderate resistance, which refers to dirty 10 thickness of hardened layer, and 20 thickness of priming coat is 0.1 μ
M, the thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, and the thickness of Ag layers 40 is 50nm, and the thickness of PET base material layer 50 is 50 μm, Al
The thickness of layer 60 is 30nm, and the number that ink layer 70 prints is 3 times, i.e., thickness is 0.7 μm.
Embodiment 11
It it is 4 times difference lies in 70 print pass of ink layer such as the reflectance coating that embodiment 9 provides, i.e., thickness is 1.0 μm.
Embodiment 12
It it is 6 times difference lies in 70 print pass of ink layer such as the reflectance coating that embodiment 9 provides, i.e., thickness is 1.5 μm.
Embodiment 13
Such as the reflectance coating that embodiment 6 provides, the thickness that moderate resistance refers to dirty hardened layer 10 is 4 μm, and the thickness of priming coat 20 is
0.1 μm, the thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, and the thickness of Ag layers 40 is 50nm, and the thickness of PET base material layer 50 is 25 μ
The thickness of m, Al layer 60 is 30nm, and the number that ink layer 70 prints is 4 times, i.e., thickness is 1.0 μm.
Embodiment 14
Such as the reflectance coating that embodiment 13 provides, the thickness difference lies in PET base material layer 50 is 38 μm.
Embodiment 15
Such as the reflectance coating that embodiment 13 provides, the thickness difference lies in PET base material layer 50 is 75 μm.
The conventional black reflectance coating of high silver lustre visible on the market includes Over coating as shown in Fig. 2, belong to composite material
Layer 30, Ag layers 40, PET base material layer 50, hot dry glue composite layer 90, PET base material layer 80, Al layers 60 and ink layer 70.
In order to compare individual black reflectance coating (reflectance coating provided by the invention) of silver and (the comparative example offer of the black reflectance coating of composite silver
Reflectance coating) performance, the warpage situation especially after reliability, we select shrinking percentage to approach, the different PET bases of thickness
Material (MD≤- 0.20%, TD≤- 0.04%) and tunica albuginea (containing barium sulfate) base material.
Comparative example 1
As shown in Fig. 2, the black reflectance coating of high silver lustre that comparative example 1 provides includes oxygen fish tail and waterproof layer, Ag layers, PET base material
Layer, hot dry glue composite layer, PET base material layer, Al layers and ink layer.
Wherein the thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, and the thickness of Ag layers 40 is 50nm, the thickness of PET base material layer 50
It is 25 μm to spend, and the thickness of hot dry glue composite layer 90 is 4 μm, and the thickness of PET base material layer 80 is 50 μm, and the thickness of Al layers 60 is
30nm, the number that ink layer 70 prints are 4 times, and for formula using the ink coating fluid of no fluorine element auxiliary agent, i.e. thickness is 1.0 μm.
The material of oxygen fish tail and waterproof layer is acrylic.
Comparative example 2
Such as the black reflectance coating of high silver lustre that comparative example 1 provides, wherein 30 thickness of oxygen fish tail and waterproof layer is 0.2 μm, Ag layers 40
Thickness for 50nm, the thickness of PET base material layer 50 is 36 μm, and the thickness of hot dry glue composite layer 90 is 4 μm, PET base material layer 80
Thickness for 36 μm, the thickness of Al layers 60 is 30nm, and the number that ink layer 70 prints is 4 times, and formula is using no fluorine element auxiliary agent
Ink coating fluid, i.e. thickness are 1.0 μm.
Comparative example 3
Such as the black reflectance coating of high silver lustre that comparative example 1 provides, the wherein thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, Ag layers
40 thickness is 50nm, and the thickness of PET base material layer 50 is 50 μm, and the thickness of hot dry glue composite layer 90 is 4 μm, PET base material layer
80 thickness is 25 μm, and the thickness of Al layers 60 is 30nm, and the number that ink layer 70 prints is 4 times, is formulated using no fluorine element auxiliary agent
Ink coating fluid, i.e., thickness be 1.0 μm.
Comparative example 4
As shown in figure 3, comparative example 5 provide the black reflectance coating of high silver lustre include oxygen fish tail and waterproof layer, Ag layers, substrate layer,
Hot dry glue composite layer, tunica albuginea substrate layer and ink layer；The black reflectance coating of high silver lustre further includes hardening coat, priming coat.
The thickness that its moderate resistance refers to dirty hardened layer is 4 μm, and the thickness of priming coat is 0.1 μm, the thickness of oxygen fish tail and waterproof layer 30
It is 0.2 μm to spend, and the thickness of Ag layers 40 is 50nm, and the thickness of PET base material layer 50 is 50 μm, and the thickness of hot dry glue composite layer 90 is
4 μm, the thickness of tunica albuginea substrate layer (containing barium sulfate material) 80 is 25 μm, and the number that ink layer 70 prints is 4 times, and formula is adopted
With the ink coating fluid of no fluorine element auxiliary agent, i.e. thickness is 1.0 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of priming coat is acrylic.
The material of fish tail and waterproof layer is acrylic.
Comparative example 5
Such as the black reflectance coating of high silver lustre that comparative example 4 provides, the thickness that moderate resistance refers to dirty hardened layer is 4 μm, the thickness of priming coat
It is 0.1 μm to spend, and the thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, and the thickness of Ag layers 40 is 50nm, the thickness of PET base material layer 50
It is 36 μm, the thickness of hot dry glue composite layer 90 is 4 μm, and the thickness of tunica albuginea substrate layer (containing barium sulfate material) 80 is 36 μm,
The number that ink layer 70 prints is 4 times, and for formula using the ink coating fluid of no fluorine element auxiliary agent, i.e. thickness is 1.0 μm.
Comparative example 6
Such as the black reflectance coating of high silver lustre that comparative example 4 provides, the thickness that moderate resistance refers to dirty hardened layer is 4 μm, the thickness of priming coat
It is 0.1 μm to spend, and the thickness of oxygen fish tail and waterproof layer 30 is 0.2 μm, and the thickness of Ag layers 40 is 50nm, the thickness of PET base material layer 50
It is 25 μm, the thickness of hot dry glue composite layer 90 is 4 μm, and the thickness of tunica albuginea substrate layer (containing barium sulfate material) 80 is 50 μm,
The number that ink layer 70 prints is 4 times, and for formula using the ink coating fluid of no fluorine element auxiliary agent, i.e. thickness is 1.0 μm.
Comparative example 7
Such as the black reflectance coating of high silver lustre that comparative example 1 provides, the reflectance coating further includes the dirty hardened layer of anti-finger and priming coat, resists
The thickness for referring to dirty hardened layer is 4 μm, and the thickness of priming coat is 0.1 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of priming coat is acrylic.
Comparative example 8
Such as the black reflectance coating of high silver lustre that comparative example 2 provides, the reflectance coating further includes the dirty hardened layer of anti-finger and priming coat, resists
The thickness for referring to dirty hardened layer is 4 μm, and the thickness of priming coat is 0.1 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of priming coat is acrylic.
Comparative example 9
Such as the black reflectance coating of high silver lustre that comparative example 3 provides, the reflectance coating further includes the dirty hardened layer of anti-finger and priming coat, resists
The thickness for referring to dirty hardened layer is 4 μm, and the thickness of priming coat is 0.1 μm.
The anti-coating fluid for referring to dirty hardening coat includes six official's polyurethane acrylic resin prepolymers of 30 parts by weight, and 18
Three official's polyurethane acrylic resin prepolymer of parts by weight, 12 parts by weight, three official's acrylate monomer, 3.6 parts by weight photoinitiators
(photoinitiator 184), 0.3 parts by weight fluorine auxiliary agent and the mixing of 40 weight parts organic solvents.Wherein, organic solvent is ethyl acetate.
The material of priming coat is acrylic.
The reflecting properties testing result for the reflectance coating semi-finished product that 1 embodiment 1-5 of table is provided
| Performance | Silver-colored face reflectivity |
| Embodiment 1 | 90.34% |
| Embodiment 2 | 93.36% |
| Embodiment 3 | 96.57% |
| Embodiment 4 | 96.79% |
| Embodiment 5 | 96.83% |
From the comparing result in table 1 it can be found that silver layer reflectivity can increase with the increase of silver thickness, but such as
It is smaller for its raising influence of reflectivity at 550nm even if increasing the thickness of silver layer for embodiment 3,4,5, that is, implement
Example 3 has begun to reach a relatively good value.
The main performance testing result for the reflectance coating that 2 embodiment 6-9 of table is provided
| Performance | Black flour reflectivity | Black flour is sampled | Adhesive force | Water contact angle |
| Embodiment 6 | 10.28% | Brilliant black | 60/100 | 104.23° |
| Embodiment 7 | 12.32% | Brilliant black | 90/100 | 104.34° |
| Embodiment 8 | 15.67% | Brilliant black | 100/100 | 104.35° |
| Embodiment 9 | 21.98% | Superbright is black | 100/100 | 104.29° |
From the comparing result in table 2 it can be found that the adhesive force of the reflectivity of black flour, taste and ink layer with Al layers
Thickness is closely bound up, and the reflectivity of black flour is as Al layers of thickness increases and gradually increases, and adhesive force aspect, likewise as Al
Layer thickness increases and increases.But at present, on the market for client, this black product of silver for taste is upper, prefers
It is mute black, in terms of the black flour reflectivity for, it is more lower better to be desirable to reflectivity.In embodiment 6-9, water contact angle is essentially identical,
Thickness with Al layers is unrelated.Therefore, in the case where adhesive force is up to standard, the Al layers in embodiment 8 reach above-described embodiment 8 and 9
One more figure of merit.
The main performance testing result of reflectance coating that 3 embodiment 8 of table, embodiment 10-12 are provided
From the comparing result in table 3 it can be found that ink layer printing number, i.e. coating thickness, with the black flour of material
Reflectivity, taste and water contact angle have direct relationship, when print pass is 2 times or 3 times, black flour reflectivity changes
It is very big, still belong to brilliant black in terms of taste, embody the essence of metallochrome, when print pass is 4 times, black flour reflectivity reaches
4.16%, whole taste is mute black, and water contact angle has also reached 107.24 ° simultaneously, further increases print pass, performance boost
Space is little.
The main performance testing result of reflectance coating that 4 embodiment 11 of table, embodiment 13-15 are provided
The comparing result from table 4 is it can be found that influence of the selection of base material layer thickness for reflectivity in the black reflectance coating of silver
Substantially do not have；The influence of warpage during for producing offline, the thin base material of thickness, angularity when producing offline is bigger, reliability
Afterwards, the variation of warpage is all not much different substantially, in rational range (≤3mm).In view of current machine be related to slimming and
The variation of complexity is processed, embodiment 11,15 is preferably scheme relatively.
5 embodiment 15 of table provide reflectance coating and comparative example 1-9 provide the black reflectance coating of high silver lustre it is main
Performance test results
Comparing result from table 5, comparative example 1,7 or 2,8 or 3,9 find silver layer face exist one layer it is anti-refer to dirt hardened layer,
Reflectance coating can be effectively improved with the wearability between light guide plate, so as to effectively improve the assembling yield of material.From embodiment 15
With comparative example 4-9 it can be found that the black reflectance coating of silver provided by the invention includes individual base material, the black reflectance coating of silver provided by the invention
Production it is offline when warpage and reliability after warpage be better than comparative example 4-9 offer compound high silver lustre reflectance coating；It compares simultaneously
Compared with the PET base material aluminized, using the tunica albuginea base material containing barium sulfate drawing and forming, warpage is more difficult to management and control, warpage after reliability
More serious, the reflectance coating that embodiment 15 provides has further raising for subsequently assembling yield, will particularly with warpage
Seek high machine.
It these are only the preferred embodiment of patent of the present invention, be not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is done any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of reflectance coating, which is characterized in that the reflectance coating successively include hardening coat, priming coat, oxygen fish tail and waterproof layer,
Ag layers, substrate layer, Al layers and ink layer.
2. reflectance coating according to claim 1, which is characterized in that in preparation process, the hardening coat is first configured to
Coating fluid.
3. reflectance coating according to claim 2, which is characterized in that it is pre- that the coating fluid of the hardening coat includes acrylate
Polymers, acrylate monomer, photoinitiator, fluorine element additive and organic solvent.
4. reflectance coating according to claim 1, which is characterized in that the material of the priming coat is selected from acrylic resin or poly-
One kind or combination of the two in urethane.
5. reflectance coating according to claim 1, which is characterized in that the material of the oxygen fish tail and waterproof layer is selected from propylene
Acid ester polymer.
6. reflectance coating according to claim 1, which is characterized in that described Ag layers is carried out by the way of physical vapour deposition (PVD)
It prepares.
7. reflectance coating according to claim 1, which is characterized in that Ag layers of thickness is 30-80nm, and the thickness of substrate layer is
25-75 μm, Al layers of thickness is 0-60nm, and the thickness of ink layer is 0.5-1.5 μm.
A kind of 8. method for preparing the reflectance coating described in any one of claim 1-7, which is characterized in that the method includes with
Lower step：
(1) it is first pre-processed using high transparency base material, is then deposited Ag layers in the one side of base material；
(2) it is coated with oxygen fish tail and waterproof layer in Ag layer surfaces；
(3) one layer of priming coat is coated in oxygen waterproofing protection layer surface, for the coating of subsequent curing liquid；
(4) hardening bath is coated on priming coat, hardening coat is obtained after curing；
(5) in the another side evaporating Al layer of PET；
(6) it carries out covering protective film on hardening coat surface；
(7) by the way of silk-screen printing ink is printed at Al layers；
(8) slitting is carried out, packs shipment.
9. the preparation method of reflectance coating according to claim 8, which is characterized in that the silk-screen number of the ink is 2-6
It is secondary.
10. reflectance coating according to claim 1, which is characterized in that the angularity when reflectance coating produces offline is 0-
1mm, the angularity after reliability are 0-3mm, reflectivity ＞ 96.0%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810017687.8A CN108178839B (en) | 2018-01-09 | 2018-01-09 | Reflective film |
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| CN109870753A (en) * | 2018-12-21 | 2019-06-11 | 宁波激智科技股份有限公司 | A kind of dirty silver-colored reflectance coating of the anti-finger of super bright high reliability |
| CN112415814A (en) * | 2021-01-06 | 2021-02-26 | 广东中强精英电子科技有限公司 | Backlight module with light leakage prevention high-reflection side reflection structure |
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|---|---|
| CN108178839B (en) | 2023-11-10 |
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