CN102490429B - A kind of transparent hardened film with low interference line - Google Patents
A kind of transparent hardened film with low interference line Download PDFInfo
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- CN102490429B CN102490429B CN201110334397.4A CN201110334397A CN102490429B CN 102490429 B CN102490429 B CN 102490429B CN 201110334397 A CN201110334397 A CN 201110334397A CN 102490429 B CN102490429 B CN 102490429B
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Abstract
A kind of transparent hardened film with low interference line, it applies transparent hard layer on support, described hardened layer comprises the first coating and is positioned at the second coating on the first coating, the refractive index of described first coating is 1.57 ~ 1.69, thickness is 0.05 ~ 0.25 μm, and the refractive index of described second coating is 1.45 ~ 1.60, thickness is 1 ~ 5 μm.The interference line that this transparent hardened film tool is extremely low, the hardness of more than 2H, meets the ejection formation tensile property requirement of more than 6mm height simultaneously, can be applicable to the application such as screen display, in-mold decoration.
Description
Technical field
The present invention relates to a kind of transparent hardened film with low interference line.
Background technology
Because the plastic sheeting of polyester etc. has excellent character in mechanical performance, dimensional stability, heat resistance, the transparency etc., therefore it can be used as the multi-purpose base films such as in-mold decoration (IMD) material or screen display material and extensive use.
But this plastic sheeting, because the case hardness of film surface is low, and anti-wear performance is also not enough, by easily incurring loss with its surfaces such as the contacting of other solid matter, friction, scratchings, the damage produced on surface can make the economic worth of film significantly reduce, and film just can not be used at short notice.Therefore, it is known that when forming base film by polyester film, the hardened layer that marresistance and abrasion performance etc. are excellent is set in the above.
The hardened layer on cured film surface and the refractive index of support are generally different, between hardened layer and support, the difference of refractive index can form interface phase, when its surface is penetrated in illumination, primary event light and the interface phase secondary reflection light on cured film surface will inevitably interfere phenomenon because wave path-difference exists, the interference of light degree varies of different wave length causes, see in different angles, the rainbow shape that can produce in various degree interferes line, the existence of this interference line can affect the visual effect of product, affect the application of product, therefore, interference line must be eliminated.
Line is interfered for eliminating or reducing, known technology generally adopts: improve the accuracy of coating thickness, increase the refractive index of hardened layer to reduce the method for refringence, base material dissolves or swelling to reduce the method etc. of interference fringe, but the existence of these methods is high to coating accuracy requirement, light transmittance significantly reduces, cannot meet the defects such as the shaping tensile property of IMD requires.
Summary of the invention
The technical problem that application claims solves is to provide a kind of transparent hardened film with low interference line, and the application that can meet flat display field can meet again the shaping tensile property requirement of IMD.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of transparent hardened film with low interference line, support applies transparent hard layer, described hardened layer comprises the first coating and is positioned at the second coating on the first coating, the refractive index of described first coating is 1.57 ~ 1.69, thickness is 0.05 ~ 0.25 μm, and the refractive index of described second coating is 1.45 ~ 1.60, thickness is 1 ~ 5 μm.
The refractive index of the first above-mentioned coating is 1.59 ~ 1.62.
The thickness of above-mentioned second coating is 2 ~ 3 μm.
The first above-mentioned coating contains film forming matter or the refractive index film forming matter and the high index of refraction metallic compound that are less than 1.57 that refractive index is 1.57 ~ 1.69.
Above-mentioned refractive index be 1.57 ~ 1.69 film forming matter comprise and introduce aromatic compound or fused ring compound, introducing aliphatic polycyclic compound, introduce sulphur or epithio based compound or their composition.
The metallic compound of above-mentioned high index of refraction can be titanium dioxide or tin indium oxide.
The second above-mentioned coating contains acrylic monomers or their composition of more than the polyurethane acroleic acid prepolymer of more than a kind of 3 degrees of functionality, 3 degrees of functionality.
Polyurethane (methyl) acrylic ester prepolymers more than 3 above-mentioned degrees of functionality is pentaerythrite three (methyl) acrylate hexylene glycol vulcabond carbamate prepolymer, pentaerythrite three (methyl) acrylate toluene di-isocyanate(TDI) carbamate prepolymer, pentaerythrite three (methyl) acrylate isoflurane chalcone diisocyanate carbamate prepolymer or their mixture.
(methyl) acrylate monomers more than 3 above-mentioned degrees of functionality is pentaerythrite three (methyl) acrylate monomer, pentaerythrite four (methyl) acrylate monomer, dipentaerythritol three (methyl) acrylate monomer, dipentaerythritol four (methyl) acrylate monomer, dipentaerythritol five (methyl) acrylate monomer, dipentaerythritol six (methyl) acrylate monomer, trimethylolpropane tris (methyl) acrylate monomer or their mixture.
Compared with prior art, tool of the present invention has the following advantages:
1. hardened layer of the present invention adopts two coating structure, and by control first coating, the refractive index of the second coating and thickness, when ensureing effectively to solve interference line, make transparent hardened film provided by the invention have the hardness of more than 2H, the ejection formation tensile property requirement of more than 6mm height can be met.
2. transparent hardened film provided by the invention, the application that can meet flat display field can meet again the shaping tensile property requirement of IMD.
Detailed description of the invention
In order to effectively solve interference line, and the shaping tensile property requirement of the high rigidity meeting IMD, the hardened layer in the present invention have employed the double-decker of the first coating and the second coating.The refractive index of the first coating controls 1.57 ~ 1.69, and THICKNESS CONTROL is in the scope of 0.05 ~ 0.25 μm, and preferred index is 1.59 ~ 1.62; The refractive index of the second coating controls 1.45 ~ 1.60, and thickness is 1 ~ 5 micron, and preferred thickness is 2 ~ 3 microns.
First coating provided by the invention has good pliability, makes cured film meet the requirement of shaping tensile property; Second coating has higher hardness and crocking resistance, makes cured film meet the requirement of IMD to its hardness.
In order to make the first coating have applicable index requirements, be film forming matter or the refractive index film forming matter and the high index of refraction metallic compound that are less than 1.57 of 1.57 ~ 1.69 containing refractive index in the first coating.The rate of penetrating be 1.57 ~ 1.69 film forming matter comprise and introduce aromatic compound or fused ring compound, introducing aliphatic polycyclic compound, introduce sulphur or epithio based compound or their composition; The metallic compound of high index of refraction can be titanium dioxide or tin indium oxide.
In order to make hardened layer give the enough hardness of cured film and wearability, application claims second coating has higher hardness and good wearability, and refractive index is 1.45 ~ 1.60 simultaneously; Hardness can solve from the crosslink density of raisingization resin, contains the polyurethane acroleic acid prepolymer of more than a kind of 3 degrees of functionality, acrylic monomers more than 3 degrees of functionality or their composition in the second coating of the present invention.Be specifically related to: pentaerythrite three (methyl) acrylate monomer, pentaerythrite four (methyl) acrylate monomer, dipentaerythritol three (methyl) acrylate monomer, dipentaerythritol four (methyl) acrylate monomer, dipentaerythritol five (methyl) acrylate monomer, dipentaerythritol six (methyl) acrylate monomer, trimethylolpropane tris (methyl) acrylate monomer, pentaerythrite three (methyl) acrylate hexylene glycol vulcabond carbamate prepolymer, pentaerythrite three (methyl) acrylate toluene di-isocyanate(TDI) carbamate prepolymer, pentaerythrite three (methyl) acrylate isoflurane chalcone diisocyanate carbamate prepolymer etc.Meanwhile, by the THICKNESS CONTROL of the second coating at 1 ~ 5 μm, when the thickness of upper hardened layer is lower than 1 μm, cured film is difficult to reach a higher hardness and good anti-wear performance; When the thickness of upper hardened layer is greater than 5 μm, then cured film is difficult to the requirement of the performance meeting shaping stretching.
Crosslinked in order to make the film forming matter in the first coating, the second coating occur, also add light trigger in the coating fluid of the first coating, the second coating.Do not specially require as the light trigger used in the present invention, as long as can be embodied as membrane substance occurs crosslinked, the light trigger that can exemplify has: cracking type initator: as: 2-hydroxy-methyl phenyl-propane-1-ketone (1173), 1-hydroxy-cyclohexyl phenyl ketone (184), 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl-1-acetone (907), benzoin dimethylether (651), 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO) etc.; Photoinitiator (hydrogen-abstraction): as benzophenone (BP), 2-isopropyl thioxanthone (ITX) etc.Preferred: 2-hydroxy-methyl phenyl-propane-1-ketone (1173) and 1-hydroxy-cyclohexyl phenyl ketone (184).These light triggers may be used alone, can also be used in combination.
In order to improve the flatness of coating, in the first coating in the present invention, the coating fluid of the second coating, levelling agent can also be added.Levelling agent of the present invention is preferably organosiloxane or organic-silicon-modified acrylic acid levelling agent as BYK-307, BYK-377, BYK-354, BYK-306, BYK-333, Levaslip407, Levaslip410, Levaslip411, Levaslip432, Levaslip466 etc.
As required, the coating fluid of the first coating, the second coating can also use solvent dilution.As long as transparent hard layer of the present invention can be formed on support, conventional organic solvent can be used and without any restriction.The example of organic solvent comprises: aliphatic hydrocarbon as hexane, heptane and cyclohexane; Aromatic hydrocarbons is as toluene and dimethylbenzene; Halogenated hydrocarbons is as carrene and dichloroethanes; Alcohols as methyl alcohol, ethanol, propyl alcohol and butanols; Ketone as acetone, butanone, methyl ethyl ketone, 2 pentanone, and isophorone; Ester is as ethyl acetate and butyl acetate; And cellosolve based solvent is as ethyl cellosolve.Organic solvent can be used alone or combinationally uses with two or more.The concentration of coating fluid and viscosity can object according to the present invention suitably be selected.
As long as can form coating, the present invention has no particular limits coating process, can use conventional method, and as stick coating method, scraper for coating method, Mayer stick coating method, rolling method, scraper plate rubbing method, bar seam rubbing method and gravure coating process form coating.Preferred stripe seam and gravure coating process.
Support in the present invention is preferably plastic sheeting, the example that can enumerate comprises: polyester film, as the laminated film etc. of PET (PET), polycarbonate film (PC), polymethyl methacrylate film (PMMA), ABS and PET laminated film, PC and PMMA.Preferably PET (PET), polycarbonate film (PC), more preferred PET (PET).
Support thickness have no particular limits.Usually, described thickness at 20-300 micron, preferably in the scope of 50-200 micron.When this thickness is less than 20 microns, mechanical strength not, and will will have such possibility, and namely cured film distortion is too large and durability is inadequate; When thickness is more than 300 microns, increase difficulty of processing and cost increase.Therefore, the thickness outside appeal scope is worthless.
Support in the present invention must be transparent, and in 400nm ~ 700nm wave-length coverage, its light transmission rate is preferably more than 80%, more preferably more than 90%.
Below in conjunction with specific embodiment, the present invention is specifically described, but the present invention is not limited to this.
Embodiment 1
First coating applications liquid:
PN-62501.00 weight portion,
Butanone 38.8 weight portion,
BYK3770.10 weight portion,
1840.10 weight portion,
The PN-6250 of 1.0 weight portions [Jin Tuan trade Co., Ltd, with the aromatic acrylates of 10%BZA dilution, refractive index 1.573] be dissolved in the butanone solvent of 38.8 weight portions, add 0.1 weight portion and there is the levelling agent BYK377 [being made by Bi Kehua length of schooling] of polydimethylsiloxaneskeleton skeleton structure and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 0.1 weight portion, obtain the first coating applications liquid.
[Chinese Lekai Film Group Co manufactures, trade name above-mentioned coating fluid to be applied to the polyethylene terephthalate thin film that thickness is 125 micrometer optical levels; PG12-125] a face on, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the first coating that thickness is 0.25 micron.
Second coating applications liquid:
EB51294.0 weight portion,
EM-24116.0 weight portion,
Butanone 28.6 weight portion,
BYK3070.1 weight portion,
1841.0 weight portion,
By the aliphatic polyurethane six acrylic ester prepolymer EB5129 of 4.0 weight portions, [Qing Te sufacing (Shanghai) Co., Ltd. manufactures, degree of functionality 6] and 6.0 weight portions ethoxyquin tetramethylol methane tetraacrylate monomer EM-2411 [Changxing Chemical Industry Co Ltd manufacture, degree of functionality 4] be dissolved in the butanone solvent of 28.6 weight portions, add the levelling agent BYK307 [being made by Bi Kehua length of schooling] with polydimethylsiloxaneskeleton skeleton structure of 0.1 weight portion and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 1.0 weight portions, obtain coating fluid.
Coating fluid is applied in above-mentioned first coating, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the hardened layer that thickness is 2.5 microns, obtain transparent hardened film, survey its correlated performance.
Embodiment 2
First coating applications liquid:
PN-32800.65 weight portion,
Butanone 38.795 weight portion,
Nano TiO 2 dispersion liquid 0.39 weight portion,
BYK3770.1 weight portion,
1840.065 weight portion,
The PN-3280 of 0.65 weight portion [Jin Tuan trade Co., Ltd, aromatic acrylates, refractive index 1.490] be dissolved in the butanone solvent of 38.795 weight portions, add 0.85 weight portion nano TiO 2 titanium oxide dispersion [Xuancheng Jingrui New Material Co., Ltd., average grain diameter 15nm, solid content 15%], 0.1 weight portion has the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of the levelling agent BYK377 [being made by Bi Kehua length of schooling] of polydimethylsiloxaneskeleton skeleton structure and 0.065 weight portion, obtains coating fluid.
[Chinese Lekai Film Group Co manufactures, trade name above-mentioned coating fluid to be applied to the polyethylene terephthalate thin film that thickness is 125 micrometer optical levels; PG12-125] a face on, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the ground floor that thickness is 0.15 micron.
Second coating applications liquid:
UXE100010.0 weight portion,
Levaslip4320.1 weight portion,
Butanone 28.6 weight portion,
1841.0 weight portion,
To 10.0 parts by weight of polyurethane acrylic ester prepolymer UXE1000, [chemical drug chemical industry (Wuxi) Co., Ltd manufactures, degree of functionality 4] in, add the levelling agent Levaslip432 [manufacture of moral modest (Shanghai) Chemical Co., Ltd.] with polydimethylsiloxaneskeleton skeleton structure of 0.1 weight portion and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 1.0 weight portions, dilute with the butanone solvent of 28.6 weight portions, obtain coating fluid.
Coating fluid is applied in above-mentioned first coating, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the hardened layer that thickness is 3.0 microns, obtain transparent hardened film, survey its correlated performance.
Embodiment 3
First coating applications liquid:
PN-68000.40 weight portion,
Butanone 39.46 weight portion,
BYK3770.1 weight portion,
1840.04 weight portion,
The PN-6800 of 0.40 weight portion [Jin Tuan trade Co., Ltd, aromatic series diacrylate, refractive index 1.608] be dissolved in the butanone solvent of 39.46 weight portions, add 0.1 weight portion and there is the levelling agent BYK377 [being made by Bi Kehua length of schooling] of polydimethylsiloxaneskeleton skeleton structure and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 0.04 weight portion, obtain coating fluid.
[Chinese Lekai Film Group Co manufactures, trade name above-mentioned coating fluid to be applied to the polyethylene terephthalate thin film that thickness is 125 micrometer optical levels; PG12-125] a face on, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the first coating that thickness is 0.1 micron.
Second coating applications liquid:
EB51296.0 weight portion,
EM-24214.0 weight portion,
1841.0 weight portion,
BYK3070.1 weight portion,
Butanone 28.6 weight portion,
By the aliphatic polyurethane six acrylic ester prepolymer EB5129 of 6.0 weight portions, [Qing Te sufacing (Shanghai) Co., Ltd. manufactures, degree of functionality 6] and 4.0 weight portions ethoxyquin tetramethylol methane tetraacrylate monomer EM-2421 [Changxing Chemical Industry Co Ltd manufacture, degree of functionality 4] be dissolved in the butanone solvent of 28.6 weight portions, add the levelling agent BYK307 [being made by Bi Kehua length of schooling] with polydimethylsiloxaneskeleton skeleton structure of 0.1 weight portion and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 1.0 weight portions, obtain coating fluid.
Coating fluid is applied in above-mentioned first coating, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the hardened layer that thickness is 2.5 microns, obtain transparent hardened film, survey its correlated performance.
Embodiment 4
First coating applications liquid material:
PN-61000.70 weight portion,
Butanone 39.13 weight portion,
BYK3770.1 weight portion,
1840.07 weight portion,
The PN-6100 of 0.70 weight portion [Jin Tuan trade Co., Ltd, aromatic acrylates, refractive index 1.620] be dissolved in the butanone solvent of 39.13 weight portions, add 0.1 weight portion and there is the levelling agent BYK377 [being made by Bi Kehua length of schooling] of polydimethylsiloxaneskeleton skeleton structure and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 0.07 weight portion, obtain coating fluid.
[Chinese Lekai Film Group Co manufactures, trade name above-mentioned coating fluid to be applied to the polyethylene terephthalate thin film that thickness is 125 micrometer optical levels; PG12-125] a face on, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the first coating that thickness is 0.15 micron.
Second coating applications liquid:
EB51295.5 weight portion,
EM-24213.5.0 weight portion,
1841.0 weight portion,
BYK3070.1 weight portion,
Butanone 29.6 weight portion,
By the aliphatic polyurethane six acrylic ester prepolymer EB5129 of 5.5 weight portions, [Qing Te sufacing (Shanghai) Co., Ltd. manufactures, degree of functionality 6] and 3.5 weight portions ethoxyquin tetramethylol methane tetraacrylate monomer EM-2421 [Changxing Chemical Industry Co Ltd manufacture, degree of functionality 4] be dissolved in the butanone solvent of 29.6 weight portions, add the levelling agent BYK307 [being made by Bi Kehua length of schooling] with polydimethylsiloxaneskeleton skeleton structure of 0.1 weight portion and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 1.0 weight portions, obtain coating fluid.
Coating fluid is applied in above-mentioned first coating, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the hardened layer that thickness is 2.0 microns, obtain transparent hardened film, survey its correlated performance.
Embodiment 5
First coating applications liquid:
PN-32800.35 weight portion,
Butanone 39.005 weight portion,
Nano TiO 2 dispersion liquid 0.46 weight portion,
BYK3770.1 weight portion,
1840.035 weight portion,
The PN-3280 of 0.35 weight portion [Jin Tuan trade Co., Ltd, aromatic acrylates, refractive index 1.490] be dissolved in the butanone solvent of 39.005 weight portions, add 0.46 weight portion nano TiO 2 titanium oxide dispersion [Xuancheng Jingrui New Material Co., Ltd., average grain diameter 15nm, solid content 15%], 0.1 weight portion has the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of the levelling agent BYK377 [being made by Bi Kehua length of schooling] of polydimethylsiloxaneskeleton skeleton structure and 0.035 weight portion, obtains coating fluid.
[Chinese Lekai Film Group Co manufactures, trade name above-mentioned coating fluid to be applied to the polyethylene terephthalate thin film that thickness is 125 micrometer optical levels; PG12-125] a face on, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the first coating that thickness is 0.05 micron.
Second coating applications liquid:
EB51298.0 weight portion,
EM-24215.0 weight portion,
1841.3 weight portion,
BYK3070.1 weight portion,
Butanone 25.3 weight portion,
By the aliphatic polyurethane six acrylic ester prepolymer EB5129 of 8.0 weight portions, [Qing Te sufacing (Shanghai) Co., Ltd. manufactures, degree of functionality 6] and 5.0 weight portions ethoxyquin tetramethylol methane tetraacrylate monomer EM-2421 [Changxing Chemical Industry Co Ltd manufacture, degree of functionality 4] be dissolved in the butanone solvent of 25.3 weight portions, add the levelling agent BYK307 [being made by Bi Kehua length of schooling] with polydimethylsiloxaneskeleton skeleton structure of 0.1 weight portion and the light trigger 184 [being manufactured by Tianjin proud son of heaven Chemical Co., Ltd.] of 1.3 weight portions, obtain coating fluid.
Coating fluid is applied in above-mentioned first coating, after 70-90 DEG C to the dry 2min of the coating formed, with the light quantity of 250mJ/cm2, be cured by the coating of Ultraviolet radiation to drying, and form the hardened layer that thickness is 5.0 microns, obtain transparent hardened film, survey its correlated performance.
Comparative example 1
Cured film is prepared according to the step identical with embodiment 1, difference is: PN-6250 [the Jin Tuan trade Co., Ltd in base coat material, with the aromatic acrylates of 10%BZA dilution, refractive index 1.573] change into PN-3280 [Jin Tuan trade Co., Ltd, aromatic acrylates, refractive index 1.490], survey its performance.
Comparative example 2
Prepare cured film according to the step identical with embodiment 2, difference is: by changing coating weight, the thickness of hardened layer changes into 7.0 microns, surveys its performance.
Comparative example 3
Prepare cured film according to the step identical with embodiment 3, difference is: by changing coating weight, the thickness of priming coat changes into 0.4 micron, surveys its performance.
Table 1: embodiment and comparative example test result
In table:
(1) assay method of coating index of refraction:
Use interfere type film thickness gauge [manufacturer: U.S. FILMETRICS, model: F20-UV] test.
(2) judgement of line is interfered
Place cured film at the straight lower 30cm place of 3 wavelength incandescent lamps, observe rainbow line, and assess according to following standard:
Do not find to interfere line to be counted " ◎ ",
Find very slight color, the interference line that ripple is very little counts "○",
Find that color is more shallow, the interference line that ripple is less is counted " △ ",
Find significantly to interfere line to count "×".
(3) pencil hardness test
Method according to standard GB/T6739-1996 is measured.
(4) abrasion test method
The surface #0000 steel wire bobbles of transparent hardening coat carries out reciprocating friction, and it bears a heavy burden for 100g/cm2, and frictional distance is 5-6cm.Observe and assessed by the scuffing situation on rubbed cured film surface, not occur that the thin the highest Rubbing number scratched carries out metering assessment.
(5) resistance to crimpiness method of testing
Print is cut into: long 10cm × wide 2cm shape rectangular, outside with cured film, the rod iron being respectively 2.0mm in diameter is wound around, after launch successively, observe the hair check situation of hardened surface, and assess according to following standard:
Have no crackle, cracking and coating shedding to count " ◎ ",
Only occur that extremely slight crackle counts "○",
There is slight crackle, have no cracking and coating shedding count " △ ",
Occur that obvious crackle, cracking and coating shedding count "×".
(6) stretch forming method of testing
Different cured film print is carried out shaping stretching according to 7-8mm height and 90 ° of angles, and whether have crackle, cracking and coating shedding disadvantage, and assess according to following standard if observing differently curved lower hardened face after stretching:
Have no crackle, cracking and coating shedding to count " ◎ ",
Only occur that extremely slight crackle counts "○",
There is slight crackle, have no cracking and coating shedding count " △ ",
Occur that obvious crackle, cracking and coating shedding count "×".
(7) light transmittance, mist degree test
Haze meter is used [to be manufactured by Hitachi, Ltd; Model: " U3000 "], measure total light transmittance (Tt) and mist degree (H).
Claims (3)
1. one kind has the transparent hardened film of low interference line, it is characterized in that, it applies transparent hard layer on support, described hardened layer comprises the first coating and is positioned at the second coating on the first coating, the refractive index of described first coating is 1.57 ~ 1.69, thickness is 0.05 ~ 0.25 μm, and the refractive index of described second coating is 1.45 ~ 1.60, thickness is 2 ~ 3 μm;
Described first coating contains the film forming matter that refractive index is 1.57 ~ 1.69, or containing film forming matter and high index of refraction metallic compound that refractive index is less than 1.57; The metallic compound of described high index of refraction is titanium dioxide or tin indium oxide;
Described second coating contains acrylic monomers or their composition of more than the polyurethane acroleic acid prepolymer of more than a kind of 3 degrees of functionality, 3 degrees of functionality;
Polyurethane acroleic acid prepolymers more than described 3 degrees of functionality is pentaerythrite three (methyl) acrylate hexylene glycol vulcabond carbamate prepolymer, pentaerythrite three (methyl) acrylate toluene di-isocyanate(TDI) carbamate prepolymer, pentaerythrite three (methyl) acrylate isoflurane chalcone diisocyanate carbamate prepolymer or their mixture;
Described refractive index be 1.57 ~ 1.69 film forming matter comprise and introduce aromatic compound or fused ring compound, introducing aliphatic polycyclic compound, introduce sulphur or epithio based compound or their composition;
Also light trigger is added in the coating fluid of described first coating, the second coating.
2. transparent hardened film according to claim 1, is characterized in that, the refractive index of described first coating is 1.59 ~ 1.62.
3. transparent hardened film according to claim 2, it is characterized in that, acrylic monomers more than described 3 degrees of functionality is pentaerythrite three (methyl) acrylate monomer, pentaerythrite four (methyl) acrylate monomer, dipentaerythritol three (methyl) acrylate monomer, dipentaerythritol four (methyl) acrylate monomer, dipentaerythritol five (methyl) acrylate monomer, dipentaerythritol six (methyl) acrylate monomer, trimethylolpropane tris (methyl) acrylate monomer or their mixture.
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| CN103738025B (en) * | 2013-12-25 | 2016-04-06 | 东莞市纳利光学材料有限公司 | A kind of high rigidity screen protecting film and preparation method thereof |
| CN103911067A (en) * | 2014-03-19 | 2014-07-09 | 苏州袭麟光电科技产业有限公司 | Protection film with high hardness, super wearing resistance and no newton ring, and its preparation method |
| CN104250517A (en) * | 2014-09-04 | 2014-12-31 | 卢岳 | Nanometer protective membrane for electronic device screen and preparation method thereof |
| CN105044803B (en) * | 2015-08-13 | 2017-05-31 | 宁波雅歌新材料科技有限公司 | A kind of high transmittance anti-interference line optical thin film and preparation method thereof |
| CN109765647A (en) * | 2018-12-28 | 2019-05-17 | 张家港康得新光电材料有限公司 | A kind of transparent polyimide film |
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| CN101680968A (en) * | 2008-03-21 | 2010-03-24 | 木本股份有限公司 | Film for optical use, laminate, and touch panel |
| CN101831239A (en) * | 2010-05-11 | 2010-09-15 | 中国乐凯胶片集团公司 | Transparent hardened film for in-mold decoration |
| CN101885255A (en) * | 2010-06-30 | 2010-11-17 | 中国乐凯胶片集团公司 | Shallow fringe transparent hard coating film for in-mold decoration |
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2011
- 2011-10-29 CN CN201110334397.4A patent/CN102490429B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101680968A (en) * | 2008-03-21 | 2010-03-24 | 木本股份有限公司 | Film for optical use, laminate, and touch panel |
| CN101831239A (en) * | 2010-05-11 | 2010-09-15 | 中国乐凯胶片集团公司 | Transparent hardened film for in-mold decoration |
| CN101885255A (en) * | 2010-06-30 | 2010-11-17 | 中国乐凯胶片集团公司 | Shallow fringe transparent hard coating film for in-mold decoration |
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| CN102490429A (en) | 2012-06-13 |
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