Summary of the invention
In view of this, the object of the invention is to prior art to improve, two-sided cured film of a kind of anti and preparation method thereof is provided, while making cured film stacked together, can slide, the blocking action while reducing rolling, plays the effect of antiblocking.
For solving the above-mentioned problems in the prior art, the present invention carries out hardening treatment in the one side of PET base material, improves coatingsurface hardness to 3H, can prevent that PET coating is by scratch; And the another side of PET base material adds some nano-powders in formulation for coating material, under ultraviolet lighting, harden, form anti (Anti-Blocking is called for short AB) cured film.There is part particle projection on this AB layer surface, increased like this space between AB hardened face and high rigidity hardened face, reduced the vacuum tightness between coating, while making AB layer and hardened layer stacked together, can slide, blocking action while reducing rolling, can meet the performance requriements of ito thin film high rigidity, high-penetration and low haze again simultaneously.
Concrete, the two-sided cured film of anti of the present invention, comprise base material, (one side of base material is carried out after hardening treatment hardness in the coating of 3H to be coated on the 3H hardened layer of described base material one side surface, be called for short in full 3H hardened layer) and (another side of base material carries out playing after hardening treatment the Anti-Blocking coating of antiblocking effect to be coated on the AB hardened layer on described base material opposite side surface, be called for short in full AB hardened layer), according to mass fraction meter, described 3H hardened layer comprises following component:
Described AB hardened layer comprises following component:
Wherein, described polyfunctionality oligopolymer is 6 functionality and above aliphatic urethane acrylate or aromatic urethane origoester acrylate; Described polyfunctionality monomer is 3 functionality and above acrylate monomer; Described low functionality acrylate monomer is 3 functionality and following acrylate monomer; Described nano silica powder is the nano silica powder of particle diameter 10~800nm; Described flow agent B is response type modified polyorganosiloxane flow agent; Described wetting dispersing agent is the wetting dispersing agent containing acid pigment affinity groups.
Preferably, described polyfunctionality monomer is one or more in pentaerythritol triacrylate, tetramethylol methane tetraacrylate, double pentaerythritol C5 methacrylate, dipentaerythritol acrylate, Viscoat 295, ethoxyquin Viscoat 295, trimethylolpropane trimethacrylate.
Preferably, described low functionality acrylate monomer is methacrylic acid-2-hydroxy methacrylate, acrylamide, dimethacrylate-1,6-hexylene glycol ester, diacrylate-1,6-hexylene glycol ester, ethylene glycol diacrylate, diacrylate triethyleneglycol ester, diacrylate tripropylene glycol ester, diacrylate are to one or more in DOPCP, Viscoat 295, trishydroxymethyl pentane trimethacrylate, TriMethylolPropane(TMP) pentaerythritol triacrylate.
Preferably; described light trigger A is 1-hydroxy-cyclohexyl phenyl ketone (184), 2-hydroxy-methyl phenyl-propane-1-ketone (1173), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (907), benzoin dimethylether (651), benzophenone (BP), 2-isopropyl thioxanthone (ITX), 2; 4,6-(trimethylbenzoyl) one or more in-diphenyl phosphine oxide (TPO).
Further, described light trigger A is 1-hydroxy-cyclohexyl phenyl ketone (184), 2,4,6-(trimethylbenzoyl) a kind of or its mixture in-diphenyl phosphine oxide (TPO).
Preferably, described flow agent A is acrylic acid or the like or silicone based flow agent.As: BYK-333, BYK-307, BYK-377, BYK-378, BYK-UV3500, BYK-306, tego Glide400, tego Glide100, tego Glide405, tego Glide406, tego Glide450, tego Flow370 etc.
Preferably, described organic solvent A is one or more the mixture in ethyl acetate, butylacetate, methyl alcohol, ethanol, Virahol, isopropylcarbinol, mibk, butanone, toluene, dimethylbenzene, pimelinketone.
Preferably; described photoinitiator b is 1-hydroxy-cyclohexyl phenyl ketone (184), 2-hydroxy-methyl phenyl-propane-1-ketone (1173), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (907), benzoin dimethylether (651), benzophenone (BP), 2-isopropyl thioxanthone (ITX), 2; 4,6-(trimethylbenzoyl) one or more in-diphenyl phosphine oxide (TPO).
Further, described photoinitiator b is 1-hydroxy-cyclohexyl phenyl ketone (184).
Preferably, described nano silica powder particle diameter is 10~500nm.
Described flow agent B can be BYK-313, BYK-370, BYK-371, tego Glide410, tego Rad2100, tego Rad2500, tego Rad2250, tego Rad2700 etc.
Described wetting dispersing agent can be BYK110, BYK111, BYK102, BYK145, BYK2059, BYK180, BYK168, tego Dispers670, tego Dispers710, tego Dispers655 etc.
Preferably, described organic solvent B is one or more the mixture in ethyl acetate, butylacetate, methyl alcohol, ethanol, Virahol, isopropylcarbinol, mibk, acetone, butanone, toluene, dimethylbenzene, pimelinketone.
The present invention also provides a kind of method of preparing the two-sided cured film of above-mentioned anti, comprises the steps:
1) provide a substrate layer;
2) be coated on a face of described substrate layer after above-mentioned each component of 3H hardened layer is mixed, dry after uv irradiating solidify;
3) be coated on another face of described substrate layer after above-mentioned each component of AB hardened layer is mixed, dry after uv irradiating solidify, obtain the two-sided cured film of anti.
When the nano silica powder that adds particle diameter and be 10nm~800nm in the one side coating of base material is realized the effect of two-sided cured film antiblocking when stacked, often can encounter particle aggregation, coating mist degree is higher or antiblocking effect is poor problem.The wetting dispersing agent that contains acid pigment affinity groups by interpolation solves the scattering problem of silicon-dioxide, makes silicon-dioxide be difficult for reuniting, and reduces coating mist degree.Add response type modified polyorganosiloxane leveling auxiliary agent simultaneously, by the part uncompatibility of auxiliary agent, control particle floating but entirely do not float over coatingsurface.So both guarantee two-sided cured film antiblocking effect, do not affected again the mist degree of coating.
Wherein 3H hardened layer has higher hardness, can scrape resistant, and there are some particles projections on AB hardened layer surface, gives again coating good antiblocking effect, while making film take-up, AB hardened layer and 3H hardened layer can not be sticked together.The two-sided cured film that adopts aforesaid method to prepare, has higher penetration coefficient, and the optical properties such as low haze, can be used as ITO film.
The present invention adds the silicon-dioxide powdery that particle diameter is less in a finishing coat of base material, adopts the wetting dispersing agent containing acid pigment affinity groups, and nano silicon is disperseed preferably.Add modified polyorganosiloxane auxiliary agent simultaneously, make particle entirely not float over coatingsurface, guaranteed the good antiblocking effect of two-sided cured film, do not affect again the optical property of coating.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.
Embodiment 1
The components in mass portion of 3H hardened layer is counted:
In 60 parts of CN9010NS oligopolymer (Sartomer manufacture) and 30 parts of EM235 monomers (Changxing Chemical Industry Co Ltd's manufacture), add 5 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture).With the relative mass amount ratio that comprises of 60 parts, be to obtain mixture after the butylacetate of 1:1 and the mixed solvent of Virahol dilute, then add 0.1 part of auxiliary agent UV3500(BYK to manufacture), stir, obtain 3H hardened layer composition.
Gained 3H hardened layer composition is coated on line rod on a face of the polyethylene terephthalate that thickness is 100 microns of optical grade (PET) film, after dry 2min, be 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the 3H hardened layer of 3 microns.
The components in mass portion of AB hardened layer is counted:
In 50 parts of 6195-100 oligopolymer (Changxing Chemical Industry Co Ltd's manufacture) and 40 parts of M220 monomers (providing color chemical industry manufacture), add 1 part of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd. to manufacture), 0.5 part of high manufacture of response type modified polyorganosiloxane leveling auxiliary agent tego Rad2100(enlightening).With obtaining mixture after the butylacetate dilution of 60 parts, then add 1 part of HTSi-01-A(Nanjing Haitai company limited to manufacture, particle diameter 300~500nm) and the dispersant B YK111 of 0.1 part, even by the high rotating speed dispersed with stirring of clarifixator, obtain AB hardened layer composition.
Gained AB hardened layer composition is coated on another face of PET film that above-mentioned one side scribbles 3H hardened layer with line rod, after dry 2min, is 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the AB hardened layer of 3 microns.
Embodiment 2
The components in mass portion of 3H hardened layer is counted:
In 80 parts of 6145-100 oligopolymer (Changxing Chemical Industry Co Ltd's manufacture) and 20 parts of EM242 monomers (Changxing Chemical Industry Co Ltd's manufacture), add 1 part of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd. to manufacture).With the relative mass amount ratio that comprises of 40 parts, be to obtain mixture after the butylacetate of 1:1 and the mixed solvent of ethyl acetate dilute, then add 5 parts of auxiliary agent 333(BYK to manufacture), stir, obtain 3H hardened layer composition.
Gained 3H hardened layer composition is coated on line rod on a face of the polyethylene terephthalate that thickness is 100 microns of optical grade (PET) film, after dry 2min, be 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the 3H hardened layer of 3 microns.
The components in mass portion of AB hardened layer is counted:
In 90 parts of EB5129 oligopolymer (manufacture of Allnex company) and 30 parts of SM623 monomers (Jiangsu three lignify works are manufactured), add 10 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture), 0.01 part of high manufacture of response type modified polyorganosiloxane leveling auxiliary agent tego Rad2500(enlightening).After ethyl acetate mixed solvent dilution with the butylacetates of 60 parts and 20 parts, obtain mixture, then add 10 parts of HTSi-03(Nanjing Haitai company limiteds to manufacture, particle diameter 10~20nm) and the dispersant B YK168 of 1 part, even by the high rotating speed dispersed with stirring of clarifixator, obtain AB hardened layer composition.
Gained AB hardened layer composition is coated on another face of PET film that above-mentioned one side scribbles 3H sclerosis glue with line rod, after dry 2min, is 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the AB hardened layer of 3 microns.
Embodiment 3
The components in mass portion of 3H hardened layer is counted:
In 70 parts of U900 oligopolymer (Bayer A.G's manufacture) and 40 parts of EB40 monomers (manufacture of Allnex company), add 8 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture) and 2 parts of light trigger TPO(Tianjin Jiu Chemical Co., Ltd.s manufactures).After mixed solvent dilution with 40 parts of butylacetates and 40 parts of Virahols, obtain mixture, then add 1 part of auxiliary agent 333(BYK to manufacture), stir, obtain 3H hardened layer composition.
Gained 3H hardened layer composition is coated on line rod on a face of the polyethylene terephthalate that thickness is 100 microns of optical grade (PET) film, after dry 2min, be 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the 3H hardened layer of 3 microns.
The components in mass portion of AB hardened layer is counted:
In 80 parts of DH-328 aromatic urethane origoester acrylates (ancient cooking vessel good photochemical Science and Technology Ltd. in Shenzhen manufactures) and 30 parts of SM626 monomers (Jiangsu three lignify works are manufactured), add 5 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture), 5 parts of response type modified polyorganosiloxane leveling auxiliary agent BYK-370(BYK manufacture).After ethyl acetate mixed solvent dilution with the butylacetates of 50 parts and 40 parts, obtain mixture, then add 8 parts of HTSi-05(Nanjing Haitai company limiteds to manufacture, particle diameter 500~800nm) and the dispersant B YK168 of 0.5 part, even by the high rotating speed dispersed with stirring of clarifixator, obtain AB hardened layer composition.
Gained AB hardened layer composition is coated on another face of PET film that above-mentioned one side scribbles 3H sclerosis glue with line rod, after dry 2min, is 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the AB hardened layer of 3 microns.
Embodiment 4
The components in mass portion of 3H hardened layer is counted:
In 60 parts of EB8415 oligopolymer (manufacture of Allnex company) and 40 parts of SR399 monomers (Sartomer manufacture), add 5 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture) and 3 parts of light trigger TPO(Tianjin Jiu Chemical Co., Ltd.s manufactures).With obtaining mixture after 50 parts of butyl acetate solvent dilutions, then add 0.5 part of auxiliary agent 377(BYK to manufacture), stir, obtain 3H hardened layer composition.
Gained 3H hardened layer composition is coated on line rod on a face of the polyethylene terephthalate that thickness is 100 microns of optical grade (PET) film, after dry 2min, be 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the 3H hardened layer of 3 microns.
The components in mass portion of AB hardened layer is counted:
In 60 parts of CN9013 aliphatic urethane acrylate oligopolymer (manufacture of Sartomer company limited) and 30 parts of SM623 monomers (Jiangsu three lignify works are manufactured), add 8 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture), 1 part of response type modified polyorganosiloxane leveling auxiliary agent BYK-370(BYK manufactures).With obtaining mixture after the ethyl acetate solvents dilution of 50 parts, then add 5 parts of TT600(Evonik Degussa Corp. to manufacture, particle diameter 60nm) and the dispersant B YK111 of 0.1 part, the high rotating speed dispersed with stirring of use clarifixator is even, obtains AB hardened layer composition.
Gained AB hardened layer composition is coated on another face of PET film that above-mentioned one side scribbles 3H sclerosis glue with line rod, after dry 2min, is 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the AB hardened layer of 3 microns.
Comparative example
The components in mass portion of 3H hardened layer is counted:
In 80 parts of 6145-100 oligopolymer (Changxing Chemical Industry Co Ltd's manufacture) and 20 parts of EM242 monomers (Changxing Chemical Industry Co Ltd's manufacture), add 1 part of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd. to manufacture).With the relative mass amount ratio that comprises of 40 parts, be to obtain mixture after the butylacetate of 1:1 and the mixed solvent of ethyl acetate dilute, then add 5 parts of auxiliary agent 333(BYK to manufacture), stir, obtain 3H hardened layer composition.
Gained 3H hardened layer composition is coated on line rod on a face of the polyethylene terephthalate that thickness is 100 microns of optical grade (PET) film, after dry 2min, be 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the 3H hardened layer of 3 microns.
The components in mass portion of AB hardened layer is counted:
In 80 parts of EB5129 oligopolymer (manufacture of Allnex company) and 50 parts of SM623 monomers (Jiangsu three lignify works are manufactured), add 8 parts of light trigger 184(Tianjin proud son of heaven Chemical Co., Ltd.s to manufacture), 0.5 part of leveling auxiliary agent BKY-358(BYK manufactures).After n-butyl acetate mixed solvent dilution with the ethyl acetate of 30 parts and 40 parts, obtain mixture, then add 1 part of UNA-206(Shanghai Xi Meng Chemical Co., Ltd. to manufacture, particle diameter 2 μ m) and the dispersant B YK101 of 1 part, even by the high rotating speed dispersed with stirring of clarifixator, obtain AB hardened layer composition.
Gained AB hardened layer composition is coated on another face of PET film that above-mentioned one side scribbles 3H sclerosis glue with line rod, after dry 2min, is 300mJ/cm by ultraviolet lighting intensity at 80 ℃
2uV-light irradiate 2 minutes, obtain thickness and be the AB hardened layer of 3 microns.
Each embodiment test result of table 1
Each correlated performance testing method is as follows:
1) coating transmittance, mist degree test
(German BYK manufactures, model: total transmitance (T) and the mist degree (H) of AT-4727) measuring coating to utilize transmission mist shadow instrument.
2) coat-thickness test
Adopt the thickness tester that tramps with one's feet (Marl, Germany manufacture, model: Millimar C1216) testing coating thickness.
3) pencil hardness
According to the method for standard GB/T6739-1996, utilize hardness of film tester (Yasuda manufacture, the model: 553-M) measure of pencil scraping.
4) appearance of coat
Range estimation AB hardened layer outward appearance, and assess according to following standard:
Appearance of coat has no brilliant point or particle is counted " ◎ ";
Appearance of coat only occurs that a small amount of crystalline substance is put or particle is counted " zero ";
Appearance of coat occurs that a large amount of particle cluster accumulations count " ╳ ".
5) antiblocking test
Print is cut into two A4 size shapes.An one side that scribbles 3H hardened layer is wherein piled up with the one side that another scribbles AB hardened layer, at two 2KG counterweights that bear a heavy burden above film, then respectively two films is pulled toward left and right, see and whether can slide, and assess according to following standard:
After heavy burden, two PET films pull to slide completely toward left and right respectively counts " ◎ ";
After heavy burden, two PET films have slight blocked force to count " zero " respectively when left and right pulls;
After heavy burden, two PET films draw respectively motionless counting " ╳ " completely when left and right pulls.
The test data of above embodiment and comparative example shows, adds silicon-dioxide powdery that particle diameter is 10~800nm and containing the wetting dispersing agent of acid pigment affinity groups, can make dispersion liquid more stable in AB hardened layer, is difficult for reuniting, and coating mist degree is lower.Add modified polyorganosiloxane auxiliary agent simultaneously, silicon dioxide granule is partly floated, thereby guarantee the antiblocking performance of two-sided cured film excellence.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.