CN106634462A - Hard coating film with high dyne value - Google Patents

Hard coating film with high dyne value Download PDF

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Publication number
CN106634462A
CN106634462A CN201611207128.0A CN201611207128A CN106634462A CN 106634462 A CN106634462 A CN 106634462A CN 201611207128 A CN201611207128 A CN 201611207128A CN 106634462 A CN106634462 A CN 106634462A
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cured film
hardened layer
layer coating
worth
coating fluid
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CN106634462B (en
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徐倩倩
王辉
刘玉磊
史良
赵俊武
胡鑫
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Hefei Lucky Science and Technology Industry Co Ltd
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Hefei Lucky Science and Technology Industry Co Ltd
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention discloses a hard coating film with a high dyne value, comprising a PET supporter, and a hard coating layer formed by solidifying after coating hard coating layer coating on at least one surface of the PET supporter, wherein the hard coating layer coating has the following components in parts by weight: 15-50 parts of matrix resin, 2-10 parts of oxide particles, 0.05-5.0 parts of surface additive, 0.05-7.0 parts of photoinitiator and 40-80 parts of solvent. The dyne value of the hard coating film provided by the invention can reach 38Dyne-46Dyne, thus being capable of meeting operating requirements of customers on subsequent ITO coating technology and ink printing technology.

Description

One kind is up to because being worth cured film
Technical field
The present invention relates to coating composition, especially a kind of with up to because of the cured film being worth.
Background technology
Cured film is a kind of film product carried out on PET supports obtained by Surface hardening treatment.The product has good Optical property well, excellent damage resistant, heat resistance and apparent mass.It is mainly used in touch screen industry, is widely used in touching Control panel, liquid crystal display, instrument face plate, mobile phone, tablet PC, digital camera, notebook and industrial display Device etc..In the market cured film product category is various, and common hardness 1H～4H has volume production, in subsequent treatment, except right The requirement of key property, also requires that its cementation zone has good tack to ink, to ensure excellent printing effect, ITO plated films, to reach more preferable ITO coating effects, also have certain requirement with cured film product to its adhesion property.Research It was found that, cured film product surface dyne value is higher, and adhesion property is better, and subsequent ink printing and coating effects are also better.Market Upper existing cured film product surface dyne is worth mostly in 32Dyne～36Dyne or so, and its dyne is worth meeting over time and storage The difference for depositing condition is presented different degrees of decay, causes printing and coating effects to be deteriorated, and coating is easy to fall off, it is difficult to long-term to meet The use requirement of downstream client.
In order to improve the surface tension of cured film so as to stable up to because of value, so as to more preferable for downstream client Used, in the industry in the urgent need to finding suitable hardening formula and production method, made a kind of with up to because of the cured film of value Product.
The content of the invention
The main object of the present invention is to provide a kind of up to because of value cured film, dyne is worth in more than 38Dyne, to guarantee There is excellent printing performance and adhesion property in ink printing and ITO coating process.
It is that, up to this purpose, the present invention is employed the following technical solutions：
One kind is up to because value cured film, including PET supports and PET support at least one sides are coated with hardened layer coating The hardened layer that liquid solidify to form, the component and parts by weight of the hardened layer coating fluid are：
Weight portion～50 weight portion of matrix resin 15；
Weight portion～10 weight portion of oxide particle 2；
Weight portion～5.0 weight portion of surface modifier 0.05；
Weight portion～7.0 weight portion of light trigger 0.05；
Weight portion～80 weight portion of solvent 40；
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
Wherein：η is the viscosity of the hardened layer coating fluid, unit mPa.s；P is the UV solidifications of the hardened layer coating fluid Energy, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout system of the hardened layer coating fluid Number,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively The baking temperature of n dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence is through each temperature The time of degree section is respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
Above-mentioned to be up to because being worth cured film, the matrix resin is polyester acrylate, epoxy acrylate, polyurethane propylene One or more in acid esters or polyether acrylate.
Above-mentioned to be up to because being worth cured film, the oxide particle is in silicon dioxide granule or metal oxide particle Plant or several.
It is above-mentioned up to because being worth cured film, the surface modifier is the alkyl-modified organosilicon of aralkyl, polyether-modified organic One kind in silicon, Polyacrylate Modified by Polysiloxane, the polyester resin change properties of organic silicon class surface modifier of acid functional group containing propylene Or it is several.
It is above-mentioned up to because being worth cured film, the light trigger be 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyls- One or more in 1- phenyl -1- acetone.
Above-mentioned to be up to because being worth cured film, the solvent is water-alcohol class mixed solvent or esters -one class mixed solvent.
Above-mentioned up to because of value cured film, the product drying solidifies using stage drying technique, and institute's segments is 3 sections～9 Section, each dryer section setting different temperatures.
Above-mentioned to be up to because being worth cured film, the dryer section baking temperature is 293K～393K.
Above-mentioned to be up to because being worth cured film, the hardened layer coating solution mode is micro gravure coating, comma roller coating Or the coating of slit type extrusion pressing type.
It is above-mentioned that up to because being worth cured film, the PET supports that body thickness is 50 μm～188 μm, hardened layer apply thickness be 0.8 μm～ 3.5μm。
Compared with prior art,
1st, hardened layer coating fluid of the present invention can be formed up to because of value, high rigidity, wear-resisting and tool on PET supports surface There is the hardened layer of excellent optical property, printing performance and good ITO coating performances.
2nd, prepared cured film dyne value disclosure satisfy that follow-up ITO coating process, ink up to 38Dyne～46Dyne The use requirement of typography.
3rd, the present invention adopts stage drying technique, is coated with according to the hardened layer coating fluid average intrinsic viscosity and hardened layer Fluid solid content, selects baking temperature, the drying time of difference UV solidification energies and different temperatures section.On the one hand the hardening is controlled Layer dry rate, by the reaction rate between alternating temperature process control macromolecular compound chemical bond and response time, makes described hard Change layer to be gradually dried.The hardening layer surface produces the chain polymer of different length because of extent of chemical reaction difference, described Hardening layer surface produces tiny microstructural differences, it is ensured that the hardened layer has stable being up to because of value, the raising hardening The surface then performance of layer.Because being in this way to change the apparent property of the hardened layer by changing chemical constitution, change Structures shape its property is learned, will not impact be produced on its surface chemical structure in later stage storage transport, so as to ensure that State the stability of cured film product surface dyne value.On the other hand, using stage drying, temperature is gradual change, also ensure that institute Stating cured film product will not affect following process to use in dry run because temperature jump produces obvious warpage.
What the 4th, the present invention was provided is up to because value cured film is testing (85 DEG C/500h), hot and humid experiment (temperature through high temperature Degree 60 DEG C, humidity 90RH/500h), thermal shock experiment (temperature is circulated 100 times by -40 DEG C to 60 DEG C, and each temperature stops 1h) Afterwards, surface dynes value can still be maintained at more than 38Dyne, and every key property without significant change.
Specific embodiment
Technical scheme is further illustrated with reference to specific embodiment.
Embodiment 1
The each component and parts by weight of cured film coating fluid be：
In the acrylate of 14g aliphatic six, [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures, trade name：571] in [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures, trade name to add 7g bisphenol-A epoxy acrylic resins：127-TP20], stirring 5g silica nanometer additives [Bi Ke chemistry manufactures, trade name are added after uniform：NANOBYK-3651], it is again stirring for uniform The alkyl-modified organosilicon of 0.05g surface modifier aralkyl [Bi Ke chemistry manufactures, trade name are added afterwards：BYK-322], 2g light draws [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures, trade name to send out agent 1- hydroxycyclohexyl phenyl ketones：Doublecure 184], 49g methylisobutylketones and the dilution of 22.9g butanone are stirring evenly and then adding into, 1-2h is stood after being sufficiently stirred for, obtain the hardened layer Coating fluid.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 50 micro- Rice, it is 0.8 micron to control to apply thickness.Jing test coateds fluid viscosity is 2.31mPa.s, and solid content is 21%, Jing 293K-333K- 358K stage dryings, by the time of each dryer section 90s-60s-120s is respectively, and then carries out UV solidifications, UV solidification energies About 0.43J/cm2, obtain described up to because of value cured film after UV completion of cures.
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
Wherein：η is the viscosity of the hardened layer coating fluid, unit mPa.s；P is the UV solidifications of the hardened layer coating fluid Energy, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout system of the hardened layer coating fluid Number,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively The baking temperature of n dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence is through each temperature The time of degree section is respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
Described is 46Dyne up to because the Jing tests dyne of value cured film are worth, and through high temperature (85 DEG C/500h), high temperature height are tested Wet experiment (temperature 60 C, humidity 90%RH/500h), thermal shock experiment (temperature by -40 DEG C to 60 DEG C circulate 100 times, each - 40 DEG C and 60 DEG C of circulation is each to stop 1h) after, it is described to be up to because value cured film surface dynes value still keep 46Dyne, and respectively Item key property is without significant change.
Embodiment 2
The each component and parts by weight of cured film coating fluid be：
In the solvent modified polyurethane acrylate resins of 12g, [Taiwan Changxing Chemical Industry Co Ltd manufactures, commodity Name：DR-U092] [Sartomer Asia company limited manufactures middle addition 3g epoxy acrylates, trade name：CN104NS], stirring is equal 2g silica nanometer additives [Bi Ke chemistry manufactures, trade name are added after even：NANOBYK-3651], after being again stirring for uniformly Add 3g surface modifier organic silicon modified by polyether [Bi Ke chemistry manufactures, trade name：BYK-325], 7.0g light trigger 1- hydroxyls [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures cyclohexyl phenyl ketone, trade name：Doublecure 184], after stirring 48.5g methylisobutylketones and the dilution of 31.5g propylene glycol monomethyl ethers are added, 1-2h is stood after being sufficiently stirred for, obtain the hardened layer Coating fluid.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 188 micro- Rice, it is 1.5 microns to control to apply thickness.It is 2.03mPa.s that Jing tests above-mentioned coating fluid viscosity, and solid content is 15%, Jing 313K- 333K-363K-348K stage dryings, by the time of each dryer section 60s-60s-60s-60s is respectively, and is then carried out UV and is consolidated Change, UV solidification energies about 0.49J/cm2, obtain described up to because of value cured film after UV completion of cures.
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
Wherein：η is the viscosity of the hardened layer coating fluid, unit mPa.s；P is the UV solidifications of the hardened layer coating fluid Energy, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout system of the hardened layer coating fluid Number,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively The baking temperature of n dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence is through each temperature The time of degree section is respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
Described is 44Dyne up to because the Jing tests dyne of value cured film are worth, and through high temperature (85 DEG C/500h), high temperature height are tested Wet experiment (temperature 60 C, humidity 90%RH/500h), thermal shock experiment (temperature by -40 DEG C to 60 DEG C circulate 100 times, each - 40 DEG C and 60 DEG C of circulation is each to stop 1h) after, it is described to be up to because value cured film surface dynes value still keep 44Dyne, and respectively Item key property is without significant change.
Embodiment 3
The each component and parts by weight of cured film coating fluid be：
In 30g polyurethane acrylate resins, [Sartomer Asia company limited manufactures, trade name：CN750] middle addition 9g Zinc-oxide nano additive [Bi Ke chemistry manufactures, trade name：NANOBYK-3860], it is stirring evenly and then adding into 1.5g surface modifiers [this special chemical company of hamming, trade name：Adherant ADK], 7g light trigger 2- hydroxy-2-methyl -1- phenyl -1- third [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures ketone, trade name：Doublecure 1173], it is stirring evenly and then adding into 52.5g different Propanol dilutes, and 1-2h is stood after being sufficiently stirred for, and obtains the hardened layer coating fluid.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 125 micro- Rice, it is 3.5 microns to control to apply thickness.It is 3.4mPa.s that Jing tests above-mentioned coating fluid viscosity, and solid content is 30%, Jing 293K-313K- 328K-348K-368K-393K-358K-338K-323K stage dryings, by the time of each dryer section 30s-30s- is respectively 60s-30s-45s-15s-45s-60s-60s, then carries out UV solidifications, UV solidification energies about 0.38J/cm2, after UV completion of cures Obtain described up to because of value cured film.
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
Wherein：η is the viscosity of the hardened layer coating fluid, unit mPa.s；P is the UV solidifications of the hardened layer coating fluid Energy, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout system of the hardened layer coating fluid Number,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively The baking temperature of n dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence is through each temperature The time of degree section is respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
Described is 46Dyne up to because the Jing tests dyne of value cured film are worth, and through high temperature (85 DEG C/500h), high temperature height are tested Wet experiment (temperature 60 C, humidity humidity 90%RH/500h), thermal shock experiment (temperature by -40 DEG C to 60 DEG C circulate 100 times, Each -40 DEG C and 60 DEG C of circulation is each to stop 1h) after, it is described up to because value cured film surface dynes value can still be maintained at 44Dyne More than, and every key property is without significant change.
Embodiment 4
The each component and parts by weight of cured film coating fluid be：
In 50g polyester acrylate resins, [Taiwan Changxing Chemical Industry Co Ltd manufactures, trade name：DR- E582] in add 4.65g surface treateds aluminium oxide nano additive [Bi Ke chemistry manufacture, trade name：NANOBYK- 3610], it is stirring evenly and then adding into 5g surface modifier organic silicon modified by polyether [Bi Ke chemistry manufactures, trade name：BYK-325]、 [Taiwan Double Bond Chemical Ind.,Co.,Ltd. manufactures 0.35g light trigger 1- hydroxycyclohexyl phenyl ketones, trade name： Doublecure 184], the dilution of 40g butyl acetates is stirring evenly and then adding into, 1～2h is stood after being sufficiently stirred for, obtain described hard Change layer coating fluid.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 125 micro- Rice, it is 2.0 microns to control to apply thickness.It is 4.22mPa.s that Jing tests above-mentioned coating fluid viscosity, and solid content is 50%, Jing 303K- 328K-363K-358K-318K stage dryings, are respectively 60s-50s-45s-65s-60s, so by the time of each dryer section After carry out UV solidifications, UV solidification energies about 0.37J/cm2, obtain described up to because of value cured film after UV completion of cures.
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
Wherein：η is the viscosity of the hardened layer coating fluid, unit mPa.s；P is the UV solidifications of the hardened layer coating fluid Energy, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout system of the hardened layer coating fluid Number,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively The baking temperature of n dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence is through each temperature The time of degree section is respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
Described is 46Dyne up to because the Jing tests dyne of value cured film are worth, and through high temperature (85 DEG C/500h), high temperature height are tested Wet experiment (temperature 60 C, humidity 90%RH/500h), thermal shock experiment (temperature by -40 DEG C to 60 DEG C circulate 100 times, each - 40 DEG C and 60 DEG C of circulation is each to stop 1h) after, it is described be up to because value cured film surface dynes value can still be maintained at 44Dyne with On, and every key property is without significant change.
Comparative example 1
Using hardened layer coating fluid formula used by embodiment 1.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 50 micro- Rice, it is 0.8 micron to control to apply thickness, and UV solidifications, UV solidification energies about 0.43J/cm are carried out Jing after 348K temperature is dried 120s2, UV Cured film product is obtained after completion of cure.
The cured film Jing tests dyne value is 36Dyne, and through high temperature (85 DEG C/500h), hot and humid experiment are tested The experiment of (temperature 60 C, humidity 90%RH/500h), thermal shock (temperature is circulated 100 times by -40 DEG C to 60 DEG C, and each circulation - 40 DEG C and 60 DEG C each stop 1h) after, the cured film surface dynes value is 30Dyne.
Comparative example 2
Using hardened layer coating fluid formula used by embodiment 3.
By the hardened layer coating solution in PET supports it is two-sided on, the PET supports that body thickness is 125 micro- Rice, it is 3.5 microns to control to apply thickness, and UV solidifications, UV solidification energies about 0.37J/cm are carried out Jing after 368K temperature is dried 180s2, UV Cured film product is obtained after completion of cure.
The cured film Jing tests dyne value is 36Dyne, and through high temperature (85 DEG C/500h), hot and humid experiment are tested The experiment of (temperature 60 C, humidity 90%RH/500h), thermal shock (temperature is circulated 100 times by -40 DEG C to 60 DEG C, and each circulation - 40 DEG C and 60 DEG C each stop 1h) after, the cured film surface dynes value is 30Dyne.
Tested using Britain's Sherman Treaters dyne pens.
Test result：
Presently preferred embodiments of the present invention is the foregoing is only, not to the restriction of other embodiment of the present invention, to this Equivalent changes, modifications or replacement that bright technical scheme is made, all should fall within the protection domain of patent of the present invention.

Claims (10)

1. a kind of up to because value cured film, including PET supports and PET support at least one sides are coated with hardened layer coating fluid The hardened layer solidifying to form, it is characterised in that the component and parts by weight of the hardened layer coating fluid be：
Weight portion～50 weight portion of matrix resin 15；
Weight portion～10 weight portion of oxide particle 2；
Weight portion～5.0 weight portion of surface modifier 0.05；
Weight portion～7.0 weight portion of light trigger 0.05；
Weight portion～80 weight portion of solvent 40；
The viscosity of the hardened layer coating fluid, solid content and dry solidification process conditions meet below equation：
ln η 3.27 × P 2 × S C × 1.85 = t 1 T 1 e k 1 + t 2 T 2 e k 2 + t 3 T 3 e k 3 + ... + t n T n e k n T θ 4 ,
Wherein：η for hardened layer coating fluid viscosity, unit mPa.s；P is the UV solidification energies of the hardened layer coating fluid, unit J/cm2；SC is the solid content percentage ratio of the hardened layer coating fluid；K is the tuningout coefficient of the hardened layer coating fluid,N be through n dryer section；T is baking temperature, unit K；T1-T2-T3-...-TnFinger is followed successively by respectively n The baking temperature of dryer section；T is coated product through the time of each baking temperature section, unit s；Correspondence passes through each temperature section Time be respectively t1-t2-t3-...-tn；TθFor standard temperature, Tθ=273.15K.
2. it is according to claim 1 up to because being worth cured film, it is characterised in that the matrix resin is polyester acrylic One or more in ester, epoxy acrylate, urethane acrylate or polyether acrylate.
3. it is according to claim 2 up to because being worth cured film, it is characterised in that the oxide particle is titanium dioxide silicon grain One or more in son or metal oxide particle.
4. it is according to claim 3 up to because being worth cured film, it is characterised in that the surface modifier is aralkyl alkyl Modified organic silicon, organic silicon modified by polyether, Polyacrylate Modified by Polysiloxane, the polyester modification of acid functional group containing propylene have One or more in machine silicon class surface modifier.
5. it is according to claim 4 up to because being worth cured film, it is characterised in that the light trigger is 1- hydroxy-cyclohexyls One or two in phenyl ketone or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
6. it is according to claim 5 up to because being worth cured film, it is characterised in that the solvent is water-alcohol class mixed solvent Or esters -one class mixed solvent.
7. it is according to claim 6 up to because being worth cured film, it is characterised in that the product drying solidification is dry using segmentation Drying process, institute's segments is 3 sections～9 sections, each dryer section setting different temperatures.
8. according to claim 7 up to because being worth cured film, it is characterised in that the dryer section baking temperature be 293K～ 393K。
9. according to any one of claim 1～8 up to because being worth cured film, it is characterised in that the hardened layer coating fluid Coating method is micro gravure coating, comma roller coating or the coating of slit type extrusion pressing type.
10. according to claim 9 up to because being worth cured film, it is characterised in that the PET support body thickness be 50 μm～ 188 μm, thin hardened layer is 0.8 μm～3.5 μm.
CN201611207128.0A 2016-12-23 2016-12-23 One kind is up to because being worth cured film Active CN106634462B (en)

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CN112552728A (en) * 2020-12-11 2021-03-26 佛山市建春友金属科技有限公司 Stainless steel coating capable of efficiently resisting bacteria and fingerprints and preparation method thereof
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CN113625374A (en) * 2021-07-12 2021-11-09 安徽菲尔慕材料有限公司 Manufacturing process of polyimide hardened film of flexible high-hardness high-folding screen

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