CN104228257B - A kind of single or double optics sclerosis composite membrane and preparation method thereof - Google Patents
A kind of single or double optics sclerosis composite membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104228257B CN104228257B CN201410464420.5A CN201410464420A CN104228257B CN 104228257 B CN104228257 B CN 104228257B CN 201410464420 A CN201410464420 A CN 201410464420A CN 104228257 B CN104228257 B CN 104228257B
- Authority
- CN
- China
- Prior art keywords
- resin coating
- double
- layer
- composite membrane
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of single or double optics sclerosis composite membrane, it is characterized in that: by basement membrane, and apply and be solidificated in basement membrane single or double hardened resin coating form; Described basement membrane is the two-layer composite membrane of biaxial tension optical grade A, B or A, B, A sandwich diaphragm; Thick 100 ~ 250 μm of basement membrane, thick coating 1 ~ 10 μm.Preparation method is: polyester slice respectively through No. 1, No. 2 extruder melting slabs, vertical pull into base thin slice, again by the surface of hardening resin coating liquid at base thin slice, drying, horizontally to draw, thermal finalization, ultraviolet light polymerization, obtain single or double optics sclerosis composite membrane; Hardening resin coating fluid forms by containing 35% aqueous emulsion of polyurethane, Nano silica sol, surfactant, levelling agent, defoamer, light trigger and resistance to yellow agent.The present invention adopts one-step method to process, and the single or double optics sclerosis composite membrane of preparation is applicable to touching-type monitor field.
Description
Technical field
The invention belongs to optical surface sclerosis composite membrane and manufacture thereof, relate to a kind of single or double (or claiming single/two-sided) optics sclerosis composite membrane and preparation method thereof.The present invention adopts the coating adhesive (i.e. hardening resin coating fluid) of preparation, one-step method processes one side or double-faced forming surface optical sclerosis composite membrane, and the single or double optics sclerosis composite membrane of preparation is mainly used in touching-type monitor field.
Background technology
In recent years, along with the fast development of touch giant-screen and Flexible Displays, sclerosis polyester film is widely used as the indispensable material of one, not only can prevent display screen from scratching as protective material, and can as display structural material.Mainly adopt now and apply a kind of ultraviolet light (UV) cured resin on optical polyester film, make it have certain hardness.But there is following shortcoming in existing technology: (1) polyester film is when carrying out transparent UV type cure process, and surface easily produces interferes rainbow line; (2) in hardening coat, add the large inorganic particle of particle diameter, although hardness can improve like this, affect light transmittance and mist degree; (3) scratch resistance capability is low, and resistance to chemical attack, color inhibition, tack are not good; (4) present processing method all adopts off-line to be coated with and produces, and complex process, efficiency are low, cost is high; (5) organic solvent that technology today uses has adverse effect to environment.
At present, not yet find that employing is by first for the composite sheet of the materials such as different polyester longitudinal stretching and through coating composite membrane last layer light-cured polyurethane hardening resin online, again through cross directional stretch and thermal finalization, through ultraviolet light polymerization, for the preparation of the optics sclerosis composite membrane of touch display screen, with and preparation method thereof.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, particularly existing touch-screen optics sclerosis composite membrane production and processing complexity, ambient influnence, the problem such as light transmittance is low, mist degree is high, provides one to be specially adapted to display screen, single or double optics of good performance and to harden composite membrane and preparation method thereof.
Content of the present invention is: a kind of single or double optics sclerosis composite membrane, is characterized in that: by basement membrane, and apply and the hardened resin coating being solidificated in basement membrane single or double forms;
Described basement membrane is the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm;
The two-layer composite membrane of described biaxial tension optical grade is made up of A, B two membranes, and A layer is 10% ~ 20%:80% ~ 90% with the ratio of the thickness of B layer;
Described biaxial tension optical grade sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 20% ~ 30%:70% ~ 80% with the ratio of the thickness of B layer;
Described single or double optics hardens composite membrane by A tunic compound, B tunic compound respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, obtain through longitudinal stretching, single or double coating hardening resin coating fluid, oven dry, cross directional stretch, thermal finalization and ultraviolet light polymerization;
Described hardened resin coating is by A tunic compound, B tunic compound is respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, longitudinal stretching becomes by A, B is two-layer or by A, B, after the THIN COMPOSITE blank of A tri-layers composition, adopt on the single or double of online coating method hardening resin coating liquid is two-layer at this or the THIN COMPOSITE blank of three layers, drying, cross directional stretch, after thermal finalization, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then through ultraviolet light polymerization, at the hardened resin coating that membrane surface obtains,
The preparation method of described A tunic compound is: by 99.88% ~ 99.935% poliester chip, 0.015% ~ 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% ~ 0.1% heat stabilizer composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C ~ 285 DEG C temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
The preparation method of described B tunic compound is: get each raw material by the mass percent composition of 99.9% ~ 99.95% poliester chip, 0.05% ~ 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C ~ 285 DEG C temperature, granulation, namely obtained B tunic compound, for subsequent use;
The preparation method of described hardening resin coating fluid is: in (preparation that can weigh) container, under agitation add 40 ~ 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 ~ 4 weight portion Nano silica sol is added successively under stirring, 0.5 ~ 1.5 parts surfactant, 0.1 ~ 0.5 weight portion levelling agent, 0.1 ~ 0.5 weight portion defoamer, 1 ~ 8 weight portion light trigger, the resistance to yellow agent of 0.1 ~ 0.8 weight portion, finally add 1 ~ 8 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid,
Described Nano silica sol is the nanometer grade silica emulsion of average grain diameter 100nm, can select Dutch Akzo Nobel N.V.
trade mark product or other commercially available prod;
Described surfactant is polyethers, can select the TERGITOL of Dow Chemical
tMtMN-6 trade mark product or other commercially available prod;
Described levelling agent can select the Dynol of US Air gasification chemical product company
tM604 trade mark products or other commercially available prod;
Described defoamer is organic silicon polyether copolymer, can select the TERGITOL of Dow Chemical
tMl-61 trade mark product or other commercially available prod;
Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, i.e. light trigger 659;
Described resistance to yellow agent can select CHISORB1300 trade mark product or other commercially available prod of Taiwan Double Bond Chemical Ind.,Co.,Ltd.;
Described reactive diluent is tri (propylene glycol) diacrylate.
In content of the present invention: the thickness of described basement membrane can be 100 ~ 250 μm, and the hardened resin coating thickness on each surface of basement membrane can be 1 ~ 10 μm.
In content of the present invention: the viscosity of described obtained hardening resin coating fluid can be 72 ~ 142mPas at temperature 25 DEG C.
In content of the present invention: the described pH containing 35% aqueous emulsion of polyurethane (that is: containing percentage by weight in aqueous emulsion of polyurethane is the polyurethane of 35%) is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C; Described 35% aqueous emulsion of polyurethane that contains can select U.S. CYTEC company
the aqueous emulsion of polyurethane product of the trade mark or other commercially available prod; Described 35% aqueous emulsion of polyurethane that contains also can use homemade aqueous emulsion of polyurethane, the preparation method of self-control aqueous emulsion of polyurethane is: adopt prior art, with polyether Glycols, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, triethanolamine, deionized water etc. for raw material, prepare aqueous emulsion of polyurethane.
Another content of the present invention is: a kind of preparation method of single or double optics sclerosis composite membrane, is characterized in that step is:
A, preparation A tunic compound: by 99.88% ~ 99.935% poliester chip, 0.015% ~ 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% ~ 0.1% heat stabilizer composition gets each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C ~ 285 DEG C temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
B, preparation B tunic compound: get each raw material by the mass percent composition of 99.9% ~ 99.95% poliester chip, 0.05% ~ 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C ~ 285 DEG C temperature, granulation, namely obtained B tunic compound, for subsequent use;
C, prepare hardening resin coating fluid: in (preparation that can weigh) container, under agitation add 40 ~ 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 ~ 4 weight portion Nano silica sol is added successively under stirring, 0.5 ~ 1.5 parts surfactant, 0.1 ~ 0.5 weight portion levelling agent, 0.1 ~ 0.5 weight portion defoamer, 1 ~ 8 weight portion light trigger, .1 the resistance to yellow agent of ~ 0.8 weight portion, finally add 1 ~ 8 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid,
Described Nano silica sol is the nanometer grade silica emulsion of average grain diameter 100nm, can select Dutch Akzo Nobel N.V.
trade mark product or other commercially available prod;
Described surfactant is polyethers, can select the TERGITOL of Dow Chemical
tMtMN-6 trade mark product or other commercially available prod;
Described levelling agent can select the Dynol of US Air gasification chemical product company
tM604 trade mark products or other commercially available prod;
Described defoamer is organic silicon polyether copolymer, can select the TERGITOL of Dow Chemical
tMl-61 trade mark product or other commercially available prod;
Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, i.e. light trigger 659;
Described resistance to yellow agent can select CHISORB1300 trade mark product or other commercially available prod of Taiwan Double Bond Chemical Ind.,Co.,Ltd.;
Described reactive diluent is tri (propylene glycol) diacrylate;
D, prepare single or double optics sclerosis composite membrane: the obtained B tunic compound of the A tunic compound that step a is obtained and step b respectively through No. 1 single screw extrusion machine and No. 2 single screw extrusion machines at 285 DEG C of temperature after melting, (after measuring pump accurate measurement) is by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 12 ~ 20 DEG C of cold drums, cooling forms compound slab, 3 ~ 5m is entered long with the speed of 10 ~ 30m/ minute, after the longitudinal stretching section stretching 2.2 ~ 3.8 times of temperature 65 ~ 95 DEG C, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 22 ~ 114m/ minute, 15 ~ 45 DEG C are cooled to 1 ~ 3 second, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that the hardening resin coating fluid that step c is obtained is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 5 ~ 9m long, the preheating section removing moisture that temperature is 100 ~ 135 DEG C, then long at 8 ~ 12m, the cross directional stretch section of temperature 135 ~ 155 DEG C stretches 2.2 ~ 3.8 times, long through 10 ~ 16m again, the heat-setting section sizing that temperature is 225 ~ 245 DEG C 0.1 ~ 0.8 minute, obtain the basement membrane that single or double has hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, again through temperature 60 ~ 80 DEG C, the rolling after cooling in 0.1 ~ 1 minute and at room temperature two stages, i.e. obtained single or double optics sclerosis composite membrane finished product.
In another content of the present invention: the two-layer composite membrane of the optical grade of biaxial tension described in steps d is made up of A, B two membranes, the reasonable of thickness of A layer and B layer is 10% ~ 20%:80% ~ 90%.
In another content of the present invention: the optical grade of biaxial tension described in steps d sandwich diaphragm is made up of A, B, A trilamellar membrane successively, the reasonable of thickness of A layer and B layer is 20% ~ 30%:70% ~ 80%.
In another content of the present invention: the thickness of basement membrane described in steps d can be 100 ~ 250 μm, this thickness is not containing the thickness of hardened resin coating; The hardened resin coating thickness on each surface of described basement membrane can be 1 ~ 10 μm, and described hardened resin coating thickness can be controlled by the applicator roll and two-layer or three layers of THIN COMPOSITE blank relative velocity and pressure roller and applicator roll clearance distance adjusting online apparatus for coating.
In another content of the present invention: the pH containing 35% aqueous emulsion of polyurethane (that is: containing percentage by weight in aqueous emulsion of polyurethane is the polyurethane of 35%) described in step c is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C; Described 35% aqueous emulsion of polyurethane that contains can select U.S. CYTEC company
the aqueous emulsion of polyurethane product of 7655 trades mark or other commercially available prod; Described 35% aqueous emulsion of polyurethane that contains also can use homemade aqueous emulsion of polyurethane, the preparation method of self-control aqueous emulsion of polyurethane is: adopt prior art, with polyether Glycols, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, triethanolamine, deionized water etc. for raw material, prepare aqueous emulsion of polyurethane.This aqueous emulsion of polyurethane be white slightly blue light, with polyester film tack excellence, water white transparency, color inhibition, film forming excellence.
In another content of the present invention: the solidification of ultraviolet light cross-linking described in steps d is preferably and adopts 200W/cm light-focusing type high-pressure mercury-vapor lamp to carry out, and irradiation energy is 800mj/cm
2.
Compared with prior art, the present invention has features and beneficial effect:
(1) optical level polyester film that the present invention uses adopts multi-layer co-extruded, decreases the interference rainbow line of polyester film surface, brilliant point, adds the adhesive force of hardening coat, improve light transmittance, reduce mist degree;
(2) the optical grade polyester base film that the present invention is used adopts multi-layer co-extruded, and top layer silica not only can solve optical thin film production run, but also can improve hardness;
(3) the polyurethane resin viscosity of the present invention's use is little, and filming performance is good, and tack is excellent, and state of cure is high, and coating hardness can reach 4H;
(4) the online coating method of the present invention's employing, at multilayer complex films surface application hardening resin, solve list/double sided optical sclerosis multilayer complex films yellowing resistance, △ E≤1.2 can be reached through the method obtained list/double sided optical sclerosis multilayer complex films yellowing resistance;
(5) the present invention adopts the production method of biaxial tension and online coating, can One-step production list/double sided optical sclerosis multilayer complex films, simplifies production technology, enhances productivity and coating accuracy, reduce environmental pollution, operation is easy, easily operates, practical.
Detailed description of the invention
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
The preparation of Part I A tunic compound and B tunic compound
Basic technology and raw material:
By 99.88% ~ 99.935% poliester chip, 0.015% ~ 0.02% 30 ~ 100nm silica, 0.05% ~ 0.1% heat stabilizer mass percent composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C ~ 285 DEG C temperature by double screw extruder, granulation, obtained A tunic compound is for subsequent use.
Each raw material is got by the mass percent composition of 99.9% ~ 99.95% poliester chip, 0.05% ~ 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C ~ 285 DEG C temperature, granulation, obtained B tunic compound is for subsequent use.
Embodiment 1-1A ~ 1-5A:
The formula components of A tunic compound (rear title " A layered material ") 1-1A ~ 1-5A and consumption are as following table:
Embodiment 1-1B ~ 1-5B:
The formula components of B tunic compound (rear title " B layered material ") 1-1B ~ 1-5B and consumption are as following table:
The preparation of Part II hardening resin coating fluid
Basic craft course:
In the preparation container that can weigh, under agitation add 40 ~ 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip denier pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 ~ 4 weight portion Nano silica sol is added successively under stirring, 0.5 ~ 1.5 parts surfactant, 0.1 ~ 0.5 weight portion levelling agent, 0.1 ~ 0.5 weight portion defoamer, 1 ~ 8 weight portion light trigger, the resistance to yellow agent of 0.1 ~ 0.8 weight portion, finally add 1 ~ 8 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, again drip denier triethylamine and adjust pH to 9.5, stir 30 minutes again, obtained hardening resin coating fluid, its viscosity is 72 ~ 142mPas at 25 DEG C.
Embodiment 2-1:
Hardening resin coating fluid formula of the present invention 1 (this 1# hardening resin coating fluid viscosity at 25 DEG C is 72mPas):
Embodiment 2-2:
Hardening resin coating fluid formula of the present invention 2 (this 2# hardening resin coating fluid viscosity at 25 DEG C is 74mPas):
Embodiment 2-3:
Hardening resin coating fluid formula of the present invention 3 (this 3# hardening resin coating fluid viscosity at 25 DEG C is 80mPas):
Embodiment 2-4:
Hardening resin coating fluid formula of the present invention 4 (this 4# hardening resin coating fluid viscosity at 25 DEG C is 82mPas):
Embodiment 2-5:
Hardening resin coating fluid formula of the present invention 5 (this 5# hardening resin coating fluid viscosity at 25 DEG C is 91mPas):
Embodiment 2-6:
Hardening resin coating fluid formula of the present invention 6 (this 6# hardening resin coating fluid viscosity at 25 DEG C is 92mPas):
Embodiment 2-7:
Hardening resin coating fluid formula of the present invention 7 (this 7# hardening resin coating fluid viscosity at 25 DEG C is 99mPas):
Embodiment 2-8:
Hardening resin coating fluid formula of the present invention 8 (this 8# hardening resin coating fluid viscosity at 25 DEG C is 102mPas):
Embodiment 2-9:
Hardening resin coating fluid formula of the present invention 9 (this 9# hardening resin coating fluid viscosity at 25 DEG C is 108mPas):
Example 2-10:
Hardening resin coating fluid formula of the present invention 10 (this 10# hardening resin coating fluid viscosity at 25 DEG C is 111mPas):
Embodiment 2-11:
Hardening resin coating fluid formula of the present invention 11 (this 11# hardening resin coating fluid viscosity at 25 DEG C is 119mPas):
Embodiment 2-12:
Hardening resin coating fluid formula of the present invention 12 (this 12# hardening resin coating fluid viscosity at 25 DEG C is 120mPas):
Embodiment 2-13:
Hardening resin coating fluid formula of the present invention 13 (this 13# hardening resin coating fluid viscosity at 25 DEG C is 128mPas):
Embodiment 2-14:
Hardening resin coating fluid formula of the present invention 14 (this 14# hardening resin coating fluid viscosity at 25 DEG C is 130mPas):
Embodiment 2-15:
Hardening resin coating fluid formula of the present invention 15 (this 15# hardening resin coating fluid viscosity at 25 DEG C is 139mPas):
Embodiment 2-16:
Hardening resin coating fluid formula of the present invention 16 (this 16# hardening resin coating fluid viscosity at 25 DEG C is 142mPas):
The preparation of Part III single or double optics sclerosis composite membrane
1, basic craft course:
The A layered material prepare above-mentioned detailed description of the invention Part I and B layered material are respectively through No. 1 single screw extrusion machine, No. 2 single screw extrusion machines are at 285 DEG C of temperature after melting, (after measuring pump accurate measurement) is by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 12 ~ 20 DEG C of cold drums, cooling forms compound slab, 3 ~ 5m is entered long with the speed of 10 ~ 30m/ minute, after the longitudinal stretching section stretching 2.2 ~ 3.8 times of temperature 65 ~ 95 DEG C, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 22 ~ 114m/ minute, 15 ~ 45 DEG C are cooled to 1 ~ 3 second, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that hardening resin coating fluid prepared by above-mentioned detailed description of the invention Part II is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 5 ~ 9m long, the preheating section removing moisture that temperature is 100 ~ 135 DEG C, then long at 8 ~ 12m, the cross directional stretch section of temperature 135 ~ 155 DEG C stretches 3.0 ± 0.8 times, long at 10 ~ 16m through temperature again, the heat-setting section sizing of 225 ~ 245 DEG C 0.1 ~ 0.8 minute, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of its membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, now the coating layer thickness in each face is 1 ~ 10 μm, again through 60 ~ 80 DEG C, the rolling after cooling in 0.1 ~ 1 minute and at room temperature two stages, obtain single or double optics sclerosis composite membrane finished product.
The thickness of described basement membrane is 100 ~ 250 μm, and this thickness is not containing the thickness of hardened resin coating.The A layer of two stratotype basement membranes is 10% ~ 20%:80% ~ 90% with the ratio of B layer thickness, and the A layer of three stratotype basement membranes is 20% ~ 30%:70% ~ 80% with the ratio of B layer thickness.
Described ultraviolet light polymerization adopts 200W/cm light-focusing type high-pressure mercury-vapor lamp, and irradiation energy is 800mj/cm
2.
Embodiment 3-1 ~ 3-16 is mono-/and double sided optical sclerosis performance test methods that is two-layer or sandwich diaphragm is as follows:
Hardness test: according to GB/T6739-2006 standard, adopt Tianjin instrument plant to the sclerosis of list/double sided optical two-layer or sandwich diaphragm test.
Tack: according to GB-T9286-1998 standard, adopts hundred lattice methods to test hardened resin coating.
Light transmittance and mist degree: according to ASTMD1003 standard, in employing the light transmittance/mist degree analyzer WGT-S of company of Nereid section to the sclerosis of list/double sided optical two-layer or sandwich diaphragm test.
Solvent resistance test: under room temperature state, be coated with print to be immersed in respectively in ethanol, ethyl acetate, acetone and toluene 30 minutes, with distilled water cleaning after taking-up, filter paper blots, and whether observe print surface has the phenomenon of albefaction and corrosion, print whether to have metaboly.If there is no the above phenomenon, represent with " √ ".
Acid and alkali-resistance is tested: at 50 DEG C, be coated with print and place 10 minutes in 20% hydrochloric acid solution, taking-up distilled water cleans, and filter paper blots.In the tack by hundred lattice method testing coatings and base material, reach 100/100 expression and pass through, represent with " √ ", otherwise then use "×"; At 50 DEG C, be coated with sample mass fraction be in 5% sodium hydroxide solution place 20 seconds, taking-up distilled water cleans, filter paper blots, hardened resin coating and tacks that are two-layer or sandwich diaphragm base material are being tested by hundred lattice methods, reach 100/100 expression to pass through, represent with " √ ", otherwise then use "×".
Yellowing resistance is tested: by HG/T3828-2006 standard, to the sclerosis of list/double sided optical, two-layer or sandwich diaphragm carries out the test of anti-yellowing property.
2, embodiment 3-1 ~ 3-16 single-side optical hardens the test performance result of two-layer composite membrane
Double sided optical harden two-layer composite membrane structure by biaxial tension optical grade composite membrane (two-layer) for basement membrane and coating thereof and the hardened resin coating being solidificated in this basement membrane two-sided form, basement membrane thickness is 100 ~ 250 μm, and the coating layer thickness on each surface is 1 ~ 10 μm.The performance test results of its product sees the following form 1:
Table 1: single-side optical harden two-layer composite membrane adopt material, specification and performance indications table
Continued 1:
Table 1 note:
(1) comparative example 1*, 2*, 3*, in table represent respectively certain three company commercially available take pet film as the performance data of sclerosis polyester film (mono-layer single-face sclerosis) three kinds of products of basement membrane.
(2), according to the tack in the known table of standard GB/T9286-1998 all reach 0 grade, illustrate that the harden tack of the hardening coat of two-layer composite membrane and basement membrane of single-side optical of the present invention is better.
(3), according to test result in table: harden two-layer composite membrane solvent resistant, acid-proof alkaline of single-side optical of the present invention is excellent.
(4), according to data in table: single-side optical of the present invention hardens, and to compare the light transmittance of commercially available prod A, B and C high for two-layer composite membrane, and haze value is low, has excellent optical property.
(5), according to standard HG/T3828-2006: resistance to ag(e)ing △ E≤1.2 in table, illustrate that the harden hardening coat yellowing resistance of two-layer composite membrane of single-side optical of the present invention is better.
The test performance of 3, embodiment 3-17 ~ 3-32 double sided optical sclerosis sandwich diaphragm
The structure of double sided optical sclerosis sandwich diaphragm by biaxial tension optical grade composite membrane (three layers) for basement membrane and coating thereof and the hardened resin coating being solidificated in this basement membrane two-sided form, basement membrane thickness is 100 ~ 250 μm, and the coating layer thickness on each surface is 1 ~ 10 μm.The performance test results of its product sees the following form 2:
Table 2: double sided optical sclerosis sandwich diaphragm adopts material, specification and performance indications table
Continued 2:
Table 2 note:
Comparative example 1** in table, 2**, 3** represent respectively certain three company commercially available take pet film as the performance data of sclerosis polyester film (single-layer double-side sclerosis) three kinds of products of basement membrane.
Embodiment 4:
A kind of single or double optics sclerosis composite membrane, by basement membrane, and apply and the hardened resin coating being solidificated in basement membrane single or double forms;
Described basement membrane is the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm;
The two-layer composite membrane of described biaxial tension optical grade is made up of A, B two membranes, and A layer is 10%:90% with the ratio of the thickness of B layer;
Described biaxial tension optical grade sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 20%:80% with the ratio of the thickness of B layer;
Described single or double optics hardens composite membrane by A tunic compound, B tunic compound respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, obtain through longitudinal stretching, single or double coating hardening resin coating fluid, oven dry, cross directional stretch, thermal finalization and ultraviolet light polymerization;
Described hardened resin coating is by A tunic compound, B tunic compound is respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, longitudinal stretching becomes by A, B is two-layer or by A, B, after the THIN COMPOSITE blank of A tri-layers composition, adopt on the single or double of online coating method hardening resin coating liquid is two-layer at this or the THIN COMPOSITE blank of three layers, drying, cross directional stretch, after thermal finalization, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then through ultraviolet light polymerization, at the hardened resin coating that membrane surface obtains,
The preparation method of described A tunic compound is: by 99.88% poliester chip, 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.1% heat stabilizer composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
The preparation method of described B tunic compound is: get each raw material by the mass percent composition of 99.9% poliester chip, 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
The preparation method of described hardening resin coating fluid is: in (preparation that can weigh) container, under agitation add 40 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 weight portion Nano silica sol is added successively under stirring, 0.5 parts surfactant, 0.1 weight portion levelling agent, 0.1 weight portion defoamer, 1 weight portion light trigger, the resistance to yellow agent of 0.1 weight portion, finally add 1 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid.
Embodiment 5:
A kind of single or double optics sclerosis composite membrane, by basement membrane, and apply and the hardened resin coating being solidificated in basement membrane single or double forms;
Described basement membrane is the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm;
The two-layer composite membrane of described biaxial tension optical grade is made up of A, B two membranes, and A layer is 20%:80% with the ratio of the thickness of B layer;
Described biaxial tension optical grade sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 30%:70% with the ratio of the thickness of B layer;
Described single or double optics hardens composite membrane by A tunic compound, B tunic compound respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, obtain through longitudinal stretching, single or double coating hardening resin coating fluid, oven dry, cross directional stretch, thermal finalization and ultraviolet light polymerization;
Described hardened resin coating is by A tunic compound, B tunic compound is respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, longitudinal stretching becomes by A, B is two-layer or by A, B, after the THIN COMPOSITE blank of A tri-layers composition, adopt on the single or double of online coating method hardening resin coating liquid is two-layer at this or the THIN COMPOSITE blank of three layers, drying, cross directional stretch, after thermal finalization, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then through ultraviolet light polymerization, at the hardened resin coating that membrane surface obtains,
The preparation method of described A tunic compound is: by 99.935% poliester chip, 0.015% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% heat stabilizer composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 285 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
The preparation method of described B tunic compound is: get each raw material by the mass percent composition of 99.95% poliester chip, 0.05% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 285 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
The preparation method of described hardening resin coating fluid is: in (preparation that can weigh) container, under agitation add 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 4 weight portion Nano silica sols are added successively under stirring, 1.5 parts surfactant, 0.5 weight portion levelling agent, 0.5 weight portion defoamer, 8 weight portion light triggers, the resistance to yellow agent of 0.8 weight portion, finally add 8 parts by weight of activated diluents, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid.
Embodiment 6:
A kind of single or double optics sclerosis composite membrane, by basement membrane, and apply and the hardened resin coating being solidificated in basement membrane single or double forms;
Described basement membrane is the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm;
The two-layer composite membrane of described biaxial tension optical grade is made up of A, B two membranes, and A layer is 15%:85% with the ratio of the thickness of B layer;
Described biaxial tension optical grade sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 25%:75% with the ratio of the thickness of B layer;
Described single or double optics hardens composite membrane by A tunic compound, B tunic compound respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, obtain through longitudinal stretching, single or double coating hardening resin coating fluid, oven dry, cross directional stretch, thermal finalization and ultraviolet light polymerization;
Described hardened resin coating is by A tunic compound, B tunic compound is respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, longitudinal stretching becomes by A, B is two-layer or by A, B, after the THIN COMPOSITE blank of A tri-layers composition, adopt on the single or double of online coating method hardening resin coating liquid is two-layer at this or the THIN COMPOSITE blank of three layers, drying, cross directional stretch, after thermal finalization, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then through ultraviolet light polymerization, at the hardened resin coating that membrane surface obtains,
The preparation method of described A tunic compound is: by 99.91% poliester chip, 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.07% heat stabilizer composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 275 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
The preparation method of described B tunic compound is: get each raw material by the mass percent composition of 99.92% poliester chip, 0.08% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 275 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
The preparation method of described hardening resin coating fluid is: in (preparation that can weigh) container, under agitation add 57 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 2 weight portion Nano silica sols are added successively under stirring, 1 parts surfactant, 0.3 weight portion levelling agent, 0.3 weight portion defoamer, 4 weight portion light triggers, the resistance to yellow agent of 0.4 weight portion, finally add 4 parts by weight of activated diluents, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid.
In above-described embodiment 4 ~ 6: described Nano silica sol is the nanometer grade silica emulsion of average grain diameter 100nm, Dutch Akzo Nobel N.V. can be selected
trade mark product or other commercially available prod;
In above-described embodiment 4 ~ 6: described surfactant is polyethers, the TERGITOL of Dow Chemical can be selected
tMtMN-6 trade mark product or other commercially available prod;
In above-described embodiment 4 ~ 6: the levelling agent in described hardening resin coating fluid can select the Dynol of US Air gasification chemical product company
tM604 trade mark products or other commercially available prod; Described defoamer is organic silicon polyether copolymer, can select the TERGITOL of Dow Chemical
tMl-61 trade mark product or other commercially available prod; Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, i.e. light trigger 659; Described resistance to yellow agent can select CHISORB1300 trade mark product or other commercially available prod of Taiwan Double Bond Chemical Ind.,Co.,Ltd.; Described reactive diluent is tri (propylene glycol) diacrylate.
In above-described embodiment 4 ~ 6: the thickness of described basement membrane can be arbitrary in 100 ~ 250 μm, and the hardened resin coating thickness on each surface of basement membrane can be in 1 ~ 10 μm arbitrary.
In above-described embodiment 4 ~ 6: the viscosity of described obtained hardening resin coating fluid is 72 ~ 142mPas at temperature 25 DEG C.
In above-described embodiment 4 ~ 6: the described pH containing 35% aqueous emulsion of polyurethane (that is: containing percentage by weight in aqueous emulsion of polyurethane is the polyurethane of 35%) is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C; Described 35% aqueous emulsion of polyurethane that contains can select U.S. CYTEC company
the aqueous emulsion of polyurethane product of the trade mark or other commercially available prod; Described 35% aqueous emulsion of polyurethane that contains also can use homemade aqueous emulsion of polyurethane, the preparation method of self-control aqueous emulsion of polyurethane is: adopt prior art, with polyether Glycols, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, triethanolamine, deionized water etc. for raw material, prepare aqueous emulsion of polyurethane.
Embodiment 7:
A preparation method for single or double optics sclerosis composite membrane, step is:
A, preparation A tunic compound: by 99.88%% poliester chip, 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.1% heat stabilizer composition gets each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 285 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
B, preparation B tunic compound: get each raw material by the mass percent composition of 99.9% poliester chip, 0.05%0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 285 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
C, prepare hardening resin coating fluid: in (preparation that can weigh) container, under agitation add 40 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 weight portion Nano silica sol is added successively under stirring, 1 parts surfactant, 0.3 weight portion levelling agent, 0.3 weight portion defoamer, 5 weight portion light triggers, the resistance to yellow agent of 0.5 weight portion, finally add 5 parts by weight of activated diluents, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid,
D, prepare single or double optics sclerosis composite membrane: the obtained B tunic compound of the A tunic compound that step a is obtained and step b respectively through No. 1 single screw extrusion machine and No. 2 single screw extrusion machines at 285 DEG C of temperature after melting, (after measuring pump accurate measurement) is by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 12 DEG C of cold drums, cooling forms compound slab, 5m is entered long with the speed of 10m/ minute, the longitudinal stretching section of temperature 65 DEG C stretches after 2.2 times, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 22m/ minute, 15 ~ 45 DEG C are cooled to 3 seconds, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that the hardening resin coating fluid that step c is obtained is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 5m long, the preheating section removing moisture that temperature is 135 DEG C, then long at 8m, the cross directional stretch section of temperature 155 DEG C stretches 2.2 times, long through 10m again, the heat-setting section that temperature is 245 DEG C is shaped 0.1 minute, obtain the basement membrane that single or double has hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, again through temperature 60 C, the rolling after cooling in 1 minute and at room temperature two stages, i.e. obtained single or double optics sclerosis composite membrane finished product,
The two-layer composite membrane of the optical grade of biaxial tension described in steps d is made up of A, B two membranes, and A layer is 10%:90% with the ratio of the thickness of B layer; The optical grade of biaxial tension described in steps d sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 20%:80% with the ratio of the thickness of B layer; The thickness of basement membrane described in steps d is 100 μm, and this thickness is not containing the thickness of hardened resin coating; The hardened resin coating thickness on each surface of described basement membrane is 1 μm.
Embodiment 8:
A preparation method for single or double optics sclerosis composite membrane, step is:
A, preparation A tunic compound: by 99.935% poliester chip, 0.015% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% heat stabilizer composition gets each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
B, preparation B tunic compound: get each raw material by the mass percent composition of 99.95% poliester chip, 0.05% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
C, prepare hardening resin coating fluid: in (preparation that can weigh) container, under agitation add 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 4 weight portion Nano silica sols are added successively under stirring, 1.5 parts surfactant, 0.5 weight portion levelling agent, 0.5 weight portion defoamer, 8 weight portion light triggers, the resistance to yellow agent of 0.8 weight portion, finally add 8 parts by weight of activated diluents, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid,
D, prepare single or double optics sclerosis composite membrane: the obtained B tunic compound of the A tunic compound that step a is obtained and step b respectively through No. 1 single screw extrusion machine and No. 2 single screw extrusion machines at 285 DEG C of temperature after melting, (after measuring pump accurate measurement) is by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 20 DEG C of cold drums, cooling forms compound slab, 3m is entered long with the speed of 30m/ minute, the longitudinal stretching section of temperature 95 DEG C stretches after 3.8 times, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 114m/ minute, 15 ~ 45 DEG C are cooled to 3 seconds, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that the hardening resin coating fluid that step c is obtained is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 9m long, the preheating section removing moisture that temperature is 100 DEG C, then long at 12m, the cross directional stretch section of temperature 135 DEG C stretches 3.8 times, long through 16m again, the heat-setting section that temperature is 225 DEG C is shaped 0.8 minute, obtain the basement membrane that single or double has hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, again through temperature 80 DEG C, the rolling after cooling in 0.1 minute and at room temperature two stages, i.e. obtained single or double optics sclerosis composite membrane finished product,
The two-layer composite membrane of the optical grade of biaxial tension described in steps d is made up of A, B two membranes, and A layer is 20%:80% with the ratio of the thickness of B layer; The optical grade of biaxial tension described in steps d sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 30%:70% with the ratio of the thickness of B layer; The thickness of basement membrane described in steps d is 250 μm, and this thickness is not containing the thickness of hardened resin coating; The hardened resin coating thickness on each surface of described basement membrane is 10 μm.
Embodiment 9:
A preparation method for single or double optics sclerosis composite membrane, step is:
A, preparation A tunic compound: by 99.9% poliester chip, 0.017% particle diameter be 30 ~ 100nm silica, the mass percent of 0.083% heat stabilizer composition gets each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 270 DEG C of temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
B, preparation B tunic compound: get each raw material by the mass percent composition of 99.92% poliester chip, 0.08% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 270 DEG C of temperature, granulation, namely obtained B tunic compound, for subsequent use;
C, prepare hardening resin coating fluid: in (preparation that can weigh) container, under agitation add 56 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip (denier) pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 2.2 weight portion Nano silica sols are added successively under stirring, 1.1 parts surfactant, 0.3 weight portion levelling agent, 0.3 weight portion defoamer, 5 weight portion light triggers, the resistance to yellow agent of 0.5 weight portion, finally add 5 parts by weight of activated diluents, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripping (denier), stir 30 minutes again, i.e. obtained hardening resin coating fluid,
D, prepare single or double optics sclerosis composite membrane: the obtained B tunic compound of the A tunic compound that step a is obtained and step b respectively through No. 1 single screw extrusion machine and No. 2 single screw extrusion machines at 285 DEG C of temperature after melting, (after measuring pump accurate measurement) is by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 16 DEG C of cold drums, cooling forms compound slab, 4m is entered long with the speed of 20m/ minute, the longitudinal stretching section of temperature 80 DEG C stretches after 3 times, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 68m/ minute, 15 ~ 45 DEG C are cooled to 2 seconds, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that the hardening resin coating fluid that step c is obtained is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 7m long, the preheating section removing moisture that temperature is 115 DEG C, then long at 10m, the cross directional stretch section of temperature 145 DEG C stretches 3 times, long through 13m again, the heat-setting section that temperature is 235 DEG C is shaped 0.5 minute, obtain the basement membrane that single or double has hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, again through temperature 70 C, the rolling after cooling in 0.6 minute and at room temperature two stages, i.e. obtained single or double optics sclerosis composite membrane finished product,
The two-layer composite membrane of the optical grade of biaxial tension described in steps d is made up of A, B two membranes, and A layer is 15%:85% with the ratio of the thickness of B layer; The optical grade of biaxial tension described in steps d sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 25%:75% with the ratio of the thickness of B layer; The thickness of basement membrane described in steps d is 175 μm, and this thickness is not containing the thickness of hardened resin coating; The hardened resin coating thickness on each surface of described basement membrane is 5.5 μm.
In above-described embodiment 7 ~ 9: the Nano silica sol in described hardening resin coating fluid is the nanometer grade silica emulsion of average grain diameter 100nm, Dutch Akzo Nobel N.V. can be selected
trade mark product or other commercially available prod; Described surfactant is polyethers, can select the TERGITOL of Dow Chemical
tMtMN-6 trade mark product or other commercially available prod; Described levelling agent can select the Dynol of US Air gasification chemical product company
tM604 trade mark products or other commercially available prod; Described defoamer is organic silicon polyether copolymer, can select the TERGITOL of Dow Chemical
tMl-61 trade mark product or other commercially available prod; Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, i.e. light trigger 659; Described resistance to yellow agent can select CHISORB1300 trade mark product or other commercially available prod of Taiwan Double Bond Chemical Ind.,Co.,Ltd.; Described reactive diluent is tri (propylene glycol) diacrylate.
In above-described embodiment 7 ~ 9: the thickness of basement membrane described in steps d can also be arbitrary in 100 ~ 250 μm, this thickness is not containing the thickness of hardened resin coating; The hardened resin coating thickness on each surface of described basement membrane can be in 1 ~ 10 μm arbitrary, and described hardened resin coating thickness can be controlled by the applicator roll and two-layer or three layers of THIN COMPOSITE blank relative velocity and pressure roller and applicator roll clearance distance adjusting online apparatus for coating.
In above-described embodiment 7 ~ 9: the pH containing 35% aqueous emulsion of polyurethane (that is: containing percentage by weight in aqueous emulsion of polyurethane is the polyurethane of 35%) described in step c is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C; Described 35% aqueous emulsion of polyurethane that contains can select U.S. CYTEC company
the aqueous emulsion of polyurethane product of the trade mark or other commercially available prod; Described 35% aqueous emulsion of polyurethane that contains also can use homemade aqueous emulsion of polyurethane, the preparation method of self-control aqueous emulsion of polyurethane is: adopt prior art, with polyether Glycols, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, triethanolamine, deionized water etc. for raw material, prepare aqueous emulsion of polyurethane.This aqueous emulsion of polyurethane be white slightly blue light, with polyester film tack excellence, water white transparency, color inhibition, film forming excellence.
In above-described embodiment 7 ~ 9: the solidification of ultraviolet light cross-linking described in steps d is preferably and adopts 200W/cm light-focusing type high-pressure mercury-vapor lamp to carry out, and irradiation energy is 800mj/cm
2.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described weight portion can be all gram or kilogram.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described raw material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (10)
1. single or double optics sclerosis a composite membrane, it is characterized in that: by basement membrane, and apply and be solidificated in basement membrane single or double hardened resin coating form;
Described basement membrane is the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm;
The two-layer composite membrane of described biaxial tension optical grade is made up of A, B two membranes, and A layer is 10% ~ 20%:80% ~ 90% with the ratio of the thickness of B layer;
Described biaxial tension optical grade sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 20% ~ 30%:70% ~ 80% with the ratio of the thickness of B layer;
Described single or double optics hardens composite membrane by A tunic compound, B tunic compound respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, obtain through longitudinal stretching, single or double coating hardening resin coating fluid, oven dry, cross directional stretch, thermal finalization and ultraviolet light polymerization;
Described hardened resin coating is by A tunic compound, B tunic compound is respectively through No. 1 extruder and No. 2 extruder meltings, extrude at two-layer or three layers co-extrusion die head, be cooled to compound slab, longitudinal stretching becomes by A, B is two-layer or by A, B, after the THIN COMPOSITE blank of A tri-layers composition, adopt on the single or double of online coating method hardening resin coating liquid is two-layer at this or the THIN COMPOSITE blank of three layers, drying, cross directional stretch, after thermal finalization, obtain the basement membrane of hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then through ultraviolet light polymerization, at the hardened resin coating that membrane surface obtains,
The preparation method of described A tunic compound is: by 99.88% ~ 99.935% poliester chip, 0.015% ~ 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% ~ 0.1% heat stabilizer composition get each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C ~ 285 DEG C temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
The preparation method of described B tunic compound is: get each raw material by the mass percent composition of 99.9% ~ 99.95% poliester chip, 0.05% ~ 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C ~ 285 DEG C temperature, granulation, namely obtained B tunic compound, for subsequent use;
The preparation method of described hardening resin coating fluid is: in a reservoir, under agitation add 40 ~ 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 ~ 4 weight portion Nano silica sol is added successively under stirring, 0.5 ~ 1.5 parts surfactant, 0.1 ~ 0.5 weight portion levelling agent, 0.1 ~ 0.5 weight portion defoamer, 1 ~ 8 weight portion light trigger, the resistance to yellow agent of 0.1 ~ 0.8 weight portion, finally add 1 ~ 8 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripped, stir 30 minutes again, i.e. obtained hardening resin coating fluid,
Described Nano silica sol is the nanometer grade silica emulsion of average grain diameter 100nm;
Described surfactant is polyethers;
Described levelling agent selects the Dynol of Air Prod & Chem of the U.S.
tM604 trade mark products;
Described defoamer is organic silicon polyether copolymer;
Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone;
The CHISORB1300 trade mark product of Taiwan Double Bond Chemical Ind.,Co.,Ltd. is selected in described resistance to yellow agent;
Described reactive diluent is tri (propylene glycol) diacrylate.
2., by single or double optics sclerosis composite membrane according to claim 1, it is characterized in that: the thickness of described basement membrane is 100 ~ 250 μm, and the hardened resin coating thickness on each surface of basement membrane is 1 ~ 10 μm.
3., by the single or double optics sclerosis composite membrane described in claim 1 or 2, it is characterized in that: the viscosity of described obtained hardening resin coating fluid is 72 ~ 142mPas at temperature 25 DEG C.
4., by the single or double optics sclerosis composite membrane described in claim 1 or 2, it is characterized in that: the described pH containing 35% aqueous emulsion of polyurethane is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C.
5. a preparation method for single or double optics sclerosis composite membrane, is characterized in that step is:
A, preparation A tunic compound: by 99.88% ~ 99.935% poliester chip, 0.015% ~ 0.02% particle diameter be 30 ~ 100nm silica, the mass percent of 0.05% ~ 0.1% heat stabilizer composition gets each raw material, drop in feed bin and mix, after the drying that dewaters, melt extruded at 265 DEG C ~ 285 DEG C temperature by double screw extruder, granulation, namely obtained A tunic compound, for subsequent use;
B, preparation B tunic compound: get each raw material by the mass percent composition of 99.9% ~ 99.95% poliester chip, 0.05% ~ 0.1% heat stabilizer, drop in feed bin and mix, dewater after drying, by melt extruding at double screw extruder 265 DEG C ~ 285 DEG C temperature, granulation, namely obtained B tunic compound, for subsequent use;
C, prepare hardening resin coating fluid: in a reservoir, under agitation add 40 ~ 75 weight portions containing 35% aqueous emulsion of polyurethane, stir after 30 minutes, drip pH adjusting agent triethylamine again, make the pH=9.5 containing 35% aqueous emulsion of polyurethane, 0.5 ~ 4 weight portion Nano silica sol is added successively under stirring, 0.5 ~ 1.5 parts surfactant, 0.1 ~ 0.5 weight portion levelling agent, 0.1 ~ 0.5 weight portion defoamer, 1 ~ 8 weight portion light trigger, the resistance to yellow agent of 0.1 ~ 0.8 weight portion, finally add 1 ~ 8 parts by weight of activated diluent, add deionized water to total material again and reach 100 weight portions, pH to 9.5 adjusted by the triethylamine again dripped, stir 30 minutes again, i.e. obtained hardening resin coating fluid,
Described Nano silica sol is the nanometer grade silica emulsion of average grain diameter 100nm;
Described surfactant is polyethers;
Described levelling agent selects the Dynol of Air Prod & Chem of the U.S.
tM604 trade mark products;
Described defoamer is organic silicon polyether copolymer;
Described light trigger is 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone;
The CHISORB1300 trade mark product of Taiwan Double Bond Chemical Ind.,Co.,Ltd. is selected in described resistance to yellow agent;
Described reactive diluent is tri (propylene glycol) diacrylate;
D, prepare single or double optics sclerosis composite membrane: the obtained B tunic compound of the A tunic compound that step a is obtained and step b respectively through No. 1 single screw extrusion machine and No. 2 single screw extrusion machines at 285 DEG C of temperature after melting, by A, B is two-layer or successively by A, B, the co-extrusion die head that A is tri-layers is extruded, on temperature 12 ~ 20 DEG C of cold drums, cooling forms compound slab, 3 ~ 5m is entered long with the speed of 10 ~ 30m/ minute, after the longitudinal stretching section stretching 2.2 ~ 3.8 times of temperature 65 ~ 95 DEG C, THIN COMPOSITE blank through longitudinal stretching is entered cooling corona section with the speed of 22 ~ 114m/ minute, 15 ~ 45 DEG C are cooled to 1 ~ 3 second, carry out sided corona treatment, THIN COMPOSITE blank through longitudinal stretching and sided corona treatment enters online apparatus for coating, adopt the coating method of intaglio plate or bar seam or air knife that the hardening resin coating fluid that step c is obtained is carried out single or double coating to it, THIN COMPOSITE blank after coating is entered 5 ~ 9m long, the preheating section removing moisture that temperature is 100 ~ 135 DEG C, then long at 8 ~ 12m, the cross directional stretch section of temperature 135 ~ 155 DEG C stretches 2.2 ~ 3.8 times, long through 10 ~ 16m again, the heat-setting section sizing that temperature is 225 ~ 245 DEG C 0.1 ~ 0.8 minute, obtain the basement membrane that single or double has hardening resin coating fluid coating, this basement membrane and the two-layer composite membrane of biaxial tension optical grade or sandwich diaphragm, and then the hardening resin coating fluid coating of membrane surface is solidify to form fine and close hardened resin coating through ultraviolet light cross-linking, again through temperature 60 ~ 80 DEG C, the rolling after cooling in 0.1 ~ 1 minute and at room temperature two stages, i.e. obtained single or double optics sclerosis composite membrane finished product.
6., by the preparation method of single or double optics sclerosis composite membrane described in claim 5, it is characterized in that: the two-layer composite membrane of the optical grade of biaxial tension described in steps d is made up of A, B two membranes, A layer is 10% ~ 20%:80% ~ 90% with the ratio of the thickness of B layer.
7. by the preparation method of single or double optics sclerosis composite membrane described in claim 5, it is characterized in that: the optical grade of biaxial tension described in steps d sandwich diaphragm is made up of A, B, A trilamellar membrane successively, and A layer is 20% ~ 30%:70% ~ 80% with the ratio of the thickness of B layer.
8., by the preparation method of single or double optics sclerosis composite membrane described in claim 5,6 or 7, it is characterized in that: the thickness of basement membrane described in steps d is 100 ~ 250 μm; The hardened resin coating thickness on each surface of described basement membrane is 1 ~ 10 μm.
9. by the preparation method of single or double optics sclerosis composite membrane described in claim 5,6 or 7, it is characterized in that: the pH containing 35% aqueous emulsion of polyurethane described in step c is 7 ~ 8.5, particle diameter is <150nm, viscosity <200mPas at 25 DEG C.
10. by the preparation method of single or double optics sclerosis composite membrane described in claim 5,6 or 7, it is characterized in that: the solidification of ultraviolet light cross-linking described in steps d adopts 200W/cm light-focusing type high-pressure mercury-vapor lamp to carry out, and irradiation energy is 800mj/cm
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410464420.5A CN104228257B (en) | 2014-09-12 | 2014-09-12 | A kind of single or double optics sclerosis composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410464420.5A CN104228257B (en) | 2014-09-12 | 2014-09-12 | A kind of single or double optics sclerosis composite membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104228257A CN104228257A (en) | 2014-12-24 |
| CN104228257B true CN104228257B (en) | 2016-04-27 |
Family
ID=52217561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410464420.5A Active CN104228257B (en) | 2014-09-12 | 2014-09-12 | A kind of single or double optics sclerosis composite membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104228257B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108202518A (en) * | 2016-12-20 | 2018-06-26 | 新科光电材料股份有限公司 | Sputter polyester laminate and its manufacturing method |
| CN114456422B (en) * | 2022-03-10 | 2023-08-29 | 山东胜通光学材料科技有限公司 | Preparation method of high-adhesiveness thick brightening polyester base film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738026A (en) * | 2013-12-27 | 2014-04-23 | 四川东方绝缘材料股份有限公司 | Low-water-vapor-transmittance polyester film with polyurethane coatings and preparation method of polyester film |
| CN103753920A (en) * | 2013-12-27 | 2014-04-30 | 四川东方绝缘材料股份有限公司 | Multilayered co-extruded bidirectional-stretching light reflection polyester thin film and manufacturing method thereof |
| CN103869387A (en) * | 2014-03-27 | 2014-06-18 | 宁波惠之星新材料科技有限公司 | Ultraviolet light curing optic hardened film, preparing device thereof and preparing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101218146B1 (en) * | 2005-11-08 | 2013-01-03 | 도레이첨단소재 주식회사 | Biaxially-stretched polyester film for optical use |
-
2014
- 2014-09-12 CN CN201410464420.5A patent/CN104228257B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738026A (en) * | 2013-12-27 | 2014-04-23 | 四川东方绝缘材料股份有限公司 | Low-water-vapor-transmittance polyester film with polyurethane coatings and preparation method of polyester film |
| CN103753920A (en) * | 2013-12-27 | 2014-04-30 | 四川东方绝缘材料股份有限公司 | Multilayered co-extruded bidirectional-stretching light reflection polyester thin film and manufacturing method thereof |
| CN103869387A (en) * | 2014-03-27 | 2014-06-18 | 宁波惠之星新材料科技有限公司 | Ultraviolet light curing optic hardened film, preparing device thereof and preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104228257A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104228256B (en) | A kind of single or double optics sclerosis polyester film and preparation method thereof | |
| CN103612405B (en) | The method of polyester film is prepared in online coating | |
| CN101402269B (en) | Viscosity-increasing precoating film of biaxial tension | |
| CN104284938B (en) | Based on the paint base composition of polyester, blooming and the polarization plates comprising this blooming | |
| CN103738026B (en) | A kind of low water vapor transmittance polyester film of polyurethane-type coating and its preparation method | |
| CN106280697B (en) | High-covering black matte silk-screen printing ink for PET (polyethylene terephthalate) substrate | |
| CN104441709B (en) | Preparation method of polyester film for coating tag | |
| CN102186670B (en) | Method for manufacture of resin laminated body | |
| JP6812795B2 (en) | Polyvinyl alcohol-based resin for manufacturing polarizing film and its manufacturing method, polyvinyl alcohol-based film and its manufacturing method, polarizing film, polyvinyl alcohol-based resin | |
| CN204174147U (en) | Anti-scratching flat top pre-coating film | |
| JP2004001514A (en) | Coating method for manufacturing polyvinyl alcohol film and polyvinyl alcohol film | |
| CN103692748B (en) | A kind of optical polyester film | |
| CN102514275A (en) | Optical polyester thin film and preparation method thereof | |
| CN104228257B (en) | A kind of single or double optics sclerosis composite membrane and preparation method thereof | |
| CN102731808B (en) | The drying means of drying device, film and solution film-forming method | |
| CN104893525B (en) | A kind of coating fluid and hardening polyester film | |
| CN105462131A (en) | Resin composition, film, polarizing plate protective film, polarizing plate, liquid crystal display device, and bis-type alicyclic cardo phenol compound | |
| CN103753925B (en) | A kind of acrylic type coating low water vapor transmittance mylar and preparation method thereof | |
| TWI761303B (en) | Polyvinyl alcohol-based film, method for producing polyvinyl alcohol-based film, and polarizing film | |
| CN101866023B (en) | Optical polyester film and preparation method thereof | |
| CN107614578A (en) | The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film | |
| TWI798217B (en) | Polyvinyl alcohol-based film, polarizing film, polarizing plate, and method for producing polyvinyl alcohol-based film | |
| CN110421938A (en) | A kind of preparation method of tearable polyester film | |
| US20090092812A1 (en) | Transparent PVC sheet for cutting-off infrared and ultra-violet | |
| JP2002086474A (en) | Cellulose ester film, method and apparatus for manufacturing the same and polarizing plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |