CN108047473A - A kind of antistatic optical hardening film - Google Patents
A kind of antistatic optical hardening film Download PDFInfo
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- CN108047473A CN108047473A CN201711342931.XA CN201711342931A CN108047473A CN 108047473 A CN108047473 A CN 108047473A CN 201711342931 A CN201711342931 A CN 201711342931A CN 108047473 A CN108047473 A CN 108047473A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
A kind of antistatic optical hardening film including support, is coated on the antistatic backing on support surface and the hardened layer being arranged on antistatic backing.The antistatic backing is formed by curing by the coating fluid containing polyurethane resin and carbon nanotubes；The hardened layer is formed by curing by the coating fluid that the component of following portions by weight forms：Urethane acrylate oligomer, diluent, isocyanates, photoinitiator, leveling auxiliary agent and organic solvent.Antistatic optical hardening film excellent in optical properties provided by the invention, ply adhesion is good, antistatic performance is excellent, and antistatic performance will not fail because of the variation of external environment.
Description
Technical field
The present invention relates to a kind of films, are particularly used as protection kinds of displays and the antistatic optics of touch screen protective is hard
Change film.
Background technology
Plastic film is widely used due to the excellent properties in processability, quality, cost etc., but due to
Its volume resistivity is high, and appearance is easy to produce static electricity, so as to which the attachment of dust foreign matter, film can be triggered to adsorb each other, print bad etc. ask
Topic, it is therefore desirable to improve use after film surface characteristic.Antistatic material is typically added in a slice or in film table
Face is coated with one layer of priming coat containing antistatic material, and antistatic material used generally has metal oxide or lithium salts, ammonium
The surfactants such as salt.Addition metal oxide can influence the translucency and color of film, limit the application range of film；Add
The antistatic persistence for adding the surfactants such as lithium salts, ammonium salt is poor, poor heat resistance more sensitive to ambient temperature and humidity, and easily
It is oozed out in film surface, the apparent disadvantage such as stick together.Importantly, although the film that this method makes has antistatic
Function, but film surface hardness is low, adhesion strength is poor, limits its use scope.
Antistatic auxiliary, fluorine auxiliary agent are added in radiation curable coating by Chinese patent CN103351677A, pass through cloudy surface
Anti-dazzle light effect is printed off in roll-in, while has both antistatic, anti-fouling effect, this method being added to antistatic auxiliary in coating
Anti-static function can be reached, but after heatproof, moisture resistance test, there are problems that the transparency and static electricity resistance are deteriorated.China
Make coating that there is static electricity resistance by adding conducting particles in patent CN102991056A, but such as antimony-doped stannic oxide, indium-doped two
It is apparent that the conducting particles such as tin oxide can influence clear coat, generates the apparent disadvantages such as fisheye, impure point.
To sum up, how to provide the endurable antistatic optical hardening film of a kind of excellent in optical properties, static electricity resistance becomes this
Field technology personnel's urgent problem.
The content of the invention
The technical problem to be solved by the present invention is in view of the deficienciess of the prior art, providing a kind of antistatic optics hardening
Film.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of antistatic optical hardening film including support, antistatic backing and hardened layer, is applied on the surface of support and deployed troops on garrison duty
Electrostatic layer, antistatic backing are formed by curing by the coating fluid containing polyurethane resin and carbon nanotubes；It is applied on the surface of antistatic backing
Cloth hardened layer, hardened layer are formed by curing by the coating fluid that the component of following portions by weight forms：
The parts by weight of 10 parts by weight of urethane acrylate oligomer~20,
The parts by weight of 10 parts by weight of diluent~20,
The parts by weight of 5 parts by weight of isocyanates~10,
The parts by weight of 0.1 parts by weight of photoinitiator~5,
The parts by weight of 0.2 parts by weight of leveling auxiliary agent~2,
The parts by weight of 45 parts by weight of organic solvent~65,
The urethane acrylate oligomer selects the aliphatic polyurethane acrylic acid below 4 degrees of functionality and 4 degrees of functionality
Ester；The diluent selects the acrylate monomer of bifunctionality or three-functionality-degree.
Above-mentioned antistatic optical hardening film, carbon nanotubes is hydroxy functionalized single in the antistatic backing
Pipe.
Above-mentioned antistatic optical hardening film, the pencil hardness of the hardened layer is 1H~3H.
Above-mentioned antistatic optical hardening film, the isocyanates is isophorone diisocyanate, 1,5- naphthalene diisocyanates
One kind in ester, hexa-methylene -1,6- diisocyanate, hydrogenated diphenyl methane diisocyanate.
Above-mentioned antistatic optical hardening film, the thickness of the antistatic backing is 300nm~600nm；The thickness of the hardened layer
It spends for 1 μm~5 μm.
Above-mentioned antistatic optical hardening film, the support is polycarbonate film, polyethylene terephthalate is thin
One kind in film, polymethyl methacrylate film；The thickness of the support is 23 μm~250 μm.
Above-mentioned antistatic optical hardening film, the curing process of the hardened layer are first dry out solvent, baking oven in drying box
Temperature is 100 DEG C~120 DEG C, and the time is 5min~10min；Then ultraviolet light photocuring is carried out, UV Light energy is
500mJ/cm2~1000mJ/cm2。
Compared with prior art, the invention has the advantages that：
1st, the present invention by select urethane acrylate oligomer below 4 degrees of functionality and 4 degrees of functionality, bifunctionality or
The acrylate monomer of person's three-functionality-degree can control the crosslink density and curing degree of hardened layer, the carbon in antistatic backing is made to receive
Mitron conductive material can run through hardened layer, so as to harden layer surface with static electricity resistance；It is and hardened layer optical property, anti-zoned
Wound is had excellent performance, and antistatic property does not weaken with unfavorable factors such as humiture, solvent wipings.
2nd, the bifunctionality or the acrylate monomer of three-functionality-degree that the present invention uses can make hardened layer and antistatic
Layer has good cohesive force, overcomes the bad problem of adhesive force caused by UV solidification coating is shunk.In addition, what the present invention selected
Hydroxy functionalized single-walled carbon nanotube can be chemically reacted with the isocyanates in hardened layer, and carbon nanotubes is fixed on
In coating, while also increase the adhesive force of hardened layer and antistatic backing.
Description of the drawings
Fig. 1 is the structure chart of the present invention.
Each label is expressed as in figure, and 1：Support；2：Antistatic backing；3：Hardened layer.
Specific embodiment
It is suitble to the support of the present invention to have polyethylene terephthalate, makrolon, polymethyl methacrylate etc.
Plastic film or thin plate.
Being suitble to the thickness of the support of the present invention, preferred thickness is 50 μm~188 μm of transparent base for 23 μm~250 μm
Material.
The hardened layer of the present invention is by containing urethane acrylate oligomer, diluent, isocyanates, photoinitiator, stream
The coating fluid of the compositions such as flat auxiliary agent, organic solvent cures.Be suitble to the polyurethane acrylic resin of the present invention for 4 degrees of functionality and
The acrylate monomer of aliphatic urethane acrylate below 4 degrees of functionality, diluent selection difunctionality or trifunctional.Choosing
Degree of functionality relatively low resin and monomer are selected, is to control the crosslink density after curing of coatings.If the tree for selecting degree of functionality high
Fat and monomer, the coating after ultraviolet light cures have higher crosslink density, and the hardness and adhesion strength of coating surface are preferable,
But the high coating of crosslink density hinders the infiltration of carbon nanotubes in antistatic backing and runs through, the sheet resistance value of final film
Height, antistatic performance are poor.In order to ensure that coating surface has adhesion strength, it is impossible to select degree of functionality too low or flexible group
More resin.Meanwhile the thickness of antistatic backing can also influence to harden the antistatic performance of layer surface, it is also desirable to take into account hardened layer
Adhesion strength, be suitble to the present invention thin hardened layer be 1 μm~5 μm.In addition, in order to ensure to reach suitable curing degree,
It needs to select suitable ultraviolet light solidification energy.
In formula provided by the invention, the control of the dosage of urethane acrylate oligomer is in the weight of 10 parts by weight~20
Part, the control of the dosage of diluent is in the parts by weight of 10 parts by weight~20；Hardened layer coating fluid institute in the curing process in the present invention
The ultraviolet light used can be obtained from high-pressure sodium lamp, and the UV Light energy for being suitble to this formula is 500mJ/cm2~1000mJ/
cm2；The pencil hardness of hardened layer is 1H~3H.
The antistatic backing of the present invention is formed by curing by the coating fluid that polyurethane resin and carbon nanotubes form, antistatic backing
Thickness is 300nm~600nm.It is prior in order to ensure to have between antistatic backing and hardened layer good ply adhesion
It is to fix carbon nanotubes the carbon nanotubes of the present invention is suitble to select hydroxy functionalized single-walled carbon nanotube in the coating；This
During hardened layer dry out solvent with carbon nanotubes chemistry can occur for the isocyanates selected in the hardened layer of invention instead
Should, carbon nanotubes is completely fixed in the coating, antistatic property will not with external conditions such as time, humiture, soda acids and
Decline.Consider the condition of cure of isocyanates, the temperature of hardened layer dry out solvent selects 100 DEG C~120 DEG C, the time for 5min~
10min
Isocyanates in the present invention is isophorone diisocyanate, 1,5- naphthalene diisocyanates, hexa-methylene -1,6-
One kind in diisocyanate, hydrogenated diphenyl methane diisocyanate, additive amount are the parts by weight of 5 parts by weight~10.
Antistatic backing is made of with coating fluid polyurethane resin, crosslinking agent, carbon nanotubes, auxiliary agent and deionized water；It is poly-
The additive amount of urethane is the parts by weight of 2 parts by weight~15, and the additive amount of crosslinking agent is the parts by weight of 0.5 parts by weight~2, carbon nanotubes
Additive amount is the parts by weight of 2 parts by weight~10, and the additive amount of auxiliary agent is the parts by weight of 0.5 parts by weight~5, and the additive amount of deionized water is
The parts by weight of 68 parts by weight~95.
Photoinitiator in the present invention can select initiator well known to UV curing field, such as 1- hydroxy-cyclohexyl benzene
Base ketone (184), 2- hydroxy-methyl phenyl-propane -1- ketone (1173), benzoin dimethylether (651), 2,4,6 (trimethylbenzene first
Acyl group) diphenyl phosphine oxide (TPO) etc..
As needed, need to add in solvent in the coating fluid of hardened layer, conventional organic solvent can be used without appointing
What is limited, such as：Alcohols such as methanol, ethyl alcohol, propyl alcohol；Ketone such as acetone, butanone, methyl iso-butyl ketone (MIBK)；Esters such as ethyl acetate,
Butyl acetate, ethyl propionate.It is preferred that the strong ketone of dissolubility and esters.
Auxiliary agent in the present invention can select organosiloxane well known to UV curing field or organic-silicon-modified third
BYK-307, BYK-354, BYK-377 of olefin(e) acid levelling agent, such as Germany's Bi Ke chemistry, the Levaslip407 of the modest chemistry of moral,
Levaslip410, Levaslip432 etc..
With reference to specific embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to
This.
Embodiment 1
By 10g polyurethane acrylate resins (degree of functionality 4, Sartomer, trade name：CN8007NS), 20g dilutes
Agent (trifunctional monomer, Sartomer, trade name：SR9035), 9.2g isocyanates (isoflurane chalcone diisocyanate IPDI,
Ying Chuan companies), 0.1g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：1173), 1g leveling auxiliary agents (Bi Ke
Chemistry, BYK-307) and 59.7g acetone be placed in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 23 μm of polycarbonate film, antistatic backing is formed after curing；Antistatic is coated with
Liquid is by 2g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), the hydroxy functionalized single wall carbon of 2g receives
Mitron (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), (Changzhou is blue sub- for 0.5g crosslinking agents
New material Science and Technology Ltd., trade name：710), 0.5g auxiliary agents (Bi Ke chemistry, BYK-307), 95g deionized waters, stirring are equal
It is made after even.
By above-mentioned for use coating solution on antistatic backing, 10min is placed in the baking oven for being first 100 DEG C in temperature, so
With UV energy it is again afterwards 500mJ/cm2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
600nm, thin hardened layer are 4 μm, and assessment result is listed in Table 1 below.
Embodiment 2
By 20g polyurethane acrylate resins (degree of functionality 2, Sartomer, trade name：CN983NS), 10g dilutes
Agent (bifunctional monomer, Sartomer, trade name：SR508NS), 10g isocyanates (1,5- naphthalene diisocyanate NDI,
COVESTRO companies), 5g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：184), 0.2g leveling auxiliary agents (are finished
Gram chemistry, BYK-354) and 54.8g ethyl acetate be placed in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 250 μm of pet film, antistatic is formed after curing
Layer；Antistatic coating fluid is by 8g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 6g hydroxyl work(
Single-walled carbon nanotube (Suzhou Tan Feng graphenes Science and Technology Ltd., the trade name of energyization：HQNANO-CNTS-002C), 1.0g is handed over
Join agent (Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 3g auxiliary agents (Bi Ke chemistry, BYK-307), 82g go from
Sub- water is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 5min is placed in the baking oven for being first 120 DEG C in temperature, then
It is again 1000mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
300nm, thin hardened layer are 1 μm, and assessment result is listed in Table 1 below.
Embodiment 3
By 12g polyurethane acrylate resins (degree of functionality 3, Sartomer, trade name：CN8009NS), 18g dilutes
Agent (bifunctional monomer, Sartomer, trade name：SR205NS), 5g isocyanates (hydrogenated diphenyl methane diisocyanate
H12MDI, Ying Chuan company), 3g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：651), 2g leveling auxiliary agents
(the modest chemistry of moral, Levaslip407) and 60g ethyl acetate are placed in agitated kettle, coating fluid are obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 125 μm of polymethyl methacrylate film, antistatic backing is formed after curing；It is anti-
Electrostatic applications liquid is by 15g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 10g it is hydroxy functionalized
Single-walled carbon nanotube (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), 2.0g crosslinking agents
(Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 5g auxiliary agents (Bi Ke chemistry, BYK-307), 68g deionized waters,
It is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 8min is placed in the baking oven for being first 105 DEG C in temperature, then
It is again 600mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
400nm, thin hardened layer are 5 μm, and assessment result is listed in Table 1 below.
Embodiment 4
By 19g polyurethane acrylate resins (degree of functionality 4, Changxing chemistry, trade name：DR-U052), 20g diluents
(trifunctional monomer, Changxing chemistry, trade name：EM331), 10g isocyanates (hexa-methylene -1,6- diisocyanate HDI,
COVESTRO companies), 4.5g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：TPO), 1.5g leveling auxiliary agents
(the modest chemistry of moral, Levaslip410) and 45g butyl acetates are placed in agitated kettle, coating fluid are obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 50 μm of polycarbonate film, antistatic backing is formed after curing；Antistatic is coated with
Liquid is by 6g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), the hydroxy functionalized single wall carbon of 4g receives
Mitron (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), (Changzhou is blue sub- for 0.8g crosslinking agents
New material Science and Technology Ltd., trade name：710), 2g auxiliary agents (Bi Ke chemistry, BYK-307), 87.2g deionized waters, stirring are equal
It is made after even.
By above-mentioned for use coating solution on antistatic backing, 6min is placed in the baking oven for being first 110 DEG C in temperature, then
It is again 900mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
500nm, thin hardened layer are 2 μm, and assessment result is listed in Table 1 below.
Embodiment 5
By 15g polyurethane acrylate resins (degree of functionality 2, Changxing chemistry, trade name：6152B-80), 12g diluents
(bifunctional monomer, Changxing chemistry, trade name：EM3261), (it is public to win wound to 6g isocyanates by isoflurane chalcone diisocyanate IPDI
Department), 1.4g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：184), 0.6g leveling auxiliary agents (Bi Ke chemistry,
BYK-377) it is placed in 65g ethyl alcohol in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 188 μm of pet film, antistatic is formed after curing
Layer；Antistatic coating fluid is by 10g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 8g hydroxyl work(
Single-walled carbon nanotube (Suzhou Tan Feng graphenes Science and Technology Ltd., the trade name of energyization：HQNANO-CNTS-002C), 1.5g is handed over
Join agent (Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 4g auxiliary agents (Bi Ke chemistry, BYK-307), 76.5g are gone
Ionized water is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 7min is placed in the baking oven for being first 115 DEG C in temperature, then
It is again 800mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
450nm, thin hardened layer are 3 μm, and assessment result is listed in Table 1 below.
Comparative example 1
By 10g polyurethane acrylate resins (degree of functionality 6, Sartomer, trade name：CN8011NS), 20g dilutes
Agent (trifunctional monomer, Sartomer, trade name：SR9035), (isoflurane chalcone diisocyanate IPDI is won 9g isocyanates
Wound company), 2g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：1173), 1g leveling auxiliary agents (Bi Ke chemistry,
BYK-307) it is placed in 58g acetone in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 23 μm of polycarbonate film, antistatic backing is formed after curing；Antistatic is coated with
Liquid is by 2g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), the hydroxy functionalized single wall carbon of 2g receives
Mitron (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), (Changzhou is blue sub- for 0.5g crosslinking agents
New material Science and Technology Ltd., trade name：710), 0.5g auxiliary agents (Bi Ke chemistry, BYK-307), 95g deionized waters, stirring are equal
It is made after even.
By above-mentioned for use coating solution on antistatic backing, 10min is placed in the baking oven for being first 100 DEG C in temperature, so
With UV energy it is again afterwards 500mJ/cm2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
600nm, thin hardened layer are 4 μm, and assessment result is listed in Table 1 below.
Comparative example 2
By 20g polyurethane acrylate resins (degree of functionality 2, Sartomer, trade name：CN983NS), 10g dilutes
Agent (five functional monomers, Sartomer, trade name：SR399NS), 10g isocyanates (1,5- naphthalene diisocyanate NDI,
COVESTRO companies), 5g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：184), 0.2g leveling auxiliary agents (are finished
Gram chemistry, BYK-354) and 54.8g ethyl acetate be placed in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 250 μm of pet film, antistatic is formed after curing
Layer；Antistatic coating fluid is by 8g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 6g hydroxyl work(
Single-walled carbon nanotube (Suzhou Tan Feng graphenes Science and Technology Ltd., the trade name of energyization：HQNANO-CNTS-002C), 1.0g is handed over
Join agent (Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 3g auxiliary agents (Bi Ke chemistry, BYK-307), 82g go from
Sub- water is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 5min is placed in the baking oven for being first 120 DEG C in temperature, then
It is again 1000mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
300nm, thin hardened layer are 1 μm, and assessment result is listed in Table 1 below.
Comparative example 3
By 12g polyurethane acrylate resins (degree of functionality 6, Sartomer, trade name：CN8011NS), 18g dilutes
Agent (five functional monomers, Sartomer, trade name：SR399NS), 5g isocyanates (hydrogenated diphenyl methane diisocyanate
H12MDI, Ying Chuan company), 3g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：651), 2g leveling auxiliary agents
(the modest chemistry of moral, Levaslip407) and 60g ethyl acetate are placed in agitated kettle, coating fluid are obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 125 μm of polymethyl methacrylate film, antistatic backing is formed after curing；It is anti-
Electrostatic applications liquid is by 15g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 10g it is hydroxy functionalized
Single-walled carbon nanotube (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), 2.0g crosslinking agents
(Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 5g auxiliary agents (Bi Ke chemistry, BYK-307), 68g deionized waters,
It is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 8min is placed in the baking oven for being first 105 DEG C in temperature, then
It is again 600mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
400nm, thin hardened layer are 5 μm, and assessment result is listed in Table 1 below.
Comparative example 4
By 19g polyurethane acrylate resins (degree of functionality 4, Changxing chemistry, trade name：DR-U052), 20g diluents
(trifunctional monomer, Changxing chemistry, trade name：EM331), (Tianjin proud son of heaven Chemical Co., Ltd. manufactures 4.5g photoinitiators, commodity
Name：TPO), 1.5g leveling auxiliary agents (the modest chemistry of moral, Levaslip410) and 55g butyl acetates are placed in agitated kettle, are stirred evenly
After obtain coating fluid, for use.
Antistatic coating fluid is coated on 50 μm of polycarbonate film, antistatic backing is formed after curing；Antistatic is coated with
Liquid is by 6g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), the hydroxy functionalized single wall carbon of 4g receives
Mitron (Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTS-002C), (Changzhou is blue sub- for 0.8g crosslinking agents
New material Science and Technology Ltd., trade name：710), 2g auxiliary agents (Bi Ke chemistry, BYK-307), 87.2g deionized waters, stirring are equal
It is made after even.
By above-mentioned for use coating solution on antistatic backing, 6min is placed in the baking oven for being first 110 DEG C in temperature, then
It is again 900mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
500nm, thin hardened layer are 2 μm, and assessment result is listed in Table 1 below.
Comparative example 5
By 15g polyurethane acrylate resins (degree of functionality 2, Changxing chemistry, trade name：6152B-80), 12g diluents
(bifunctional monomer, Changxing chemistry, trade name：EM3261), (it is public to win wound to 6g isocyanates by isoflurane chalcone diisocyanate IPDI
Department), 1.4g photoinitiators (Tianjin proud son of heaven Chemical Co., Ltd. manufacture, trade name：184), 0.6g leveling auxiliary agents (Bi Ke chemistry,
BYK-377) it is placed in 65g ethyl alcohol in agitated kettle, coating fluid is obtained after stirring evenly, for use.
Antistatic coating fluid is coated on 188 μm of pet film, antistatic is formed after curing
Layer；Antistatic coating fluid is by 10g polyurethane resins (Zhan Xin resins Co., Ltd, trade name：UCECOAT 7655), 8g single wall carbon
Nanotube (no other groups grafting, Suzhou Tan Feng graphenes Science and Technology Ltd., trade name：HQNANO-CNTs-002)、1.5g
Crosslinking agent (Changzhou Lan Ya new materials Science and Technology Ltd., trade name：710), 4g auxiliary agents (Bi Ke chemistry, BYK-307), 76.5g
Deionized water is made after stirring evenly.
By above-mentioned for use coating solution on antistatic backing, 7min is placed in the baking oven for being first 115 DEG C in temperature, then
It is again 800mJ/cm with UV energy2Ultraviolet light to coating carry out UV curings, obtain hardened layer；Antistatic backing thickness is
450nm, thin hardened layer are 3 μm, and assessment result is listed in Table 1 below.
Table 1：The test data table of antistatic optical hardening film in each embodiment and comparative example
Sheet resistance value is the important indicator of reactive film material antistatic performance, can generally less than be had equal to 12 powers
There is anti-static function, but general resistance value is lower, and antistatic performance is more excellent.As can be seen from the table, comparative example 1, comparison
The polyurethane acrylate resin or diluent for the high functionality that example 2, comparative example 3 select, the curing degree of coating is high after UV cures,
Crosslink density is high, therefore final coating resistance value is higher, antistatic performance deviation.From comparative example 4, comparative example 5 as can be seen that reaction
Type cross-linked structure can make antistatic backing and hardened layer keep preferable ply adhesion, while carbon nanotubes is fixed on coating
In, antistatic performance is effective for a long time.In addition, light transmittance is more than 90% in table, mist degree is less than 1%, and the antistatic of this structure is hard
Change film excellent in optical properties.
The test method of properties is as follows in table：
(1) light transmittance, mist degree test
Utilize haze meter [Japanese electricity Se companies；Model：NDH2000N], measure light transmittance and mist degree.
(2) pencil hardness test
The hardness of film tester scraped using pencil is [by Shanghai Pu Shen chemical machineries Co., Ltd；Model：" BY "] it surveys
Measure pencil hardness.
(3) coating adhesion test method
Reference standard GB/T 9286, the hard coating surface of hard coat film is cut into 100 section lines with cutter, wherein each
The size of section line is 1mm × 1mm, then adheres to 3M-610 type professional tests adhesive tape (3M companies) with 2.0Kg power and draws lattice
On hard coating surface.After 3min with 180 ° of angles by 3M adhesive tapes from the sur-face peeling.Coating adhesion is stayed on base material according to counting
The number of section line of hard conating assessed, be divided into 1B, 2B, 3B, 4B and 5B totally 5 grades from low to high.
(5) sheet resistance value test method
Use megger [No.6 Electric Meter Factory；Model：PC68] measurement cured film sheet resistance
The above is only some embodiments of the present invention, is not intended to limit protection scope of the present invention.Every basis
The equivalent variations and modification that core technology of the present invention is done should all cover in the scope of patent protection of the present invention.
Claims (7)
1. a kind of antistatic optical hardening film, including support, antistatic backing and hardened layer, which is characterized in that in support
Surface is coated with antistatic backing, and antistatic backing is formed by curing by the coating fluid containing polyurethane resin and carbon nanotubes；In antistatic
The surface coating hardened layer of layer, hardened layer are formed by curing by the coating fluid that the component of following portions by weight forms：
The parts by weight of 10 parts by weight of urethane acrylate oligomer~20,
The parts by weight of 10 parts by weight of diluent~20,
The parts by weight of 5 parts by weight of isocyanates~10,
The parts by weight of 0.1 parts by weight of photoinitiator~5,
The parts by weight of 0.2 parts by weight of leveling auxiliary agent~2,
The parts by weight of 45 parts by weight of organic solvent~65；
The urethane acrylate oligomer selects the aliphatic urethane acrylate below 4 degrees of functionality and 4 degrees of functionality；Institute
State the acrylate monomer that diluent selects bifunctionality or three-functionality-degree.
2. antistatic optical hardening film according to claim 1, which is characterized in that carbon nanotubes is hydroxyl in the antistatic backing
The single-walled carbon nanotube of base functionalization.
3. antistatic optical hardening film according to claim 1, which is characterized in that the pencil hardness of the hardened layer for 1H~
3H。
4. antistatic optical hardening film according to claim 1, which is characterized in that the isocyanates is different for isophorone two
One in cyanate, 1,5- naphthalene diisocyanates, hexa-methylene -1,6- diisocyanate or hydrogenated diphenyl methane diisocyanate
Kind.
5. antistatic optical hardening film according to claim 1, which is characterized in that the thickness of the antistatic backing is 300nm
~600nm；The thickness of the hardened layer is 1 μm~5 μm.
6. antistatic optical hardening film according to claim 1, which is characterized in that the support for polycarbonate film,
One kind in pet film, polymethyl methacrylate film；The thickness of the support is 23 μm
~250 μm.
7. antistatic optical hardening film according to claim 1, which is characterized in that the curing process of the hardened layer is, first
The dry out solvent in drying box, oven temperature are 100 DEG C~120 DEG C, and the time is 5min~10min；Then ultraviolet light light is carried out
Cure, UV Light energy is 500mJ/cm2~1000mJ/cm2。
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| CN108690392A (en) * | 2018-06-20 | 2018-10-23 | 厦门祥福兴科技股份有限公司 | A kind of graphene coating and application thereof |
| CN110437730A (en) * | 2019-07-26 | 2019-11-12 | 四川羽玺新材料股份有限公司 | A kind of light weather-proof optical grade PET cured film |
| CN110698976A (en) * | 2019-11-21 | 2020-01-17 | 深圳市益达兴科技股份有限公司 | Process for producing coating with polyurethane acrylate resin |
| CN111875833A (en) * | 2020-06-16 | 2020-11-03 | 宁波惠之星新材料科技有限公司 | High-water-contact antistatic hardened film and preparation method thereof |
| CN112280085A (en) * | 2020-09-24 | 2021-01-29 | 浙江日久新材料科技有限公司 | Low-roughness MLCC functional release film capable of being used in tape casting and preparation method thereof |
| CN115521705A (en) * | 2022-10-26 | 2022-12-27 | 合肥乐凯科技产业有限公司 | Anti-static hardened film and preparation method thereof |
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| CN112280085A (en) * | 2020-09-24 | 2021-01-29 | 浙江日久新材料科技有限公司 | Low-roughness MLCC functional release film capable of being used in tape casting and preparation method thereof |
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