CN106118556B - A kind of preparation method of the anti-scratch crystal film of surface advertisement - Google Patents
A kind of preparation method of the anti-scratch crystal film of surface advertisement Download PDFInfo
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- CN106118556B CN106118556B CN201610585653.XA CN201610585653A CN106118556B CN 106118556 B CN106118556 B CN 106118556B CN 201610585653 A CN201610585653 A CN 201610585653A CN 106118556 B CN106118556 B CN 106118556B
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- film
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- crystal film
- clear hard
- coated
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F15/00—Boards, hoardings, pillars, or like structures for notices, placards, posters, or the like
- G09F15/02—Bills, posters, or the like therefor
Abstract
The invention belongs to advertising display and decorative material technical field, the preparation method of more particularly to a kind of anti-scratch crystal film of surface advertisement first prepares Optical transparent adhesive and clear hard coating；Then silicone oil is coated on polyester film, forms silicon layer, 10 30 μm of Optical transparent adhesive is then coated on silicon layer, is formed and learns substratum transparent, PET film, drying are covered in optical clear film surface；Then it is coated with clear hard coating on a pet film, forms clear hard dope layer, UV curings；Protective film finally is covered on the clear hard dope layer of above-mentioned PET film, is wound.Crystal film is had excellent performance in terms of heat aging property, UV resistant light aging, and high crystal film has self-cleaning function, and dust is not easy to adhere to, easy cleaning.Visible light transmission is more than 94%, can be used as the exploitation on the glass of store or supermarket.
Description
Technical field
The invention belongs to advertising display and decorative material technical field, the anti-scratch crystal of more particularly to a kind of surface advertisement
The preparation method of film.
Background technology
Nowadays, advertising industry rapidly develops, we are seen everywhere large scale business advertisement.It is especially outdoors or large-scale
Market, supermarket glass on can all spray it is various with exploitation pattern.The color requirements for publicizing pattern are very high, clear,
Transparent, wear-resisting, this has very high requirement to the film of advertising surface.
Film of the prior art is generally using cold lamination film, and glue uses pressure sensitive adhesive, surface covering release paper, but the time
After having grown, due to the irradiation of ultraviolet light, pressure sensitive adhesive turns yellow, so the degree bright in luster of pattern is affected.Especially
Store or the glass of ultrasound, almost can all wipe daily, so, cold lamination film of the prior art not scrubbing resistance, resistance to scraping is poor, past
Toward after half a year, protective film just has many scratches, influences entirely to publicize the transparency of pattern.
How crystal membrane technology to be continuously improved, transparency, the resistance to scraping of film are improved on the basis of preparation process is simplified
And performance so that image quality is our technical problems to be solved more preferably.
Invention content
The object of the present invention is to provide a kind of preparation method of surface advertisement crystal film, the film obtained by this method
Resistance to scraping and transparency it is very excellent, good waterproof performance is fast light, and causes the bright-colored of advertising pattern, not fugitive color,
Usage time is long.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of surface advertisement crystal film, step include
(1) optically transparent preparation：
The raw material of following weight ratio is weighed,
Above-mentioned raw materials are stirred, are stood, are filtered, detection is spare；
(2) preparation of clear hard coating：
The raw material of following weight ratio is weighed,
Above-mentioned raw materials are stirred, are stood, are filtered, detection is spare；
(3) preparation of surface advertisement crystal film：
It is coated with silicone oil on polyester film, forms silicon layer, then 10-30 μm is coated on silicon layer the step of in (1)
The Optical transparent adhesive of preparation forms and learns transparent adhesive tape, and after drying, PET film is covered in optical clear film surface；
Then the clear hard coating in squeegeeing step (2) on a pet film forms clear hard dope layer, after drying,
UV cures；
Protective film finally is covered on above-mentioned bright hard coating layer, is wound
The crystal film is from top to bottom followed successively by protection film layer, clear hard dope layer, PET film layer, optical clear glue-line, silicon
Oily release film layer.Preferably, the protection film layer is PE film layers.The material of the release film layer is PET film.
Preferably, the raw material proportioning of the Optical transparent adhesive is (percent by weight)
It according to weight ratio is 1 that the UV absorbents, which are hindered amine light stabilizer and Benzotriazole Ultraviolet Stabilizer,:
The mixture of 4-10 mixing.
The solvent is the mixed solvent of one or more of ethyl acetate, formic acid, acetone.
The curing agent is isocyanates.
The levelling agent is organosiloxane class levelling agent.
Preferably, the raw material proportioning of the clear hard coating is (percent by weight)
The esters of acrylic acid mix monomer, the mix monomer of the acrylic ester monomer containing 2-6 functional group,
In, in the esters of acrylic acid mix monomer, the acrylic ester monomer content of 4 functional groups is the 5- of mix monomer total amount
The acrylic ester monomer content of 35wt%, 5-6 functional groups is the 50-80wt% of mix monomer total amount；2-3 functional group
Acrylic ester monomer content is the 5-40wt% of mix monomer total amount.The resistance to scraping of the acrylic acid glue-line of the proportioning is very excellent
It is different.
Preferably, the acrylic ester monomer of 4 functional groups is pentaerythritol tetraacrylate；5-6 functional group
Acrylic ester monomer for five acrylate of dipentaerythrite, six acrylate of dipentaerythrite；2-3 functional group
Acrylic ester monomer is neopentylglycol diacrylate, pentaerythritol triacrylate.
The photoinitiator is Benzotriazole Ultraviolet Stabilizer；The paint solvent is ethyl acetate, formic acid or third
One kind in ketone.The low-surface-energy additive is organosiloxane or polytetrafluoroethylmodified modified additive.
The thickness of surface advertisement crystal film is 50-300 μm.
The beneficial effects of the invention are as follows：
1st, crystal film prepared by the present invention is had excellent performance in terms of heat aging property, UV resistant light aging, Er Qiegao
Crystal film has self-cleaning function, and dust is not easy to adhere to, easy cleaning.
2nd, the planarization of the crystal film prepared in invention is good, is not susceptible to refraction effect, and resistance to scraping is very good, and hardness is high,
Transparency is high, and visible light transmission is more than 94%, can be used as the exploitation on the glass of store or supermarket.
Specific embodiment
With reference to embodiment, the invention will be further described：
UV absorbents, hindered amine light stabilizer (HALS), Ciba；Benzotriazole Ultraviolet Stabilizer (UV-
328), BASF joint-stock company；Pentaerythritol tetraacrylate：Shanghai promise Thailand chemical industry；Five acrylate of dipentaerythrite gathers
Dipentaerythritol hexaacrylate, pentaerythritol triacrylate：Sartomer of the U.S.；Neopentylglycol diacrylate：On
Hai Ruishuo chemical industry；Levelling agent：Enlightening is high by 378.
Embodiment 1
1) preparation of Optical transparent adhesive：
Weigh the raw material of following weight ratio：
Polyacrylate, 45%；UV absorbents (HALS：UV-328=1：4), 1.2%；Isocyanates, 5%；Acetic acid second
Ester, 47%；Organosiloxane class levelling agent, 1.8%.
It is stirred, stands after above-mentioned raw materials are added in polymeric kettle, filter, detection is spare.
The solid content of Optical transparent adhesive obtained is 40%, and softening point temperature is 75 DEG C, apparent viscosity 5500MPa.S, is glued
Knotting strength 2.4Kg/25mm.
2), prepared by clear hard dope layer
Weigh the raw material of following weight ratio：
Esters of acrylic acid mix monomer, 50% (wherein pentaerythritol tetraacrylate 9wt%, dipentaerythrite 6 third
Olefin(e) acid ester 80wt%, pentaerythritol triacrylate 11wt%)；Benzotriazole Ultraviolet Stabilizer, 2%；Formic acid 45.5%,
Polytetrafluoroethylene (PTFE) 2.5%.It is stirred, stands, filter, detection is spare.
3), the preparation of crystal film：
Silicone oil is coated on polyester, 20 μm of Optical transparent adhesive is then coated on silicon layer, in optical clear glue-line table
Face covers PET film, then in brushing clear hard coating, after drying, UV curings；Finally in above-mentioned clear hard dope layer
Upper covering PE protective films, winding, speed of production are 30 meters/min.
Embodiment 2
1) preparation of Optical transparent adhesive：
Weigh the raw material of following weight ratio：
Polyacrylate, 50%；UV absorbents (HALS：UV-328=1：5), 1.8%；Isocyanates, 4%；Acetic acid second
Ester, 42.6%；Organosiloxane class levelling agent, 1.6%.
It is stirred, stands after above-mentioned raw materials are added in polymeric kettle, filter, detection is spare.
The solid content of Optical transparent adhesive obtained is 42%, and softening point temperature is 74 DEG C, apparent viscosity 5560MPa.S, is glued
Knotting strength 2.5Kg/25mm,.
2), prepared by clear hard dope layer
Weigh the raw material of following weight ratio：
Esters of acrylic acid mix monomer, 53.5% (wherein pentaerythritol tetraacrylate 20wt%, dipentaerythrite six
Acrylate 62wt%, pentaerythritol triacrylate 18wt%)；Benzotriazole Ultraviolet Stabilizer, 4%；Ethyl acetate
39.5%, polysiloxanes 3%.It is stirred, stands, filter, detection is spare.
3), the preparation of crystal film：
Silicone oil is coated on polyester film, 22 μm of Optical transparent adhesive is then coated on silicon layer, in optical clear glue-line
Surface covers PET film, is then coated with 1.5 μm of clear hard coating on a pet film, after drying, UV curings；Finally above-mentioned
PE protective films, winding are covered on clear hard dope layer, speed of production is 30 meters/min.
Embodiment 3
2) preparation of Optical transparent adhesive：
Weigh the raw material of following weight ratio：
Polyacrylate, 55%；UV absorbents (HALS：UV-328=1：6), 3%；Isocyanates, 2.5%；Formic acid,
38.5%；Organosiloxane class levelling agent, 1%.
It is stirred, stands after above-mentioned raw materials are added in polymeric kettle, filter, detection is spare.
The solid content of Optical transparent adhesive obtained is 42.5%, and softening point temperature is 74 DEG C, apparent viscosity 5600MPa.S,
Adhesion strength 2.5Kg/25mm.
2), prepared by clear hard dope layer
Weigh the raw material of following weight ratio：
Esters of acrylic acid mix monomer, 45% (wherein pentaerythritol tetraacrylate 15wt%, dipentaerythrite 6 third
Olefin(e) acid ester 65wt%, pentaerythritol triacrylate 20wt%)；Benzotriazole Ultraviolet Stabilizer, 3%；Ethyl acetate
48%, polysiloxanes 4%.It is stirred, stands, filter, detection is spare.
3), the preparation of crystal film：
Silicone oil is coated on polyester film, 21 μm of Optical transparent adhesive is then coated on silicon layer, in optical clear glue-line
Surface covers PET film, is then coated with 1.6 μm of clear hard coating on a pet film, after drying, UV curings；Finally above-mentioned
It is coated on clear hard dope layer and covers PE protective films, winding, speed of production is 30 meters/min.
Test：
It it is 100 DEG C in temperature, the time is 1000 small progress ultraviolet resistance burn-in tests at present, and light source is ultraviolet using UVB313
Lamp, illumination and condensation temperature are respectively 60 DEG C, 40 DEG C, and the time is 4 hours, and illumination and condensation alternately totally 1000 hours are resistance to
Yellowness index (Δ YI) after thermo-oxidative ageing and ultraviolet resistance aging presses GB2409-80《Plastics yellow colour index experimental method》Into
Row test.
It is compared simultaneously with commercially available cold lamination film：
The surface of the glue-line prepared in embodiment 1-3 is with A grades of facial canal controls, no bright spot, no particle, wireless lines.And
The alcohol resistance for changing crystal film is very good, and acidproof, alkali resistance is also very excellent.Compared with commercially available thin-film material, wearability,
The performances such as anti-flexing, hardness, initial bonding strength, peeling force are obviously improved.
By test, the flatness and deflection for the crystal film being prepared in above-described embodiment 1-3 are excellent, and light transmittance is high,
UV resistant and heat aging property are good, are used as the advertisement on windowpane, weatherability is very good, using 1 year without general
The crystal film prepared in yellow phenomenon, especially embodiment 2, performance are especially good.
Claims (5)
1. a kind of preparation method of surface advertisement crystal film, step include,
(1) preparation of Optical transparent adhesive：
The raw material of following weight ratio is weighed,
It according to weight ratio is 1 that the UV absorbents, which are hindered amine light stabilizer and Benzotriazole Ultraviolet Stabilizer,:4-10
The mixture of mixing；
Above-mentioned raw materials are stirred, are stood, are filtered, detection is spare；
(2) preparation of clear hard coating：
The raw material of following weight ratio is weighed,
Above-mentioned raw materials are stirred, are stood, are filtered, detection is spare；
The esters of acrylic acid mix monomer is the mix monomer of the acrylic ester monomer containing 2-6 functional group；Wherein, institute
It states in esters of acrylic acid mix monomer, the acrylic ester monomer content of 4 functional groups is the 5-35wt% of mix monomer total amount,
The acrylic ester monomer content of 5-6 functional group is the 50-80wt% of mix monomer total amount；The acrylic acid of 2-3 functional group
Esters monomer content is the 5-40wt% of mix monomer total amount；
(3) preparation of surface advertisement crystal film：
It is coated with silicone oil on polyester film, forms silicon layer, then prepared in (1) 10-30 μm is coated on silicon layer the step of
Optical transparent adhesive, formed optical clear glue-line, after drying, optical clear film surface cover PET film；
Then the clear hard coating in application step (2) on a pet film forms clear hard dope layer, and after drying, UV is solid
Change；
Protective film finally is covered on above-mentioned clear hard dope layer, is wound.
2. the preparation method of surface advertisement crystal film according to claim 1, it is characterised in that：In the step (1)
Solvent be ethyl acetate, the mixed solvent of formic acid, one or more of acetone.
3. the preparation method of surface advertisement crystal film according to claim 1, it is characterised in that：In the step (1)
Curing agent be isocyanates.
4. surface advertisement crystal film according to claim 1, it is characterised in that：Paint solvent in the step (2)
For one kind in ethyl acetate, formic acid or acetone.
5. surface advertisement crystal film according to claim 1, it is characterised in that：The low table in the step (2)
Face energy additive is organosiloxane or polytetrafluoroethylmodified modified additive.
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| CN201610585653.XA CN106118556B (en) | 2016-07-21 | 2016-07-21 | A kind of preparation method of the anti-scratch crystal film of surface advertisement |
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| CN201610585653.XA CN106118556B (en) | 2016-07-21 | 2016-07-21 | A kind of preparation method of the anti-scratch crystal film of surface advertisement |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041845A (en) * | 2019-04-24 | 2019-07-23 | 中山市旭森涂层材料有限公司 | A kind of antistatic Sticky Note and its preparation process |
| CN110154484A (en) * | 2019-04-24 | 2019-08-23 | 中山市旭森涂层材料有限公司 | The super antistatic crystal film of one kind and its manufacture craft |
| CN110435268A (en) * | 2019-09-18 | 2019-11-12 | 扬州市众和同盛包装材料有限公司 | Super permeable epitaxial of one kind and preparation method thereof |
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| CN101348620B (en) * | 2008-09-05 | 2010-11-10 | 中国海洋石油总公司 | UV anaerobic double curing coating |
| CN101864204B (en) * | 2010-06-09 | 2011-07-06 | 宜兴市宏泰化工有限公司 | Dedicated high-performance primer of ultraviolet-curing vacuum coating for reflector of automobile lamps |
| CN103612456B (en) * | 2013-12-04 | 2016-03-16 | 东莞市纳利光学材料有限公司 | A kind of antistatic scratching-resistingprotective protective film and preparation method thereof |
| CN105017976B (en) * | 2015-07-28 | 2018-05-08 | 浙江欧仁新材料有限公司 | A kind of anti-scratch glue and its preparation method and application |
| CN105295762B (en) * | 2015-10-23 | 2018-06-26 | 浙江欧丽数码喷绘材料有限公司 | A kind of antistatic ultrathin double-face glue |
| CN205382118U (en) * | 2016-02-22 | 2016-07-13 | 浙江欧仁新材料有限公司 | Heat conduction double -faced adhesive film material |
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Effective date of registration: 20180326 Address after: 314100, No. 78, South Town Road, Ding Industrial Park, Yao Town, Jiashan, Zhejiang, Jiaxing Applicant after: Zhejiang Ouli Digital Printing Materials Co., Ltd. Address before: 314100 Jiashan City, Jiaxing Province Yao county, Zhejiang Galaxy Road, No. 1, building 1, building 17 Applicant before: ZHEJIANG OUREN NEW MATERIAL CO., LTD. |
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Address after: 314100 No. 17, Yinhe Road, Yao Zhuang Town, Jiashan County, Jiaxing, Zhejiang. Patentee after: Zhejiang fry new material Limited by Share Ltd Address before: 314100 No. 78 South Road, Ding Gate Industrial Park, Yao Zhuang Town, Jiashan, Jiaxing, Zhejiang Patentee before: Zhejiang Ouli Digital Printing Materials Co., Ltd. |
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Denomination of invention: Preparation method for anti-scratch crystal film for surface advertisements Effective date of registration: 20181204 Granted publication date: 20180626 Pledgee: Jiashan Branch of Industrial and Commercial Bank of China Limited Pledgor: Zhejiang fry new material Limited by Share Ltd Registration number: 2018990001139 |
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