CN103009756B - With compound substrate membranes and the manufacture method thereof of surperficial solidified coating - Google Patents
With compound substrate membranes and the manufacture method thereof of surperficial solidified coating Download PDFInfo
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- CN103009756B CN103009756B CN201210526949.6A CN201210526949A CN103009756B CN 103009756 B CN103009756 B CN 103009756B CN 201210526949 A CN201210526949 A CN 201210526949A CN 103009756 B CN103009756 B CN 103009756B
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Abstract
With compound substrate membranes and the manufacture method thereof of surperficial solidified coating, comprise basement membrane, be arranged on epilamellar solidified coating, its special feature is 1. prepolymer 35-60 weight portions 2, reactive diluent 40-90 weight portions 3, light trigger 0.1-10 weight portion 4, levelling agent 0.2-5 weight portion, the manufacture method of the above-mentioned compound substrate membranes with surperficial solidified coating comprises being coated with paving solidified coating process toward membrane surface, process is cured to solidified coating, being cured process to solidified coating is use electron beam, gamma-rays, one in neutron beam or the particle beams carries out crosslinking with radiation to solidified coating.Compared with the prior art, the face coat scratch resistance performance with compound substrate membranes is good, can carry out second heat processing and forming, the solidification of face coat is by the advantage that thermal sensitivity and the efficiency of basement membrane itself affect in the present invention.
Description
Technical field
The present invention relates to a kind of technology of composite plastic.
Background technology
Modern industrialization process for modifying surface mainly still adopts the method for single-piece coating, coating is implemented mainly to brush or spraying, the modal japanning as furniture wood product surface, the method that this type of mode adopts is because the covering with paint of single products, it is low to there is utilization efficiency of coatings in the coating of single products, the unfavorable factors such as coating duration is long, and hardening time is long.Over nearly two, 30 years, surface coating modification technology rises just gradually, gradually monomer product coating method is substituted, the japanning of wherein classical case such as furniture replaced by furniture decoration Modified Membrane, the spraying coating process of notebook computer appearance replaced by pad pasting in mould (also claiming " ripple in mould film ") technique, realizes the object of quick, environmental protection, low-carbon (LC).
The coating that single products coating adopts generally can adopt thermosetting resin, therefore often there is excellent physical property, and the film base material that overlay film modified technique adopts is owing to must meet the enforcement of coating technique, it can only be a kind of flexible material, generally adopt conventional thermoplastic material, and thermoplastic in scratch resistance, the performance such as heat-resisting not as thermosetting resin, therefore particularly high-end product, thermoplastic flexible covering film material must adopt composite, just can reach requirement by surface modification.
The surface treatment means of the film base material material that overlay film process for modifying surface is used are mainly divided into two large classes, one class is hardened to the top layer of basement membrane itself, and the outer major part maintenance of basement membrane skim-coat does not change substantially, to keep flexible, can be used for coating technique, another kind of, be that compound skim coating modified layer is carried out on the surface of basement membrane.This and single workpiece are coated with unlike adopting serialization to apply completely, and coated weight is very low.
Although basement membrane case-hardening technology own is having certain research in recent years, maturity is lower, and there is the more scabrous problems such as color changes greatly.Have again a kind of similar pattern to be the mode as PET film adopting surface laminating scratch-resistant, but this mode exist and second heat processing and forming defect and double-layer films cannot occur being separated the material risk of (layering), also causes its scope of application narrower.
The top layer of compound substrate membranes adopts coating applications technology to be then comparatively ripe technology, and conventional basement membrane top layer coating technique refers to the coating material solidified technology of carrying out being coated with of UV adopting volatile paint or heat reactivity coating and coming into vogue.But conventional and coating technique exists the not enough or UV solidification brittleness of scratch resistance performance too greatly cannot the problem such as secondary operations, and the thermal sensitivity of basement membrane itself and efficiency also limit the development of conventional coating techniques.
Summary of the invention
The compound substrate membranes with surperficial solidified coating that goal of the invention of the present invention is that the face coat scratch resistance performance providing a kind of compound substrate membranes is good, can carries out second heat processing and forming, the solidification of face coat does not affect by thermal sensitivity and the efficiency of basement membrane itself and manufacture method thereof.
The present invention is achieved in that with the compound substrate membranes of surperficial solidified coating and comprises basement membrane, is arranged on epilamellar solidified coating, and its special feature is
1. prepolymer 35-60 weight portion
2, reactive diluent 40-90 weight portion
3, light trigger 0.1-10 weight portion
4, levelling agent 0.2-5 weight portion
Wherein, prepolymer is one or more in polyester based prepolymers, unsaturated polyester type prepolymer, acrylic ester type prepolymer, polyurethane-type prepolymer, polyether based prepolymers,
Reactive diluent is one or more in mono-functional reactive's diluent, polyfunctional group reactive diluent and vinyl ethers reactive diluent,
Light trigger is one or more in acetoxyl type initator, visible light photo initiators, Polymeric photoinitiators, water-soluble light trigger, dual initiator system initator,
The solidification of solidified coating uses the one in electron beam, gamma-rays, neutron beam or the particle beams to carry out crosslinking with radiation to solidified coating to form.
Prepolymer is acrylic ester type prepolymer.
Acrylic ester type prepolymer is one or more in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic resin prepolymer.
When prepolymer is epoxy acrylate, epoxy acrylate be bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates, epoxidized oil acrylate, acid and anhydride-modified propylene's acid esters in one or more.
When prepolymer is polyester acrylate, polyester acrylate is one or more in aromatic urethane acrylate, aliphatic urethane acrylate, polyether backbone urethane acrylate, polyester backbone urethane acrylate, polyolefin structure urethane acrylate, polysiloxane backbone urethane acrylate.
Reactive diluent is made up of the bisphenol a diacrylate of 1 of 20-50 weight portions, 6 hexanediyl ester and 20-40 weight portion.
1. prepolymer
Prepolymer can comprise polyester-type, unsaturated polyester type, acrylic ester type, polyurethane-type, polyether-type, more optimizedly acrylic ester type prepolymer in electronic beam curing.Acrylic polymer can be epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic resin prepolymer.Described epoxy acrylate includes but not limited to: bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates, epoxidized oil acrylate, acid and anhydride-modified propylene's acid esters; Described urethane acrylate includes but not limited to aromatic urethane acrylate, aliphatic urethane acrylate, polyether backbone urethane acrylate, polyester backbone urethane acrylate, polyolefin structure urethane acrylate, polysiloxane backbone urethane acrylate.The coating hardness synthesized by aromatic urethane acrylate, toughness, wearability are all better, but weatherability is poor, are not suitable for outdoor products and use; Aliphatic urethane acrylate cured film pliability is good, good weatherability.
2, reactive diluent
Reactive diluent, except for adjusting except system viscosity and impact construction rheological characteristic, also has the impact of the following aspects: reactive diluent is the same with prepolymer is one of principal element affecting system solidification rate; Reactive diluent is also one of film forming matter, directly affects the final performance of coating; Reactive diluent couples together formation cross-linked network HMW prepolymer molecule, and the diluent of polyfunctionality all can be easy to form cross-linked network.
Reactive diluent has mono-functional reactive's diluent, polyfunctional group reactive diluent and vinyl ethers reactive diluent.The curing rate of monofunctional diluent is slower than polyfunctional group diluent, and polyfunctional group diluent activity is higher, and functional group is higher, and reactive diluent viscosity is larger.
1,6 hexanediyl esters are a kind of bifunctional monomers, its advantage is: dilution capacity is strong, greatly active and viscosity is low, nonirritant, oral toxicity are low, due to 1, the main body of 6 hexanediyl esters is normal carbon chains, thus can provide best combination property in flexibility, adhesive force, activity and toughness etc.This secondary operations can provide precondition for cured film.
Bisphenol a diacrylate is also a kind of bifunctional monomer, smell and excitant little, the excellent film forming matter that quick solidifying is a kind of strong adhesion, mar-proof and wearability is good.
3, light trigger
Light trigger is optional composition in electronic beam curing.Light trigger contained by general curing system is all excessive, and initator remaining after illumination can decompose further out of doors and cause the reactions such as crosslinked, degraded, thus makes coating turn yellow, become fragile, and reduces the performance of film.But consider oxygen inhibition problem in radiation curing, in the present invention, also add the solution that light trigger is beneficial to oxygen inhibition problem.More novel initator comprises acetoxyl type initator, visible light photo initiators, Polymeric photoinitiators, water-soluble light trigger, dual initiator system.The present invention uses comparatively novel acetoxyl type light trigger, and this initator volatility is lower, and after illumination, produce benzoyl and phosphinylidyne free radical, can initiated polymerization, and photo-curing rate is fast, and after illumination, residual initiators is almost nil.
The manufacture method of the above-mentioned compound substrate membranes with surperficial solidified coating of the present invention realizes like this, comprise and be coated with paving solidified coating process toward membrane surface, be cured process to solidified coating, being cured process to solidified coating is use the one in electron beam, gamma-rays, neutron beam or the particle beams to carry out crosslinking with radiation to solidified coating.
When carrying out crosslinking with radiation, preferably use electron beam.
Use electron beam to carry out radiation curing, doses of electron beam radiation is very important influence factor.The performance of obtained solidified coating can be controlled by doses of electron beam radiation.The dose of radiation of electron beam of the present invention is 1-150kGy.
Compared with conventional UV-curing technology, except the face coat scratch resistance performance with compound substrate membranes is good, second heat processing and forming can be carried out, the solidification of face coat do not affect by the thermal sensitivity of basement membrane itself and efficiency, can be used for except the built-in fitting surface modification covering materials such as automobile, high ferro, aircraft, IT, the present invention also has following beneficial effect:
(1), compared with electronic beam curing solidifies with UV, coating does not limit by color, and thickness also just depends on accelerating potential
(2), electronic beam curing relatively thoroughly evenly, there is not the residual of uncured thing
(3), can not to add in electronic beam curing or trace adds light trigger, cost is lower
(4), electronic beam curing energy consumption is lower, is about 5% of UV solidification.
Detailed description of the invention:
Now the present invention is described in further detail in conjunction with the embodiments:
Compound substrate membranes with surperficial solidified coating of the present invention comprises basement membrane, is arranged on epilamellar solidified coating, and its special feature is
1. prepolymer 35-60 weight portion
2, reactive diluent 40-90 weight portion
3, light trigger 0.1-10 weight portion
4, acrylate levelling agent 0.2-5 weight portion
Wherein, prepolymer is more than one in polyester based prepolymers, unsaturated polyester type prepolymer, acrylic ester type prepolymer, polyurethane-type prepolymer, polyether based prepolymers,
Reactive diluent is more than one in mono-functional reactive's diluent, polyfunctional group reactive diluent and vinyl ethers reactive diluent,
Light trigger is more than one in acetoxyl type initator, visible light photo initiators, Polymeric photoinitiators, water-soluble light trigger, dual initiator system initator,
The solidification of solidified coating uses the one in electron beam, gamma-rays, neutron beam or the particle beams to carry out crosslinking with radiation to solidified coating to form.
Prepolymer is acrylic ester type prepolymer.
Acrylic ester type prepolymer is more than one in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic resin prepolymer.
When prepolymer is epoxy acrylate, epoxy acrylate be bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates, epoxidized oil acrylate, acid and anhydride-modified propylene's acid esters in more than one.
When prepolymer is polyester acrylate, polyester acrylate is more than one in aromatic urethane acrylate, aliphatic urethane acrylate, polyether backbone urethane acrylate, polyester backbone urethane acrylate, polyolefin structure urethane acrylate, polysiloxane backbone urethane acrylate.
Reactive diluent is made up of the bisphenol a diacrylate of 1 of 20-50 weight portions, 6 hexanediyl ester and 20-40 weight portion.
The manufacture method of the above-mentioned compound substrate membranes with surperficial solidified coating of the present invention realizes like this, comprise and be coated with paving solidified coating process toward membrane surface, be cured process to solidified coating, being cured process to solidified coating is use the one in electron beam, gamma-rays, neutron beam or the particle beams to carry out crosslinking with radiation to solidified coating.
When carrying out crosslinking with radiation, preferably use electron beam.
Use electron beam to carry out radiation curing, doses of electron beam radiation is very important influence factor.The performance of obtained solidified coating can be controlled by doses of electron beam radiation.The dose of radiation of electron beam of the present invention is 1-150kGy.
Below for the formula of the solidified coating of 8 examples selected in embodiment and after the formula of the solidified coating of 4 examples is coated on film, the surface property parameter after solidification and result display.
Embodiment:
Table 1 Example formulations forms
Solidified coating is coated on film, carries out test plastics sucking moulding with after 10kGy, 60kGy, 100kGy, 150kGy radiation curing.Carry out molding effect to the film obtained, case hardness compares, and result is as shown in table 2.
Table 2 test experiments result
Can show from table 2 result, be cured through different dose of radiations, case hardness and the pliable and tough seriousness of coating all change.Wherein case hardness adopts pencil hardness test to characterize.
Table 2 result shows, and uses the aliphatic urethane acrylate of polycarbonate backbone as prepolymer in 4 embodiments, and performance other prepolymers relative of coating more meet the requirement that I takes charge of product.Choose the aliphatic urethane acrylate of polycarbonate backbone as prepolymer, 4 embodiments are as shown in table 3:
Table 3 Example formulations forms
Solidified coating is coated on film, carries out test plastics sucking moulding with after 60kGy radiation curing.Carry out molding effect to the film obtained, case hardness compares, and result is as shown in table 4.
Table 4 test experiments result
Claims (8)
1., with the compound substrate membranes of surperficial solidified coating, it is characterized in that comprising basement membrane, being arranged on epilamellar solidified coating, solidified coating comprises
Prepolymer 35-60 weight portion
Reactive diluent 40-90 weight portion
Light trigger 0.1-10 weight portion
Levelling agent 0.2-5 weight portion
Wherein, prepolymer be comprise in the polyester based prepolymers of unsaturated polyester type prepolymer, acrylic ester type prepolymer, polyurethane-type prepolymer, polyether based prepolymers more than one,
Reactive diluent is mono-functional reactive's diluent, comprise in the polyfunctional group reactive diluent of vinyl ethers reactive diluent more than one,
Light trigger is more than one in acetoxyl type initator, visible light photo initiators, Polymeric photoinitiators, water-soluble light trigger, dual initiator system initator,
The solidification of solidified coating uses the one in electron beam, gamma-rays, neutron beam to carry out crosslinking with radiation to solidified coating to form,
Reactive diluent is made up of the bisphenol a diacrylate of 1 of 20-50 weight portions, 6 hexanediyl ester and 20-40 weight portion.
2. the compound substrate membranes with surperficial solidified coating according to claim 1, what it is characterized in that adopting in prepolymer is acrylic ester type prepolymer.
3. the compound substrate membranes with surperficial solidified coating according to claim 2, is characterized in that acrylic ester type prepolymer is more than one acrylic resin prepolymers in epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate.
4. the compound substrate membranes with surperficial solidified coating according to claim 3, when it is characterized in that prepolymer is epoxy acrylate, epoxy acrylate is more than one in bisphenol A epoxy acrylate, Epoxy Phenolic Acrylates, epoxidized oil acrylate.
5. the compound substrate membranes with surperficial solidified coating according to claim 3, it is characterized in that including in prepolymer in aromatic urethane acrylate, aliphatic urethane acrylate, polyether backbone urethane acrylate, polyester backbone urethane acrylate, polyolefin structure urethane acrylate, polysiloxane backbone urethane acrylate more than one.
6. the manufacture method of the compound substrate membranes with surperficial solidified coating according to claim 1 or 2 or 3 or 4 or 5, it is characterized in that comprising and be coated with paving solidified coating process toward membrane surface, be cured process to solidified coating, being cured process to solidified coating is use the one in electron beam, gamma-rays, neutron beam to carry out crosslinking with radiation to solidified coating.
7. the manufacture method of the compound substrate membranes with surperficial solidified coating according to claim 6, when it is characterized in that carrying out crosslinking with radiation, uses electron beam.
8. the manufacture method of the compound substrate membranes with surperficial solidified coating according to claim 7, is characterized in that the dose of radiation of electron beam is 1-150kGy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104293167B (en) * | 2014-10-28 | 2016-10-26 | 成都纳硕科技有限公司 | The high rigidity of a kind of PVC floor tile, high glaze ultraviolet-curing paint |
| CN105440933B (en) * | 2015-02-15 | 2018-10-09 | 广东天安新材料股份有限公司 | Electron beam curable coatings |
| CN106188599A (en) * | 2016-08-12 | 2016-12-07 | 苏州柯创电子材料有限公司 | A kind of high-performance double-layer PET film |
| CN107880767A (en) * | 2017-12-20 | 2018-04-06 | 广东德新科技孵化器有限公司 | A kind of scrubbable ultraviolet-cured furniture coating and preparation method thereof |
| CN110315832A (en) * | 2018-03-31 | 2019-10-11 | 孙学民 | A kind of weather-proof compact-panel of outdoor use and preparation method thereof |
| CN114196349A (en) * | 2021-12-14 | 2022-03-18 | 广州市金万正印刷材料有限公司 | Radiation-formed release liner with exhaust function and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845243A (en) * | 2009-03-28 | 2010-09-29 | 恒昌涂料（惠阳）有限公司 | Low-energy electron beam radiation curing coating and use method thereof |
| CN102140155A (en) * | 2010-02-02 | 2011-08-03 | 湖南鸿海新材料有限公司 | Ultraviolet light or electron beam-cured resin composition for blue-ray disc |
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| US7226637B2 (en) * | 2000-01-18 | 2007-06-05 | D Data Inc. | Manufacturing method for multilayer fluorescent information carriers |
| US6470128B1 (en) * | 2001-03-30 | 2002-10-22 | Alcatel | UV-curable coating composition for optical fiber for a fast cure and with improved adhesion to glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845243A (en) * | 2009-03-28 | 2010-09-29 | 恒昌涂料（惠阳）有限公司 | Low-energy electron beam radiation curing coating and use method thereof |
| CN102140155A (en) * | 2010-02-02 | 2011-08-03 | 湖南鸿海新材料有限公司 | Ultraviolet light or electron beam-cured resin composition for blue-ray disc |
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Application publication date: 20130403 Assignee: Guangdong Yaoda Financial Leasing Co., Ltd Assignor: GUANGDONG TIANAN NEW MATERIAL Co.,Ltd. Contract record no.: X2020980005499 Denomination of invention: Composite base film with surface curing coating and its manufacturing method Granted publication date: 20151118 License type: Exclusive License Record date: 20200828 |
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Denomination of invention: Composite base film with surface curing coating and its manufacturing method Effective date of registration: 20200904 Granted publication date: 20151118 Pledgee: Guangdong Yaoda Financial Leasing Co., Ltd Pledgor: GUANGDONG TIANAN NEW MATERIAL Co.,Ltd. Registration number: Y2020980005712 |