CN109694490A - A kind of changeable colour near ultraviolet cut-off PET film for vehicle window protection - Google Patents
A kind of changeable colour near ultraviolet cut-off PET film for vehicle window protection Download PDFInfo
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- CN109694490A CN109694490A CN201711051108.3A CN201711051108A CN109694490A CN 109694490 A CN109694490 A CN 109694490A CN 201711051108 A CN201711051108 A CN 201711051108A CN 109694490 A CN109694490 A CN 109694490A
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- Prior art keywords
- changeable colour
- near ultraviolet
- vehicle window
- pet film
- window protection
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/14—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 halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The present invention relates to a kind of changeable colour near ultraviolets for vehicle window protection to end PET film, it includes PET base material and the changeable colour near ultraviolet cutoff layer composition for anchoring at substrate single face, changeable colour near ultraviolet cutoff layer is fixed on substrate surface by the polymeric coating layer coating with reflection function, it is assembled using macromolecular structure, control different polymer monomer combinations, initiator amount and initiation conditions, form molecular density gradient difference, and then realize height refringence inside high molecular polymer, realize height index matching, reach the part reflection of 380-450nm wave band, realize the function of near ultraviolet cut-off.Changeable colour near ultraviolet cut-off TPU film of the invention is cheap, simple process, only need to be coated with one layer of polymeric coating layer in substrate surface, be advantageously implemented industrialization；Changeable colour near ultraviolet of the present invention for vehicle window protection ends PET film, with high transparency, excellent ageing-resistant performance, weather resistance.
Description
Technical field
The present invention relates to film applications, in particular to a kind of fenestrated membrane.
Background technique
PET film is glossy because its transparency is good, has good air-tightness and fragrance protectiveness, and excellent mechanical performance resists
Zhang Qiangdu and impact strength；PET film also has excellent heat-resisting, cold resistance and good chemical resistance and oil resistant
Property, it is therefore widely used in the fenestrated membrane of automobile.
Its effect of PET fenestrated membrane includes visual intensity in regulation room, reduces the stimulation to eyes, obstructs the purple in sunlight
The functions such as outside line and infrared ray.Outdoor ray is reduced to enter, can to avoid harm ray to the irradiation of human body, reduce to indoor dress
The possible damage of pool, reduces the injection of infrared ray, can also reduce room temperature, energy saving.Modern fenestrated membrane production technology includes
Roller coating technology or metal sputtering processes etc..Metal sputtering processes are with the high strength of magnetic principles high speed will be golden using electric field
Belong to uniform particle to be sputtered in the PET base material of high-tension, so that it is prepared into magnetron sputtering fenestrated membrane, but due to such film production
Cost is high, is equally difficult to be easily accepted by a user.
The present invention relates to a kind of changeable colour near ultraviolets for vehicle window protection to end PET film, the cut-off of changeable colour near ultraviolet
Layer on substrate surface, is assembled for the polymeric coating layer fixation with reflection function using macromolecular structure, controls different gather
Monomer adduct combination, initiator amount and initiation conditions, form molecular density gradient difference, and then realize in high molecular polymer
Portion's height refringence realizes height index matching, reaches the part reflection of 380-450nm wave band, had both had barrier high energy
The effect of light, at the same can also the place of presentation dazzle beautiful color.
Summary of the invention
In order to overcome the complex process of existing vehicle window protective film, equipment investment is high, low efficiency, higher cost.The present invention relates to
And a kind of changeable colour near ultraviolet for vehicle window protection ends PET film, which ends the letter of PET film technique
Single, at low cost, adhesive force is good, and transparency is high, can reach the part reflection of 380-450nm wave band and can present and dazzles beautiful color.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of changeable colour near ultraviolet for vehicle window protection ends PET film, which is characterized in that it include PET base material with
And anchor at the changeable colour near ultraviolet cutoff layer of substrate single face.The changeable colour near ultraviolet cutoff layer is with reflection function
Polymeric coating layer；PET base material with a thickness of 20-100 μm.
Changeable colour as described above is from different angles it can be seen that different colors, specially partially blue.
Polymeric coating layer as described above includes: the donor or receptor of hydrogen bond, achiral polymerisable monomer, Chiral polymerisable
Monomer and solvent become crosslinking polymer network by polymerization；Further, achiral polymerisable monomer or Chiral polymerisable monomer
It is similar with PET base material structure；The mass percent of the component of achiral polymerisable monomer is between 1~50%wt；Chirality can gather
The constituent mass percentage of monomer is closed between 1~70%wt；The mass percent of the component of solvent is between 1~80%wt；
Further, initiator of the mass percent of component between 0~10%wt is added, accelerates polymerization speed；The matter of component is added
Moistening flatting agent of the percentage between 0.0001~5%wt is measured, the binding ability and film forming of macromolecule and substrate are improved.
The donor or receptor of hydrogen bond as described above, contain amino, imido grpup, nitro, hydroxyl, carboxyl, pyridyl group, piperidines
One or more group in base, isonicotinic acid.
The chiral primitive of Chiral polymerisable monomer as described above is chiral isoamyl alcohol, chiral sec-octyl alcohol, chiral phenyl second
In the chloro- 4- methyl-1-hexanol of glycol, 6-, the bromo- 4- methyl-1 of 6--hexanol, isobide, anhydromannitol and Binaphthol
It is one or more.
Achiral polymerisable monomer or Chiral polymerisable monomer as described above have one or more polymerizable groups, can
Polymer-based group is acryloyl group, methylacryloyl, fluoropropene base, Chloroallyl, trifluoromethyl acrylic, oxetanes
Base, vinyl ether, vinyl ketone base, dimaleoyl imino, phenyl maleimide base, vinyl, styryl, diacetyl
One of base and epoxy group are a variety of.
Initiator as described above is multifunctional initiator and macromole evocating agent, such as crosses ketenes silane acetal, oxidation
Benzoyl, benzoin ethers, benzil ketals class, diaryl iodonium salt, triarylsulfonium salt, diphenyl iodine arsenate, benzene
Ethyl ketone class, benzophenone, 4- methoxyphenyl phenyl-iodide tetrafluoroborate, 4- methoxyphenyl phenyl-iodide hexafluoro phosphonic acids
Salt, 4- tert-butyl-phenyl iodine diphenyl iodine hexafluorophosphonate, 4- methoxyphenyl diphenyl sulfonium tetrahydro phosphonate, triphen
Base sulfonium tetraborate, 4- methoxyphenyl diphenyl sulfonium trifluoromethayl sulfonic acid ester, 4- phenyl thiophenyl diphenyl sulfonium six
One of fluorine arsenate, benzil dimethyl ketal and double-phenylphosphine oxide are a variety of.
Solvent as described above is tetrahydrofuran, acetonitrile, benzene,toluene,xylene, acetone, cyclopropanone, cyclohexanone, toluene
Cyclohexanone, dioxane, ethylene glycol, glycerine, styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether, triethanolamine,
One of hexamethylene, pentane, hexane, octane, ethyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether
Or it is several.It is preferred that having good dissolubility energy boiling point between 60 DEG C -200 DEG C polymer monomer, being non-toxic or low-toxic, corrosion-free
Property, recyclable solvent.
Macromolecule coating fluid as described above further include polymerization inhibitor, defoaming agent, diluent, ultraviolet absorbing agent, alignment agent,
One of surfactant, uv-curable glue and heat-curable glue are a variety of.
Compared with prior art, the invention has the beneficial effects that:
1. manufacture craft of the invention is simple, only it need to be coated with one layer of macromolecule coating fluid in substrate surface, prepared resulting
Changeable colour near ultraviolet ends PET film, has excellent ageing-resistant performance, weather resistance, light transmittance high, nontoxic, is applicable in
Range is wide, with squeezing out, compared with coating process, greatly reduces cost；
2. polymer monomer used in the present invention there are several compositions, two or more molecular density products may be implemented, lead to
It crosses chiral molecule cross-link together, high low-refraction collocation in same high polymer may be implemented, reach 3800-450nm wave band
Part is reflected, and realizes near ultraviolet cutoff function；Realize that the effect of different colours is presented in different angle simultaneously.
Detailed description of the invention
Fig. 1 is the polymerisable monomer structural formula in one embodiment of the invention in macromolecule coating fluid, wherein (a) is hand
Property polymerisable monomer a structural formula, (b) be achiral monomers polymerized monomer a structural formula.
Fig. 2 is the projection spectrogram of the changeable colour near ultraviolet cut-off PET film provided.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
1. the excessively smooth iron plate of tinfoil is put into baking oven first, it is baked to 70-90 DEG C (practical is normally 75-80 DEG C)；
2. 10 parts of 5% nitroaniline is secondly taken, 10 parts of Chiral polymerisable monomer (a), achiral polymerisable monomer (b) 10
Part, 20 parts of PMMA resin microsphere (average grain diameter is 10 microns), initiator crosses 0.6 part, 0.1 part levelling agent of ketenes silane acetal
100 parts, 0.2 part Solvesso150,20 parts of cyclohexanone, toluene curing agent DACH, above-mentioned material stirring is uniformly mixed, and is made
Anti-blue light macromolecule coating fluid is controlled wet-film thickness as 2-20 μm and is uniformly coated on 50 with RDS4# bar (10 μm of wet film gap)
μm the PET without any HC or primer on；
3. wet film is put on baking oven tinfoil or iron plate after the completion of coating, solvent is removed to 1min within baking 15 seconds.Due to
There are hydrogen bond action between chiral polymerized monomer and nitroaniline, Chiral polymerisable monomer molecule is migrated to nitrobenzene amine layer, with
Other polymerized monomers form concentration gradient, and then form pitch gradient；
4. finally taking the film out by 40mj/cm2-800mj/cm2UV curing, fixed pitch gradient obtains anti-blue light
Film tests its performance.Transmitted light spectrogram is as shown in Figure 2.
It is finally noted that the purpose for publicizing and implementing mode is to help to further understand the present invention, but ability
The technical staff in domain is understood that without departing from the spirit and scope of the invention and the appended claims, various replacements and
Modification is all possible.Therefore, the present invention should not be limited to embodiment disclosure of that, the scope of protection of present invention with
Subject to the range that claims define.
Claims (9)
1. the present invention relates to a kind of changeable colour near ultraviolets for vehicle window protection to end PET film, which is characterized in that it includes
PET base material and the changeable colour near ultraviolet cutoff layer for anchoring at substrate single face, the changeable colour near ultraviolet cutoff layer are tool
There is the polymeric coating layer of reflection function；PET base material with a thickness of 20-100 μm.
2. a kind of changeable colour near ultraviolet for vehicle window protection according to claim 1 ends PET film, feature exists
In: the changeable colour is from different angles it can be seen that different colors, specially partially blue.
3. a kind of changeable colour near ultraviolet for vehicle window protection according to claim 1 ends PET film, feature exists
In: the polymeric coating layer include: the donor or receptor of hydrogen bond, achiral polymerisable monomer, Chiral polymerisable monomer and molten
Agent becomes crosslinking polymer network by polymerization；Further, achiral polymerisable monomer or Chiral polymerisable monomer and PET base
Material structure is similar；The mass percent of the component of achiral polymerisable monomer is between 1~50%wt；Chiral polymerisable monomer
Constituent mass percentage is between 1~70%wt；The mass percent of the component of solvent is between 1~80%wt；Further, add
Enter initiator of the mass percent of component between 0~10%wt, accelerates polymerization speed；The mass percent that component is added exists
Moistening flatting agent between 0.0001~5%wt improves the binding ability and film forming of macromolecule and substrate.
4. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The donor or receptor of the hydrogen bond, containing in amino, imido grpup, nitro, hydroxyl, carboxyl, pyridyl group, piperidyl, isonicotinic acid
One or more group.
5. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The chiral primitive of the Chiral polymerisable monomer is chiral isoamyl alcohol, chiral sec-octyl alcohol, chiral styrene glycol, the chloro- 4- first of 6-
One or more of the bromo- 4- methyl-1 of base -1- hexanol, 6--hexanol, isobide, anhydromannitol and Binaphthol.
6. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The achiral polymerisable monomer or Chiral polymerisable monomer have one or more polymerizable groups, and polymerizable groups are propylene
Acyl group, methylacryloyl, fluoropropene base, Chloroallyl, trifluoromethyl acrylic, oxetanyl, vinyl ether, ethylene
One in base ketone base, dimaleoyl imino, phenyl maleimide base, vinyl, styryl, diacetyl and epoxy group
Kind is a variety of.
7. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The initiator is multifunctional initiator and macromole evocating agent, such as crosses ketenes silane acetal, Benzoyl Oxide, benzoin
Ethers, benzil ketals class, diaryl iodonium salt, triarylsulfonium salt, diphenyl iodine arsenate, acetophenones, hexichol first
Ketone, 4- methoxyphenyl phenyl-iodide tetrafluoroborate, 4- methoxyphenyl phenyl-iodide hexafluorophosphonate, 4- tert-butyl benzene
Base iodine diphenyl iodine hexafluorophosphonate, 4- methoxyphenyl diphenyl sulfonium tetrahydro phosphonate, triphenylsulfonium tetraboric acid
Salt, 4- methoxyphenyl diphenyl sulfonium trifluoromethayl sulfonic acid ester, 4- phenyl thiophenyl diphenyl sulfonium hexafluoro arsenate, benzene are even
One of acyl dimethyl ketal and double-phenylphosphine oxide are a variety of.
8. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The solvent is tetrahydrofuran, acetonitrile, benzene,toluene,xylene, acetone, cyclopropanone, cyclohexanone, toluene cyclohexanone, dioxy six
Ring, ethylene glycol, glycerine, styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether, triethanolamine, hexamethylene, pentane,
One or more of hexane, octane, ethyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether.It is preferred that
There is good dissolubility energy boiling point between 60-200 DEG C polymer monomer, is non-toxic or low-toxic, non-corrosive, is recyclable molten
Agent.
9. a kind of changeable colour near ultraviolet for vehicle window protection ends PET film according to claim 3, it is characterised in that:
The macromolecule coating fluid further include polymerization inhibitor, defoaming agent, diluent, ultraviolet absorbing agent, alignment agent, surfactant,
One of uv-curable glue and heat-curable glue are a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711051108.3A CN109694490A (en) | 2017-10-23 | 2017-10-23 | A kind of changeable colour near ultraviolet cut-off PET film for vehicle window protection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711051108.3A CN109694490A (en) | 2017-10-23 | 2017-10-23 | A kind of changeable colour near ultraviolet cut-off PET film for vehicle window protection |
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| Publication Number | Publication Date |
|---|---|
| CN109694490A true CN109694490A (en) | 2019-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711051108.3A Withdrawn CN109694490A (en) | 2017-10-23 | 2017-10-23 | A kind of changeable colour near ultraviolet cut-off PET film for vehicle window protection |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116970408A (en) * | 2023-08-03 | 2023-10-31 | 武汉轻工大学 | Polymer network liquid crystal material for microwaves and preparation method thereof |
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| CN105425327A (en) * | 2015-12-10 | 2016-03-23 | 北京海川利元材料科技有限公司 | Cholesteric liquid crystal and reflective-type circular polarization sheet thereof, and manufacturing method |
| CN106218172A (en) * | 2016-08-30 | 2016-12-14 | 常州山由帝杉防护材料制造有限公司 | Photochromic fenestrated membrane |
| JP2017159590A (en) * | 2016-03-10 | 2017-09-14 | 日本ゼオン株式会社 | Assembly and composite assembly |
-
2017
- 2017-10-23 CN CN201711051108.3A patent/CN109694490A/en not_active Withdrawn
Patent Citations (4)
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| CN104592876A (en) * | 2015-01-05 | 2015-05-06 | 南京攀腾科贸有限公司 | Efficient blue ray-proof PET (Polyethylene terephthalate) clear paint and preparation method thereof |
| CN105425327A (en) * | 2015-12-10 | 2016-03-23 | 北京海川利元材料科技有限公司 | Cholesteric liquid crystal and reflective-type circular polarization sheet thereof, and manufacturing method |
| JP2017159590A (en) * | 2016-03-10 | 2017-09-14 | 日本ゼオン株式会社 | Assembly and composite assembly |
| CN106218172A (en) * | 2016-08-30 | 2016-12-14 | 常州山由帝杉防护材料制造有限公司 | Photochromic fenestrated membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116970408A (en) * | 2023-08-03 | 2023-10-31 | 武汉轻工大学 | Polymer network liquid crystal material for microwaves and preparation method thereof |
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Application publication date: 20190430 |