CN117050636A - Explosion-proof functional coating and preparation method and application thereof - Google Patents
Explosion-proof functional coating and preparation method and application thereof Download PDFInfo
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- CN117050636A CN117050636A CN202210487474.8A CN202210487474A CN117050636A CN 117050636 A CN117050636 A CN 117050636A CN 202210487474 A CN202210487474 A CN 202210487474A CN 117050636 A CN117050636 A CN 117050636A
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- 238000000576 coating method Methods 0.000 title claims abstract description 140
- 239000011248 coating agent Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 25
- -1 photoinitiator Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000001723 curing Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 22
- 239000004645 polyester resin Substances 0.000 claims description 15
- 229920001225 polyester resin Polymers 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 12
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 238000003848 UV Light-Curing Methods 0.000 claims description 6
- 238000013007 heat curing Methods 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000007888 film coating Substances 0.000 abstract description 5
- 238000009501 film coating Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 10
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 208000008918 voyeurism Diseases 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an explosion-proof functional coating, a preparation method and application thereof, wherein the preparation raw materials of the explosion-proof functional coating comprise a component A and a component B, the component A comprises multifunctional acrylate resin, thermosetting resin, photoinitiator, solvent and auxiliary agent, and the component B comprises curing agent; the weight portion of the thermosetting resin is 0.8-3 times of the weight portion of the multifunctional acrylate resin. The explosion-proof functional coating has good toughness (a single paint film is arbitrarily bent at 360 degrees and is not broken), has good adhesion to glass (the surface hardness of the hardened coating can reach 5B before and after water boiling), can greatly improve the surface hardness of the hardened coating after film coating (pencil hardness is improved from HB to 4H), and can improve the impact resistance of UTG (the pen-down height of UTG after film coating is improved from 0.5cm to 4-5 cm).
Description
Technical Field
The invention belongs to the technical field of preparation and application of functional coatings, and particularly relates to an explosion-proof functional coating, a preparation method and application thereof, in particular to a high-toughness explosion-proof functional coating, and a preparation method and application thereof.
Background
With the development of display technology, various performance requirements on a screen body in a display device are gradually increased, and with the expansion of application scenes, the ultrathin glass-based flexible display panel can be applied to foldable mobile phones, notebook computers and various curled display devices. Although the ultrathin glass substrate has the advantages of good touch feeling and the like, the impact resistance mechanical property is relatively poor, for example, the drop performance and the ball drop performance can be obviously reduced along with the reduction of the thickness of the bendable ultrathin glass (UTG).
In view of the above-mentioned drawbacks. UTG is coated with an impact-resistant coating or subjected to film pasting treatment to improve impact resistance, but after common organic coating is coated or pasted, the surface hardness and scratch resistance of UTG are greatly reduced, the plastic feel is strong, the hand feeling is poor, and the advantages of high hardness, high scratch resistance and good hand feeling of glass are lost.
At this time, the surface of the impact-resistant Coating needs to be coated with a hardening Coating (Hard Coating), but the hardness is lower when the conventional thermosetting impact-resistant Coating or primer is thick (more than or equal to 30 um), the supporting force of the hardening Coating on the surface is weak, so that the pencil hardness of the surface is low when the hardening Coating is tested (the hardness of the hardening liquid can reach 5-7H when the hardening liquid is directly coated on glass, but the hardness of the conventional impact-resistant Coating or primer is generally HB only because the substrate is soft, the thickness of the hardening liquid is only 3-7 mu m, and the hardening liquid is easy to crush by pencil gravity.
The high-functionality UV (ultraviolet light curing) coating has high surface hardness, the highest pencil hardness can reach 6H, but the higher the hardness is, the worse the flexibility is, the weak adhesion to glass is, the explosion-proof function is not provided, and UTG is easy to splash when damaged, so that safety accidents are caused.
CN109266237a discloses a flexible explosion-proof film for peeping prevention, which comprises a flexible film, wherein the upper surface of the flexible film is sequentially provided with a protective layer and a high refractive index hardening layer from top to bottom; the anti-peeping layer, the organic silicon pressure-sensitive adhesive layer and the release layer are sequentially arranged on the lower surface of the flexible film from top to bottom, wherein parallel hexagonal lines are arranged on the surface of the anti-peeping layer, the side length of each parallel hexagonal line is 3mm, the line width is 2 mu m, the line depth is 3 mu m, the included angle between the straight edge and the inclined edge is 120 degrees, and the included angle between the inclined edge and the inclined edge is 60 degrees; the peep-proof layer is made of polyurethane material mixed with phthalocyanine pigment. The anti-peeping flexible explosion-proof film has very high flexibility, can play a role in better buffering in the mobile phone falling process, has a wide application range, and can be suitable for various electronic screens, in particular 2.5D and 3D cambered surface screens. However, the hardness of the rupture disk of the present invention is still further improved.
In summary, when the surface of UTG is coated, the selection of the coating is very critical, so that the development of the coating with high hardness, good toughness and explosion-proof function is very important.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an explosion-proof functional coating, and a preparation method and application thereof. The explosion-proof functional coating adopts a dual-curing system, integrates the advantages of high hardness of the UV coating, good adhesiveness to glass, good flexibility and explosion-proof function of the thermosetting coating, and therefore, the explosion-proof functional coating has strong supporting effect on hardening liquid, and the hardening coating is not easy to be crushed by a pencil during testing, so that the measured hardness is low.
The explosion-proof functional coating can be directly coated on the surface of the treated glass, has good supporting effect on the upper hardening liquid coating, and the maximum pencil hardness of the hardening liquid coating can reach 4H.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an explosion-proof functional coating, wherein the preparation raw materials of the explosion-proof functional coating comprise an A component and a B component, the A component comprises multifunctional acrylate resin, thermosetting resin, photoinitiator, solvent and auxiliary agent, and the B component comprises a curing agent;
the weight part (solid part) of the thermosetting resin is 0.8-3 times that of the multifunctional acrylate resin, for example 0.8 times, 1.2 times, 1.3 times, 1.5 times, 1.8 times, 2 times, 2.2 times, 2.3 times, 2.5 times, 2.8 times or 3 times, and the like.
The explosion-proof functional coating uses the multifunctional acrylate resin and the thermosetting resin to be matched and used together as the matrix resin, and the multifunctional acrylate resin is cured by ultraviolet light (UV curing) and has the advantages of high functionality, high crosslinking degree, high hardness of the cured coating, poor flexibility and general adhesive force to glass; the thermosetting resin has good flexibility, good adhesion to glass and explosion-proof function, and the composite performance of the prepared explosion-proof functional coating is better through the composite use of the two resins.
If the amount of the thermosetting resin is too small, the coating hardness is high, but the explosion resistance is reduced, and the adhesion to glass is correspondingly reduced, and if the amount of the multifunctional acrylate resin is too small, the coating explosion resistance and the adhesion to glass are better, but the hardness is improved slightly.
Preferably, the multifunctional acrylate resin includes any one or a combination of at least two of trifunctional acrylate resin, tetrafunctional acrylate resin, pentafunctional acrylate resin, hexafunctional acrylate resin, heptafunctional acrylate resin, octafunctional acrylate resin, nonafunctional acrylate resin, decafunctional acrylate resin, undecfunctional acrylate resin, dodecafunctional acrylate resin, tridecyl functional acrylate resin, tetradecfunctional acrylate resin, or pentadecyl functional acrylate resin, preferably hexafunctional acrylate resin.
As a preferable technical scheme of the invention, when the multifunctional acrylate resin is hexafunctional acrylate resin, the prepared explosion-proof functional coating has better performance, wide raw materials and low price. If the functionality of the multifunctional acrylate resin is lower, the hardness of the explosion-proof functional coating is improved slightly; if the functionality of the multifunctional acrylate resin is too high, the brittleness of the explosion-proof functional coating is too high, the explosion-proof function is lost, and the adhesion to glass is low.
In the present invention, the multifunctional acrylate resin may be replaced with a multifunctional acrylate monomer, and when the multifunctional acrylate monomer is used, a solvent may not be used in the system.
Preferably, the multifunctional acrylate monomer includes any one or a combination of at least two of a trifunctional acrylate monomer, a tetrafunctional acrylate monomer, a pentafunctional acrylate monomer, or a hexafunctional acrylate monomer.
Preferably, the thermosetting resin comprises a hydroxyacrylate and/or a saturated polyester resin, preferably a saturated polyester resin.
As a preferable technical scheme of the invention, when the thermosetting resin is saturated polyester resin, the resin has higher hardness after reacting with the curing agent, good adhesion to glass and a certain explosion-proof function.
Preferably, the curing agent comprises any one or a combination of at least two of hexamethylene diisocyanate trimer (HDI trimer), hexamethylene diisocyanate biuret (HDI biuret), 4' -dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI) or isophorone diisocyanate trimer.
Preferably, the photoinitiator comprises any one or a combination of at least two of 1-hydroxycyclohexyl phenyl ketone (184), ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate (TPO), or 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173).
Preferably, the solvent comprises any one or a combination of at least two of ethyl acetate, butyl acetate, cyclohexanone, ethylene glycol ethyl ether acetate or methyl isobutyl ketone.
Preferably, the auxiliary agent comprises a leveling agent and/or a drier.
Preferably, the leveling agent comprises a silicone leveling agent.
Preferably, the drier comprises an organotin drier and/or an organobismuth drier.
Preferably, the weight fraction of the curing agent is 10-50%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the weight fraction of the thermosetting resin.
Preferably, the weight portion of the photoinitiator is 2-5%, such as 2%, 3%, 4% or 5% of the weight portion of the multifunctional acrylate resin.
Preferably, the solvent is 0.5 to 2 times, for example 0.5 times, 1 time, 1.5 times or 2 times, etc. the total weight of the multifunctional acrylate resin and the thermosetting resin.
Preferably, the weight portion of the leveling agent is 0.1% -1% of the total weight portion of the multifunctional acrylate resin and the thermosetting resin, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.
Preferably, the weight fraction of the drier is 0-0.1% of the thermosetting resin, for example 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% or 0.1% etc.
In a second aspect, the present invention provides a method for preparing the explosion-proof functional coating according to the first aspect, the method comprising the following steps:
(1) Under the yellow light environment, dissolving a photoinitiator in a solvent, stirring uniformly, adding an auxiliary agent, continuously stirring, then adding a multifunctional acrylate resin and a thermosetting resin, uniformly mixing to obtain a component A, and mixing the component A with the component B when in use, and carrying out vacuum defoaming to obtain the functional coating;
(2) And (3) coating the functional coating on the surface of the bendable ultrathin glass (UTG), and performing Ultraviolet (UV) curing after heat curing to obtain the explosion-proof functional coating.
Preferably, the surface of the bendable ultrathin glass is treated by an amino coupling agent.
Preferably, the heat curing is carried out at a curing temperature of 80-95 ℃, for example 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, or the like, for a curing time of 1-2 hours, for example 1 hour, 1.5 hours, 2 hours, or the like.
Preferably, the UV curing adopts mercury lamp curing, and the accumulated energy of the UV curing is 800-1200mJ/cm 2 For example 800mJ/cm 2 、850mJ/cm 2 、900mJ/cm 2 、950mJ/cm 2 、1000mJ/cm 2 、1050mJ/cm 2 、1100mJ/cm 2 、1150mJ/cm 2 Or 1200mJ/cm 2 Etc. In a third aspect, the invention provides the explosion-proof functional coating of the first aspect, which is mainly used for coating a film on the surface of UTG bendable glass, can greatly improve the hardness of hardening liquid on the coating, and has the explosion-proof and impact-resistant functions.
Compared with the prior art, the invention has at least the following beneficial effects:
the multifunctional acrylate resin and the thermosetting resin are matched to be used together as the matrix resin, so that the prepared explosion-proof functional coating has good comprehensive performance.
(1) The explosion-proof functional coating has good adhesion with glass, and the hundred grid tests before and after water boiling can reach 5B; in the film pasting product in the prior art, the film material is pasted with glass by adopting an OCA adhesive, the adhesive force of the film material is poor, and the film material turns white after being soaked in water;
(2) The explosion-proof functional coating adopts a dual-curing (UV curing and heat curing) system, wherein the UV component has higher hardness, the thermosetting component has better toughness and has an explosion-proof function, and the functional coating integrates the advantages of the UV component and the heat-proof functional coating and has the characteristics of high hardness and strong support on the surface hardening coating; the pencil hardness of the surface layer of the film-coated product is less than 6B, and the surface hardness of the film-coated product prepared by the functional coating can reach 4H at most;
(3) The explosion-proof functional coating can greatly improve the impact resistance of UTG and can improve the falling height of UTG from 0.5cm to 4-5cm.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The relevant information of the raw materials used in the examples and comparative examples of the present invention are as follows:
(1) Multifunctional acrylate resin
Six-functional urethane acrylate resin: guangdong blue Ke Lu New material L-6601-A;
nine functional urethane acrylate resin: guangdong blue Ke Lu New material L-6901.
(2) Thermosetting resin
Saturated polyester resin: shenzhen Jia holds polymeric material 7817 (solid content 80%);
hydroxy acrylic resin: new material 1955A (solid content 55%).
(3) Curing agent
HDI trimer: bayer 3390 (NCO value 19.6%);
IPDI trimer: win T1890E (NCO value 12%).
(4) Auxiliary agent
Organosilicon leveling agent: pick chemical BYK333;
organotin drier: U.S. gas chemistry T-12.
(5) Amino coupling agent: japanese letter KBE-903.
(6) UTG:30 μm thickness specification.
Example 1
In the embodiment, the explosion-proof functional coating is provided, wherein the preparation raw materials of the explosion-proof functional coating comprise a component A and a component B, the component A comprises 50g of six-functional polyurethane acrylate resin, 125g of saturated polyester resin, 0.75g of 1-hydroxycyclohexyl phenyl ketone, 0.75g of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 80g of ethylene glycol diethyl ether acetate, 80g of methyl isobutyl ketone, 60g of ethyl acetate, 0.8g of organosilicon leveling agent and 0.03g of organotin drier, and the component B is HDI trimer curing agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, 80g of ethylene glycol diethyl ether acetate, 80g of methyl isobutyl ketone and 60g of ethyl acetate are weighed, added into a beaker, then 0.75g of each of 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate serving as a photoinitiator is added, stirred until the materials are completely dissolved, then 0.8g of an organosilicon leveling agent and 0.03g of an organotin drier are added, stirring is continued for 5 minutes, finally 50g of six-functional polyurethane acrylate resin and 125g of saturated polyester resin are added, and a component A is obtained after stirring uniformly, wherein the component A is prepared according to the following steps: component B = 10:1 (weight ratio) adding the component B, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) Uniformly coating the functional coating on the UTG surface treated by the amino coupling agent in a slit coating mode, and thermally curing at 95 ℃ for 1 hour and then curing at 1000mJ/cm 2 And curing by UV energy to obtain the explosion-proof functional coating, wherein the thickness of the coating is 30 mu m.
Example 2
In the embodiment, the preparation raw materials of the explosion-proof functional coating comprise a component A and a component B, wherein the component A comprises 100g of six-functional polyurethane acrylate resin, 125g of saturated polyester resin, 1.5g of 1-hydroxycyclohexyl phenyl ketone, 1.5g of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 130g of ethylene glycol diethyl ether acetate, 130g of ethyl acetate and 1.2g of organosilicon leveling agent, and the component B is HDI trimer curing agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, 130g of ethylene glycol diethyl ether acetate and 130g of ethyl acetate are weighed and added into a beaker, then 1.5g of each of 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate serving as a photoinitiator are added into the beaker, the mixture is stirred until the mixture is completely dissolved, then 1.2g of an organosilicon leveling agent is added, stirring is continued for 5 minutes, finally 100g of six-functional polyurethane acrylate resin and 125g of saturated polyester resin are added, and a component A is obtained after uniform stirring, and the component A is prepared according to the following steps: component B = 12:1 (weight ratio) adding the component B, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) Uniformly coating the functional coating on the UTG surface treated by the amino coupling agent in a slit coating mode, and thermally curing at 95 ℃ for 1 hour and then curing at 1000mJ/cm 2 And curing by UV energy to obtain the explosion-proof functional coating, wherein the thickness of the coating is 30 mu m.
Example 3
In the embodiment, the explosion-proof functional coating is provided, wherein the preparation raw materials of the explosion-proof functional coating comprise a component A and a component B, the component A comprises 50g of six-functional polyurethane acrylate resin, 182g of hydroxy acrylic resin, 0.75g of 1-hydroxy cyclohexyl phenyl ketone, 0.75g of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 120g of ethylene glycol diethyl ether acetate, 80g of ethyl acetate and 0.8g of organosilicon leveling agent, and the component B is HDI trimer curing agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, 120g of ethylene glycol diethyl ether acetate and 80g of ethyl acetate are weighed and added into a beaker, then 0.75g of each of 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate serving as a photoinitiator is added, the mixture is stirred until the mixture is completely dissolved, then 0.8g of an organosilicon leveling agent is added, stirring is continued for 5 minutes, finally 50g of six-functional polyurethane acrylate resin and 182g of hydroxy acrylic resin are added, and the mixture is uniformly stirred to obtain a component A, wherein the component A is prepared by the following steps: component B = 20:1 (weight ratio) adding the component B, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) Uniformly coating the functional coating on the UTG surface treated by the amino coupling agent in a slit coating mode, curing for 1 hour at 95 ℃ and then curing for 1000mJ/cm 2 And curing by UV energy to obtain the explosion-proof functional coating, wherein the thickness of the coating is 30 mu m.
Example 4
This example differs from example 1 only in that the B component (HDI trimer curing agent) is replaced by an equal mass of IPDI trimer, the ratio of A component to B component being from 10:1 is changed to 6:1.
example 5
This example differs from example 1 only in that the hexafunctional urethane acrylate resin was replaced with an equal mass of a nine functional urethane acrylate, the remainder being the same as example 1.
Comparative example 1
In the comparative example, an explosion-proof functional coating is provided, wherein the preparation raw materials of the explosion-proof functional coating comprise an A component and a B component, the A component comprises 125g of saturated polyester resin, 50g of ethylene glycol diethyl ether acetate, 25g of ethyl acetate, 0.5g of organosilicon leveling agent and 0.03g of organotin drier, and the B component is HDI trimer curing agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, 50g of ethylene glycol ethyl ether acetate and 25g of ethyl acetate are weighed, added into a beaker, then 0.5g of organosilicon leveling agent and 0.03g of organotin drier are added, stirred for 5 minutes, finally 125g of saturated polyester resin is added, and a component A is obtained after uniform stirring, and the component A is used according to the following steps: component B = 5:1 (weight ratio) adding the component B, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) And uniformly coating the functional coating on the surface of UTG treated by the amino coupling agent in a slit coating mode, and heating and curing for 1h at 95 ℃ to obtain the explosion-proof functional coating, wherein the thickness of the coating is 30 mu m.
Comparative example 2
In the comparative example, an explosion-proof functional coating is provided, wherein the preparation raw materials of the explosion-proof functional coating comprise an A component and a B component, the A component comprises 150g of six-functional polyurethane acrylate resin, 125g of saturated polyester resin, 2g of 1-hydroxycyclohexyl phenyl ketone, 2g of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 150g of ethylene glycol diethyl ether acetate, 160g of ethyl acetate and 1.5g of organosilicon leveling agent, and the B component is HDI trimer curing agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, 150g of ethylene glycol diethyl ether acetate and 160g of ethyl acetate are weighed and added into a beaker, then 2g of each of 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate serving as a photoinitiator are added, stirring is carried out until the materials are completely dissolved, then 1.5g of organosilicon leveling agent is added, stirring is continued for 5 minutes, finally 150g of six-functional polyurethane acrylate resin and 125g of saturated polyester resin are added, and a component A is obtained after uniform stirring, wherein the component A is prepared by the following steps: component B = 15:1 (weight ratio) adding the component B, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) Uniformly coating the functional coating on the UTG surface treated by the amino coupling agent in a slit coating mode, heating and curing for 1.5 hours at 90 ℃, and then curing for 1000mJ/cm 2 And curing by UV energy to obtain the explosion-proof functional coating, wherein the thickness of the coating is 30 mu m.
Comparative example 3
In this comparative example, an explosion-proof functional coating was provided, whose raw materials for preparation included 100g of a hexafunctional urethane acrylate resin, 1.5g of 1-hydroxycyclohexyl phenyl ketone, 1.5g of ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, 50g of ethylene glycol ethyl ether acetate, 50g of ethyl acetate, and 0.8g of an organosilicon leveling agent.
The preparation method of the explosion-proof functional coating comprises the following steps:
(1) Under a yellow light environment, weighing 50g of ethylene glycol diethyl ether acetate and 50g of ethyl acetate, adding into a beaker, then adding 1.5g of each of 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate serving as photoinitiators, stirring until the materials are completely dissolved, then adding 0.8g of organosilicon leveling agent, continuing stirring for 5 minutes, finally adding 100g of six-functional polyurethane acrylate, stirring uniformly, and removing bubbles in vacuum to obtain the functional coating;
(2) Uniformly coating the functional coating on the UTG surface treated by the amino coupling agent in a slit coating mode, and treating the surface with 1000mJ/cm 2 And curing by UV energy to obtain the functional coating, wherein the thickness of the coating is 30 mu m.
Performance tests were performed on the explosion-proof functional coating and UTG coated with the explosion-proof functional coating provided in examples and comparative examples, as follows:
(1) Pencil hardness: testing was performed as per GBT 6739-2006;
(2) Hundred grid test: testing according to the method of GB 9286-98;
(3) The light transmittance/haze/yellowness is tested by adopting a light splitting tester;
(4) Explosion-proof performance: the less slag that falls when UTG is crushed, the better the explosion-proof performance, the less slag the 5 stars represent, the more slag the lower the star grade.
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from table 1:
(1) The more the multifunctional acrylate in the coating, the higher the hardness of the coating, but when the amount exceeds a certain amount, the glass adhesion, the boiling resistance and the explosion resistance are reduced correspondingly.
(2) Compared with saturated polyester resin, the hydroxy acrylic resin has slightly poorer explosion resistance, and glass slag can be generated after UTG is crushed.
(3) After the HDI trimer is replaced by the IPDI trimer, the performance is not obviously different, but the HDI trimer is preferred in view of higher price and higher dosage of the IPDI trimer.
Application examples 1-5 and comparative application examples 1-3
Plasma treatment was performed on the explosion-proof functional coatings provided in application examples 1 to 5 and comparative examples 1 to 3, respectively, followed by application of a hardening coating liquid (korean solution Tech company 3352 hardening liquid) to a thickness of 5 μm, respectively, to obtain UTG coated with the explosion-proof functional coating and the hardening layer.
Comparative application example 4
In this comparative application example, a film-sticking product was provided, namely, a 25 μm pet film with a hardening coating was stuck to the UTG surface with a 25 μm oca adhesive.
The cured layers provided in application examples 1 to 5 and comparative application examples 1 to 4 and UTG coated with the explosion-proof functional coating and the cured layers were subjected to performance test as follows:
(1) Pencil hardness and hundred grid test: referring to the test methods in table 1;
(2) Pen-down characteristics: a 12g cylindrical pen point is adopted to fall down freely from a pen falling tester and is crashed on the coated film UTG, and the maximum height is UTG when the pen point is not broken for three times;
(3) Bendable characteristics: and placing the coated UTG on a book-turning type bending machine, bending for 20 ten thousand times according to R=1.5 and R=2.0, and observing whether paint films and UTG are broken or not.
The results of the performance test are shown in Table 2.
TABLE 2
Remarks: the thickness of the film coating layer of the film coating product is 35 mu m, and the film thickness of the film coating product is 50 mu m, so that the pen dropping characteristic is slightly good.
As can be seen from table 2:
(1) Impact resistance was greatly improved (drop height from 0.5 to 4-5 cm) compared to die UTG after the inventive coating was applied to the UTG surface.
(2) The more the multifunctional acrylic resin in the coating, the stronger the support to the hardened coating, the higher the pencil hardness of the hardening liquid, but beyond a certain amount, the coating adhesion and the boiling resistance are reduced.
(3) After the UTG surface is coated with the coating, compared with a film-sticking product, the pencil hardness of the surface of the coating is greatly improved.
The applicant states that the invention is illustrated by the above examples of the explosion-proof functional coating of the invention, and the method of making and using it, but the invention is not limited to, i.e. it is not meant that the invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The explosion-proof functional coating is characterized by comprising a component A and a component B, wherein the component A comprises multifunctional acrylate resin, thermosetting resin, photoinitiator, solvent and auxiliary agent, and the component B comprises curing agent;
the weight portion of the thermosetting resin is 0.8-3 times of the weight portion of the multifunctional acrylate resin.
2. The explosion-proof functional coating according to claim 1, wherein the multifunctional acrylate resin comprises any one or a combination of at least two of trifunctional acrylate resin, tetrafunctional acrylate resin, pentafunctional acrylate resin, hexafunctional acrylate resin, heptafunctional acrylate resin, octafunctional acrylate resin, nonafunctional acrylate resin, decafunctional acrylate resin, undecfunctional acrylate resin, dodecafunctional acrylate resin, tridecyl functional acrylate resin, tetradecfunctional acrylate resin, or pentadecyl functional acrylate resin, preferably hexafunctional acrylate resin.
3. The explosion-proof functional coating according to claim 1 or 2, characterized in that the thermosetting resin comprises a hydroxyacrylate and/or a saturated polyester resin, preferably a saturated polyester resin.
4. The explosion-proof functional coating according to any one of claims 1 to 3, wherein the curing agent comprises any one or a combination of at least two of hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, or isophorone diisocyanate trimer.
5. The explosion-proof functional coating according to any one of claims 1-4, wherein the photoinitiator comprises any one or a combination of at least two of 1-hydroxycyclohexyl phenyl ketone, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, or 2-hydroxy-2-methyl-1-phenyl-1-propanone.
6. The explosion-proof functional coating according to any one of claims 1-5, wherein the solvent comprises any one or a combination of at least two of ethyl acetate, butyl acetate, cyclohexanone, ethylene glycol ethyl ether acetate, or methyl isobutyl ketone.
7. The explosion-proof functional coating according to any one of claims 1 to 6, wherein the auxiliary agent comprises a leveling agent and/or a drier;
preferably, the leveling agent comprises a silicone leveling agent;
preferably, the drier comprises an organotin drier and/or an organobismuth drier.
8. The explosion-proof functional coating according to any one of claims 1 to 7, wherein the weight part of the curing agent is 10 to 50% of the weight part of the thermosetting resin;
preferably, the weight part of the photoinitiator is 2-5% of the weight part of the multifunctional acrylate resin;
preferably, the weight part of the solvent is 0.5-2 times of the total weight part of the multifunctional acrylate resin and the thermosetting resin;
preferably, the weight portion of the auxiliary agent is 0-1% of the total weight portion of the multifunctional acrylate resin and the thermosetting resin.
9. The method for producing an explosion-proof functional coating according to any one of claims 1 to 8, characterized in that the method comprises the steps of:
(1) Under the yellow light environment, dissolving a photoinitiator in a solvent, stirring uniformly, adding an auxiliary agent, continuously stirring, then adding a multifunctional acrylate resin and a thermosetting resin, stirring uniformly to obtain a component A, mixing the component A and the component B according to a proportion when in use, and carrying out vacuum defoaming to obtain the functional coating;
(2) Coating functional coating on the surface of bendable ultrathin glass, and performing Ultraviolet (UV) curing after heat curing to obtain the explosion-proof functional coating;
preferably, the surface of the bendable ultrathin glass is treated by an amino coupling agent;
preferably, the heat curing temperature is 80-95 ℃ and the heat curing time is 1-2 hours;
preferably, the UV curing adopts mercury lamp curing, and the accumulated energy of the UV curing is 800-1200mJ/cm 2 。
10. Use of an explosion-proof functional coating according to any one of claims 1-8 in a bendable ultra-thin glass surface coating.
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