CN104403554B - Ultraviolet curing coating and preparation method thereof - Google Patents
Ultraviolet curing coating and preparation method thereof Download PDFInfo
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- CN104403554B CN104403554B CN201410690943.1A CN201410690943A CN104403554B CN 104403554 B CN104403554 B CN 104403554B CN 201410690943 A CN201410690943 A CN 201410690943A CN 104403554 B CN104403554 B CN 104403554B
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- curing paint
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention provides ultraviolet curing coating and a preparation method thereof. The ultraviolet curing coating comprises the following components in parts by weight: 25-45 parts of urethane acrylate with functionality larger than or equal to six, 15-25 parts of polyurethane oligomer with an end group as vinyl ether, 10-20 parts of alicyclic epoxides, 5-15 parts of vinyl ether compounds, 10-25 parts of acrylate monomer with functionality larger than or equal to three and 2-10 parts of photoinitiator, wherein the photoinitiator comprises free-radical photoinitiator and cationic photoinitiator, and the mass ratio of the free-radical photoinitiator to the cationic photoinitiator is 0.5-2. According to the ultraviolet curing coating, a free radical and cation mixture photo-initiation system is adopted, and accordingly an obtained film has the characteristics of high hardness and low shrinkage.
Description
Technical field
The present invention relates to a kind of ultraviolet-curing paint and preparation method thereof, especially relate to one kind and be used for flexiplast system
Ultraviolet-curing paint of product surface treatment and preparation method thereof.
Background technology
Due to ultraviolet-curing paint have efficiently, energy-conservation, environmental friendliness and economic dispatch remarkable advantage, its application base material from
Initial timber extends to plastics, paper, leather and metal etc..According to its curing mechanism, ultraviolet-curing paint is mainly permissible
It is divided into free radical initiation type and cation initiation type.Cation initiation type ultraviolet-curing paint have solidification volume contraction little,
The advantages of active group time to live is long, but have such problems as that solidification rate is slow, it is big to be affected by Environmental Water.Free radical causes
Type ultraviolet-curing paint has the advantages that abundant raw material source and cheap, solidification rate is fast and do not affected by the moisture of environment,
But have such problems as to solidify that volume contraction is big and oxygen inhibition phenomenon.At this stage, it is applied to being mainly of surface of plastic products process
Free radical initiation type ultraviolet-curing paint, but the defect big due to there is solidification volume contraction, lead to it thin in flexiplast
Application on film base material is severely impacted.
Pluses and minuses are respectively had based on free radical initiation type and cation initiation type ultraviolet-curing paint, therefore in certain applications
Middle using collection free radical initiation type and cation initiation type ultraviolet-curing paint each advantage mix type ultraviolet light polymerization apply
Material.
For example, Chinese patent application 201310572563.3 discloses a kind of photocuring painting of free radical-cationic hybrid
Material, its composition 10-60% containing photosensitive organic resin by weight percentage, mix photosensitive monomer 5-40%, active solvent 10-
50%, mix light trigger 2-4%, auxiliary agent 0.1-0.2%.Wherein, photosensitive organic resin is epoxy acrylate or polyurethane
Acrylate；Mixing photosensitive monomer is γ-glycidyl ether oxygen propyl trimethyl silane or 2- (3,4- 7-oxa-bicyclo[4.1.0) ethyl
Trimethoxy silane；Active solvent is tri (propylene glycol) diacrylate, propylene glycol diacrylate, diethylene glycol dipropyl
One of olefin(e) acid ester, triethylene glycol diacrylate and phthalic acid diethylene glycol acrylate, or two of which
Mixture；Mixing light trigger is mixed to form by free radical photo-initiation and cation light initiator, and mixed proportion is had with photosensitive
Machine resin is identical with the proportioning mixing photosensitive monomer.
Chinese patent application 200980128389.5 discloses a kind of flexible matrix shrinking and crimping reduction, and this matrix applies
It is covered with the coating with dual cure systems, this coating can comprise radically curing acrylate, cationically curable aliphatic ring
Oxide, radical photosensitive initiator and cationic photosensitive initiator.But, this technical scheme employs little point of high functionality
Sub- acrylate monomer and small molecule alicyclic monomer, cured product poor in flexibility.In addition, this patent radically curing group
Divide and cationic curing component do not have chemical covalent bonds bridging, formation is interpenetrating networks cross-linking system, and Miscibility is bad,
Easily cause microphase-separated impact material property.
Chinese patent application 201110053680.X discloses a kind of cationic polymerization or cation-free radical mixed polymerization
Photopolymer System, this curing system is the photoactive of vinyl ethers and allyl ether, 1-4 by the end group of 86-89 weight portion
The solvent composition of the Photoepolymerizationinitiater initiater of weight portion and 7-13 weight portion.Because the reactive component of this Photopolymer System is ethene
After base ether or propenyl ether, therefore its solidification rate are slow, system solidifies, hardness is low.
Content of the invention
It is an object of the invention to provide ultraviolet-curing paint of a kind of high rigidity, lower shrinkage and preparation method thereof.
In order to realize foregoing invention purpose, on the one hand, the invention provides a kind of ultraviolet-curing paint, by weight
Meter, it includes following component：
Wherein, light trigger includes free radical photo-initiation and cation light initiator, and free radical photo-initiation and sun
The mass ratio of ionic photoinitiator is 0.5-2.
The ultraviolet-curing paint of the present invention adopts free radical and cation mixing light initiation system, and wherein, free radical is solid
Changing reactive component is urethane acrylate and acrylate monomer；Cationic curing reactive component is alicyclic epoxy compound
Thing；End group is urethane oligomer and vinyl ether compound not only free-radical curable but also the cationically curable of vinyl ethers.
In the ultraviolet-curing paint of the present invention, the degree of functionality of urethane acrylate is more than or equal to 6, acrylate monomer
Degree of functionality be more than or equal to 3, therefore curing reaction speed is fast, crosslinking degree big, and the hardness of obtained film is high, marresistance
Good；Simultaneously as generation cationic curing, therefore solidify volume contraction little.Particularly, end group is low for the polyurethane of vinyl ethers
Polymers and vinyl ether compound not only free-radical curable but also cationically curable, its respectively with radically curing reactive component and
Cationic curing reactive component is polymerized to form chemical covalent bonds bridging, therefore the system phase of the ultraviolet-curing paint of the present invention
Capacitive is good, and gained film will not produce microphase-separated.
Preferably, count by weight, the ultraviolet-curing paint of the present invention includes following component：Degree of functionality is more than or equal to
6 urethane acrylate 30-45 part, end group is urethane oligomer 15-25 part of vinyl ethers, alicyclic epoxide compound
10-20 part, vinyl ether compound 8-15 part, degree of functionality is more than or equal to 3 acrylate monomer 12-25 part, light trigger 2-
10 parts；Wherein, light trigger includes free radical photo-initiation and cation light initiator, and free radical photo-initiation and cation
The mass ratio of light trigger is 0.5-2.
According to a specific embodiment of the present invention, count by weight, the ultraviolet-curing paint of the present invention include as
Lower component：Degree of functionality is more than or equal to 6 urethane acrylate 35-45 part, and end group is the urethane oligomer 15- of vinyl ethers
25 parts, alicyclic epoxide compound 10-15 part, vinyl ether compound 5-15 part, degree of functionality is more than or equal to 3 acrylate list
Body 15-25 part, light trigger 2-10 part；Wherein, light trigger includes free radical photo-initiation and cation light initiator, and from
Mass ratio by base light trigger and cation light initiator is 0.5-2.
According to another embodiment of the present invention, count by weight, the ultraviolet-curing paint of the present invention includes
Following component：Degree of functionality is more than or equal to 6 urethane acrylate 25-35 part, and end group is the urethane oligomer of vinyl ethers
15-25 part, alicyclic epoxide compound 15-20 part, vinyl ether compound 5-15 part, degree of functionality is more than or equal to 3 acrylic acid
Ester monomer 10-20 part, light trigger 2-10 part；Wherein, light trigger includes free radical photo-initiation and cation light initiator,
And free radical photo-initiation is 0.5-2 with the mass ratio of cation light initiator.
According to another embodiment of the present invention, count by weight, the ultraviolet-curing paint of the present invention includes
Following component：Degree of functionality is more than or equal to 6 urethane acrylate 30-40 part, and end group is the urethane oligomer of vinyl ethers
18-23 part, alicyclic epoxide compound 12-17 part, vinyl ether compound 8-12 part, degree of functionality is more than or equal to 3 acrylic acid
Ester monomer 12-20 part, light trigger 2-10 part；Wherein, light trigger includes free radical photo-initiation and cation light initiator,
And free radical photo-initiation is 0.5-2 with the mass ratio of cation light initiator.
Preferably, in the ultraviolet-curing paint of the present invention, the quality of free radical photo-initiation and cation light initiator
Than for 1-2；It is highly preferred that free radical photo-initiation is 1-1.5 with the mass ratio of cation light initiator.
Preferably, count by weight, the ultraviolet-curing paint of the present invention further includes auxiliary agent 0.1-1.5 part.Root
According to a specific embodiment of the present invention, auxiliary agent includes levelling agent and/or defoamer.According to actual needs, the ultraviolet of the present invention
Photocureable coating can further include other suitable adjuvants such as substrate wetting agents, wetting dispersing agent and/or colouring agent.
According to another embodiment of the present invention, above-mentioned end group is the urethane oligomer of vinyl ethers is by following
Method prepares：
(1) the anhydrous dihydroxylic alcohols massage being 500-1500 by diisocyanate and molecular weight under 60-80 DEG C, nitrogen atmosphere
Your mixing of the metering than NCO/OH=1.3-2.0, and add and be equivalent to dihydroxylic alcohols and diisocyanate quality summation 0.01-
0.05% organotin catalysts, react 2-4h；
Add with step (1) in unreacted isocyanate groups equimolar amounts the vinyl ether compound of hydroxyl and
Be equivalent to the polymerization inhibitor of the whole quality summation 0.03-0.07%, react 2-4h at 60-80 DEG C.
Due to step (1) in the mensure of mole of actually unreacted isocyanate groups be very inconvenient, therefore
In the vinyl ether compound of the step (2) hydroxyl of middle addition it is and unreacted isocyanate groups equimolar amounts in theory.
And, the complexity in view of real reaction, in the present invention, addition is contained with unreacted isocyanate groups equimolar amounts
The mole that the vinyl ether compound of hydroxyl is not required for the two is essentially equal, and the mole of the two is roughly equal to be also permissible
, particularly preferably control the mole of the vinyl ether compound of hydroxyl to be slightly more than unreacted isocyanate groups
Mole.
Preferably, in step, (1) middle addition is equivalent to having of dihydroxylic alcohols and diisocyanate quality summation 0.02-0.04%
Machine tin catalyst.
Preferably, in step, (2) middle addition is equivalent to the polymerization inhibitor of the whole quality summation 0.04-0.06%.
Preferably, dihydroxylic alcohols is at least one in polyester diol, polyether Glycols, polyolefin dihydroxylic alcohols.More
Preferably, dihydroxylic alcohols is selected from polycaprolactone diols, poly adipate succinic acid ester dihydroxylic alcohols, polyneopentyl glycol adipate two
First alcohol, polyadipate hexylene glycol ester dihydroxylic alcohols, polyoxygenated propane dihydroxylic alcohols, polyoxygenated ethane dihydroxylic alcohols, polyoxytetramethylene
At least one in dihydroxylic alcohols, polyisobutene dihydroxylic alcohols.
Preferably, diisocyanate is selected from aromatic diisocyanate, aliphatic diisocyanate and alicyclic two different
At least one in cyanate.It is highly preferred that diisocyanate is selected from methyl diphenylene diisocyanate, toluene diisocynate
Ester, 1,6- hexamethylene diisocyanate, 1,3,3- trimethyl -5- isocyanate group -1- isocyanato methylcyclohexane and two rings
At least one in hexyl methane -4,4 '-diisocyanate.
Preferably, organotin catalysts are stannous octoate and/or dibutyl tin laurate.
Preferably, the vinyl ether compound of hydroxyl be selected from ethylene glycol vinyl ether, 4- hydroxy butyl vinyl ether and
At least one in cyclohexyl -1,4- dimethanol monovinyl ether.
Preferably, polymerization inhibitor is hydroquinones and/or hydroquinone monomethyl ether.
According to another embodiment of the present invention, alicyclic epoxide compound is selected from 3,4- expoxycyclohexyl first
Acid -3 ', 4 '-epoxycyclohexyethylSiOi ester, 3,4- epoxy radicals -6- methylcyclohexyl formic acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexyl,
At least one in double-(3,4- expoxycyclohexyl)-adipate ester and bicyclopentadiene dioxide.
According to another embodiment of the present invention, vinyl ether compound is selected from butanediol-Isosorbide-5-Nitrae-divinyl
In ether, triethyleneglycol divinylether, diethylene glycol divinyl ether and 1,4 cyclohexane dimethanol divinyl ether at least
A kind of.
According to another embodiment of the present invention, acrylate monomer is selected from trimethylolpropane tris acrylic acid
Ester, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate, the third oxidation trimethylolpropane
Triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate and two
At least one in pentaerythrite five/six acrylate.
According to another embodiment of the present invention, free radical photo-initiation is selected from 2- hydroxy-2-methyl -1- benzene
Base -1- acetone, 1- hydroxy-cyclohexan benzylacetone, 2,4,6- trimethyl-benzoyl diphenyl phosphine oxide, double (2,4,6- trimethylbenzene
Formyl) phenyl phosphine oxide, benzophenone, at least one in benzoin ethyl ether and benzoin dimethylether.
According to another embodiment of the present invention, cation light initiator be selected from Diaryl iodonium phosphate, two
At least one in aryl iodide stibate, triaryl sulphur hexafluoro antimonate and triaryl sulphur hexafluoro arsenate.
In order to realize the purpose of the present invention, on the other hand, the invention provides a kind of preparation side of ultraviolet-curing paint
Method, it comprises the steps：
1. prepare the urethane oligomer that end group is vinyl ethers：
(1) the anhydrous dihydroxylic alcohols massage being 500-1500 by diisocyanate and molecular weight under 60-80 DEG C, nitrogen atmosphere
Your mixing of the metering than NCO/OH=1.3-2.0, and add and be equivalent to dihydroxylic alcohols and diisocyanate quality summation 0.01-
0.05% organotin catalysts, react 2-4h；
Add with step (1) in unreacted isocyanate groups equimolar amounts the vinyl ether compound of hydroxyl and
Be equivalent to the polymerization inhibitor of the whole quality summation 0.03-0.07%, react 2-4h at 60-80 DEG C；
2. by weight, end group 1. obtained for 15-25 part step is the urethane oligomer of vinyl ethers, 25-
45 parts of degrees of functionality be more than or equal to 6 urethane acrylate, 10-20 part alicyclic epoxide compound, 5-15 part vinyl etherificate
Compound, 10-25 part degree of functionality are more than or equal to 3 acrylate monomer and the mixing of 2-10 part light trigger, obtain ultraviolet light polymerization
Coating；
Wherein, light trigger includes free radical photo-initiation and cation light initiator, free radical photo-initiation and sun from
The mass ratio of sub-light initiator is 0.5-2.
Preferably, it is simultaneously introduced auxiliary agent 0.1-1.5 part in step mixed process 2..A concrete reality according to the present invention
Apply mode, auxiliary agent is levelling agent and/or defoamer.According to actual needs, substrate wetting agents, wetting point can also be added further
Other suitable adjuvants such as powder and/or colouring agent.
According to another embodiment of the present invention, the vinyl ether compound of hydroxyl is selected from ethylene glycol vinyl
At least one in ether, 4- hydroxy butyl vinyl ether and cyclohexyl -1,4- dimethanol monovinyl ether.
The photocuring technology that ultraviolet-curing paint disclosed by the invention is caused using free radical and cation initiation mixes,
Have the remarkable advantage that solidification rate is fast and solidification volume contraction is low concurrently, simultaneously obtained hardness of film is high, marresistance is good, fits
Close the surface treatment being applied to flexible plastic film.
Below in conjunction with specific embodiment, the present invention is further illustrated, but these specific embodiments are not right
The restriction of the present invention, and some specific specific embodiment of the simply present invention.
Specific embodiment
(i) ultraviolet-curing paint and its preparation
Embodiment 1
By 100 mass parts molecular weight be 1500 polyoxytetramethylene dihydroxylic alcohols after 120 DEG C of decompression dehydration 3h, cooling
To 60 DEG C；33 mass parts methyl diphenylene diisocyanates and 0.04 mass parts stannous octoate is added, at 60 DEG C under nitrogen atmosphere
Reaction 3h；It is subsequently adding 15.3 mass parts 4- hydroxy butyl vinyl ethers and 0.08 mass parts hydroquinone monomethyl ether, anti-at 60 DEG C
Answer 2h；The urethane oligomer (a) that end group is vinyl ethers is obtained after the completion of reaction.
35 weight portion nine degree of functionality urethane acrylate (Miramer MU9500), 20 weight portion end groups are vinyl
The urethane oligomer (a) of ether, 15 weight portion 3,4- expoxycyclohexyl formic acid -3 ', 4 '-epoxycyclohexyethylSiOi ester, 10 weight portions
Butanediol -1,4- divinyl ether, 15 weight portion dipentaerythritol five/six acrylate, 3 weight portion 1- hydroxy-cyciohexyl third
Ketone, 2 weight portion triaryl sulphur hexafluoro antimonates, 0.3 weight portion levelling agent (Glide432) it is mixed and stirred for all
Even, obtain ultraviolet-curing paint.By weight, its composition is as follows：
Embodiment 2
By 100 mass parts molecular weight be 1000 poly adipate succinic acid ester dihydroxylic alcohols after 120 DEG C of decompression dehydration 3h, fall
Temperature is to 75 DEG C；42 mass parts dicyclohexyl methyl hydride -4,4 '-diisocyanate and 0.04 mass parts two bay is added under nitrogen atmosphere
Sour dibutyl tin, reacts 3h at 75 DEG C；It is subsequently adding 10.6 mass parts ethylene glycol vinyl ether and 0.08 mass parts hydroquinones,
React 3h at 75 DEG C；The urethane oligomer (b) that end group is vinyl ethers is obtained after the completion of reaction.
40 weight portion six degree of functionality urethane acrylate (Agisyn 230A3), 15 weight portion end groups are vinyl ethers
Urethane oligomer (b), 20 weight portion bicyclopentadiene dioxide, 8 weight portion diethylene glycol divinyl ether, 12 weight portions
Tetramethylol methane tetraacrylate, 2 weight portions 2,4,6- trimethyls-benzoyl diphenyl phosphine oxide, 3 weight portion Diaryl iodonium antimony
Hydrochlorate, 0.3 weight portion levelling agent (BYK-333) and 0.2 weight portion defoamer (BYK-088) are mixed and stirred for uniformly, obtaining purple
Outer photocureable coating.By weight, its composition is as follows：
Embodiment 3
By 100 mass parts molecular weight be 500 polyneopentyl glycol adipate dihydroxylic alcohols after 115 DEG C of decompression dehydration 3h,
It is cooled to 80 DEG C；58 mass parts 1,3,3- trimethyl -5- isocyanate group -1- isocyanato methylcyclohexane are added under nitrogen atmosphere
With 0.05 mass parts stannous octoate, react 3h at 80 DEG C；It is subsequently adding 20.4 mass parts cyclohexyl -1,4- dimethanol monovinyl bases
Ether and 0.09 mass parts hydroquinone monomethyl ether, react 2h at 80 DEG C；The poly- ammonia that end group is vinyl ethers is obtained after the completion of reaction
Ester oligomer (c).
30 weight portion six degree of functionality urethane acrylate (CN9010NS), 25 weight portion end groups are the poly- of vinyl ethers
Urethane oligomer (c), 10 weight portion 3,4- epoxy radicals -6- methylcyclohexyl formic acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexyl,
10 weight portion triethyleneglycol divinylether, 25 weight portion pentaerythritol triacrylates, 4 weight portion 2- hydroxy-2-methyl -1-
Phenyl -1- acetone, 2 weight portion triaryl sulphur hexafluoro arsenates, 0.4 weight portion levelling agent (BYK-UV3505) and 0.2 weight
Part defoamer (BYK-066N) is mixed and stirred for uniformly, obtaining ultraviolet-curing paint.By weight, its composition is as follows：
Embodiment 4
By 100 mass parts molecular weight be 1000 polycaprolactone diols after 110 DEG C of decompression dehydration 3h, be cooled to 65
℃；28 mass parts toluene di-isocyanate(TDI)s and 0.04 mass parts dibutyl tin laurate is added under nitrogen atmosphere, anti-at 65 DEG C
Answer 3h；It is subsequently adding 13.9 mass parts 4- hydroxy butyl vinyl ethers and 0.07 mass parts hydroquinones, react 3h at 65 DEG C；Reaction
After the completion of obtain end group be vinyl ethers urethane oligomer (d).
45 weight portion nine degree of functionality urethane acrylate (EBECRYL8602), 15 weight portion end groups are vinyl ethers
Urethane oligomer (d), 12 weight portions double-(3,4- expoxycyclohexyl)-adipate ester, 15 weight portion 1,4- hexamethylenes two
Methyl alcohol divinyl ether, 25 weight portion trimethylol-propane trimethacrylates, 4 weight portion benzoin dimethylethers, 3 weight portions
Diaryl iodonium phosphate, 0.6 weight portion levelling agent (BYK-378), 0.4 weight portion defoamer (BYK-066N) is mixed and stirred for
Uniformly, obtain ultraviolet-curing paint.By weight, its composition is as follows：
Embodiment 5
By 100 mass parts molecular weight be 500 polyoxygenated ethane dihydroxylic alcohols after 120 DEG C of decompression dehydration 3h, be cooled to 70
℃；50 mass parts 1,6- hexamethylene diisocyanate and 0.05 mass parts stannous octoate is added under nitrogen atmosphere, anti-at 70 DEG C
Answer 4h；It is subsequently adding 34.0 mass parts cyclohexyl-Isosorbide-5-Nitrae-dimethanol monovinyl ether and 0.09 mass parts hydroquinone monomethyl ether,
React 4h at 70 DEG C；The urethane oligomer (e) that end group is vinyl ethers is obtained after the completion of reaction.
35 weight portion six degree of functionality urethane acrylate (UV3600-P6), 20 weight portion end groups are vinyl ethers
Urethane oligomer (e), 20 weight portion 3,4- expoxycyclohexyl formic acid -3 ', 4 '-epoxycyclohexyethylSiOi ester, 10 weight portion three second
Double (the 2,4,6- trimethylbenzene of divinyl ether, 20 weight portion ethoxyquin trimethylolpropane trimethacrylates, 6 weight portions
Formyl) phenyl phosphine oxide, 4 weight portion triaryl sulphur hexafluoro antimonates, 0.3 weight portion levelling agent (Rad2100) and
0.2 weight portion defoamer (BYK-066N) is mixed and stirred for uniformly, obtaining ultraviolet-curing paint.By weight, its composition
As follows：
Comparative example
By 55 weight portion six degree of functionality urethane acrylate (Agisyn 230A3), 20 weight portion dipentaerythritols five/
Six acrylate, 25 weight portion pentaerythritol triacrylates, 5 weight portion 1- hydroxy-cyclohexan benzylacetones, 0.3 weight portion levelling
Agent (BYK-3505) and 0.2 weight portion defoamer (BYK-088) are mixed and stirred for uniformly, obtaining ultraviolet-curing paint.By weight
Amount part meter, its composition is as follows：
(ii) ultraviolet-curing paint performance test
Prepared by sample：The ultraviolet-curing paint of embodiment 1-5 and comparative example is respectively coated the PET being 50 μm in thickness
On plastic basis material, insert 80 DEG C of baking oven and 2min is dried, then in 350mJ/cm2Irradiation energy under film-forming, film thickness monitoring
For 3 microns.
Performance test：To the adhesive force of the ultraviolet-curing paint gained film sample using embodiment 1-5 and comparative example,
Hardness, angularity and marresistance are tested, and its result is as shown in table 1 below：
Table 1：Each ultraviolet-curing paint gained film performance test result
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| Adhesive force | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Hardness | 4H | 3H | 3H | 4H | 3H | 3H |
| Angularity | 4.8mm | 3.6mm | 3.9mm | 5.4mm | 3.2mm | 16.9mm |
| Marresistance | No abrade | No abrade | No abrade | No abrade | No abrade | No abrade |
Adhesive force：By GB/T9286-1998 test.
Hardness：By GB/T6739-2006 test.
Angularity：With reference to GB/T 25257-2010 test；The big small sample of 100mm × 100mm is taken to be positioned over level table
On, the height of sample four side warpage is measured with slide measure, and using wherein maximum as angularity numerical value；Test result takes three
The mean value of individual sample.
Marresistance：Using 0000# steel wool, in heavy burden 750g/cm2Under the conditions of, film carries out reciprocal 20 times and rubs
Wipe and test, visually observe and have or not scratch resistant.
Claims (10)
1. a kind of ultraviolet-curing paint, counts by weight, and it includes following component：
Wherein, described light trigger includes free radical photo-initiation and cation light initiator, described free radical photo-initiation
Mass ratio with described cation light initiator is 0.5-2.
2. ultraviolet-curing paint as claimed in claim 1, wherein, described end group is the urethane oligomer of vinyl ethers
Prepared by following methods：
Under 60-80 DEG C, nitrogen atmosphere by diisocyanate and molecular weight be 500-1500 anhydrous dihydroxylic alcohols in molar ratio
The metering mixing of NCO/OH=1.3-2.0, and add and be equivalent to described dihydroxylic alcohols and described diisocyanate quality summation 0.01-
0.05% organotin catalysts, react 2-4h；
(2) add with step (1) in the vinyl ether compound of hydroxyl of unreacted isocyanate groups equimolar amounts and suitable
In the polymerization inhibitor of the whole quality summation 0.03-0.07%, react 2-4h at 60-80 DEG C.
3. ultraviolet-curing paint as claimed in claim 2, wherein, the vinyl ether compound of described hydroxyl is selected from second
At least one in glycol vinyl ethers, 4- hydroxy butyl vinyl ether and cyclohexyl -1,4- dimethanol monovinyl ether.
4. ultraviolet-curing paint as claimed in claim 1, wherein, described alicyclic epoxide compound is selected from 3,4- epoxy
Butylcyclohexyl formic acid -3 ', 4 '-epoxycyclohexyethylSiOi ester, 3,4- epoxy radicals -6- methylcyclohexyl formic acid -3 ', 4 '-epoxy radicals -6 ' -
Methyl cyclohexyl, at least one in double-(3,4- expoxycyclohexyl)-adipate ester and bicyclopentadiene dioxide.
5. ultraviolet-curing paint as claimed in claim 1 is it is characterised in that described vinyl ether compound is selected from fourth two
Alcohol -1,4- divinyl ether, triethyleneglycol divinylether, diethylene glycol divinyl ether and 1,4 cyclohexane dimethanol diethyl
At least one in alkene ether.
6. ultraviolet-curing paint as claimed in claim 1 is it is characterised in that described acrylate monomer is selected from three hydroxyl first
Base propane triacrylate, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate, the third oxygen
Change trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, ethoxyquin pentaerythrite
At least one in tetraacrylate and dipentaerythritol five/six acrylate.
7. ultraviolet-curing paint as claimed in claim 1, wherein, described free radical photo-initiation is selected from 2- hydroxyl -2-
Methyl isophthalic acid-phenyl -1- acetone, 1- hydroxy-cyclohexan benzylacetone, 2,4,6- trimethyl-benzoyl diphenyl phosphine oxide, double (2,4,
6- trimethylbenzoyl) phenyl phosphine oxide, benzophenone, at least one in benzoin ethyl ether and benzoin dimethylether.
8. ultraviolet-curing paint as claimed in claim 1, wherein, described cation light initiator is selected from Diaryl iodonium
In phosphate, Diaryl iodonium stibate, triaryl sulphur hexafluoro antimonate and triaryl sulphur hexafluoro arsenate at least one
Kind.
9. a kind of preparation method of ultraviolet-curing paint, it comprises the steps：
1. prepare the urethane oligomer that end group is vinyl ethers：
Under 60-80 DEG C, nitrogen atmosphere by diisocyanate and molecular weight be 500-1500 anhydrous dihydroxylic alcohols in molar ratio
The metering mixing of NCO/OH=1.3-2.0, and add and be equivalent to described dihydroxylic alcohols and described diisocyanate quality summation 0.01-
0.05% organotin catalysts, react 2-4h；
(2) add with step (1) in the vinyl ether compound of hydroxyl of unreacted isocyanate groups equimolar amounts and suitable
In the polymerization inhibitor of the whole quality summation 0.03-0.07%, react 2-4h at 60-80 DEG C；
2. by weight, end group 1. obtained for 15-25 part step is the urethane oligomer of vinyl ethers, 25-45 part
Degree of functionality be more than or equal to 6 urethane acrylate, 10-20 part alicyclic epoxide compound, 5-15 part vinyl ether compound,
10-25 part degree of functionality is more than or equal to 3 acrylate monomer and the mixing of 2-10 part light trigger, obtains described ultraviolet light polymerization and applies
Material；
Wherein, described light trigger includes free radical photo-initiation and cation light initiator, described free radical photo-initiation
Mass ratio with described cation light initiator is 0.5-2.
10. preparation method as claimed in claim 9, wherein, the vinyl ether compound of described hydroxyl is selected from ethylene glycol
At least one in vinyl ethers, 4- hydroxy butyl vinyl ether and cyclohexyl -1,4- dimethanol monovinyl ether.
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| CN105176345B (en) * | 2015-08-18 | 2017-09-29 | 南京万儒科技实业有限公司 | Keyboard typography and the UV coating of printing and preparation method thereof |
| EP3170848A1 (en) * | 2015-11-23 | 2017-05-24 | Henkel AG & Co. KGaA | Cationic photo transfer polymerization |
| CN105670489A (en) * | 2015-12-18 | 2016-06-15 | 广州源辉化工有限公司 | Color-adjustable UV coating and spray coating use method thereof |
| CN105505197B (en) * | 2015-12-30 | 2018-07-27 | 贾学明 | Ultraviolet-curing paint and preparation method thereof |
| CN110408300B (en) * | 2018-04-26 | 2021-06-25 | 中钞特种防伪科技有限公司 | 100% solid content protective ultraviolet curing coating composition, coating and application thereof |
| TWI666670B (en) * | 2018-05-18 | 2019-07-21 | 致伸科技股份有限公司 | Keycap structure and manufacturing method thereof |
| CN113563794A (en) * | 2018-09-26 | 2021-10-29 | 苏州泛普科技股份有限公司 | High-hardness coating for teaching blackboard |
| CN110885253A (en) * | 2019-11-26 | 2020-03-17 | 嘉兴饶稷科技有限公司 | Laser scanning ceramic printing process |
| CN114058289A (en) * | 2020-08-07 | 2022-02-18 | 宁波安特弗新材料科技有限公司 | UV visbreaking adhesive and UV visbreaking adhesive tape |
| CN112430306B (en) * | 2020-11-17 | 2022-07-29 | 南京工程学院 | Self-reinforcing photochromic material and preparation method thereof |
| CN114409871B (en) * | 2022-03-04 | 2024-01-30 | 中科擎昆(东莞)科技有限公司 | Multifunctional resin, preparation method thereof and UV (ultraviolet) curing strippable coating material |
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| US20100276059A1 (en) * | 2009-04-30 | 2010-11-04 | Dong Tian | UVV curable coating compositions and method for coating flooring and other substrates with same |
| CN102558491A (en) * | 2011-10-20 | 2012-07-11 | 湖北固润科技股份有限公司 | Polyurethane oligomer taking vinyl ether as end group and synthesis method |
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