CN117363162A - Low-viscosity rapid UV-LED curing cationic composition and preparation method thereof - Google Patents
Low-viscosity rapid UV-LED curing cationic composition and preparation method thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 230000002708 enhancing effect Effects 0.000 claims abstract description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 13
- -1 glycidyl ester Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 230000001965 increasing effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 125000003566 oxetanyl group Chemical group 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000001723 curing Methods 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
Abstract
The invention discloses a low-viscosity rapid UV-LED curing cationic composition and a preparation method thereof, wherein the composition comprises the following components in percentage by weight based on 100% of the total mass of the composition: 30% -70% of alicyclic epoxy compound; 10% -70% of reactive diluent; 1-8% of a photoinitiator; 0.1-2% of a sense enhancing agent; 10% -30% of color paste; 2-5% of auxiliary agent. The invention has the advantages that the viscosity can be reduced, the curing speed of the UV-LED can be further improved, and the cured product has better adhesive force, chemical resistance and heat resistance.
Description
Technical Field
The invention relates to the technical field of photo-curing, in particular to a low-viscosity rapid UV-LED curing cationic composition and a preparation method thereof.
Background
The photo-curing technology is widely applied to the field of paint and ink due to the outstanding advantages of high efficiency, energy conservation, environmental protection and the like; the traditional UV curing light source mainly comprises a high-pressure mercury lamp, but has the defects of low energy efficiency, large heating value, short service life, ozone pollution, heavy metal mercury and the like, so that the development and use of a novel energy-saving and environment-friendly curing light source tend to take place, and the UV-LED light source has the characteristics of high luminous efficiency, long service life, energy conservation, environment friendliness, less heat release and the like, overcomes the defects of the traditional light source, and has more and more related products;
the photo-curing technology can be divided into UV free radical curing and cationic curing, the former has wider application, but has the problem of difficult oxygen polymerization inhibition and surface drying, and particularly, the low-viscosity thin-coating LED curing limits the application of the low-viscosity thin-coating LED curing in certain fields; the cationic photo-curing oxygen-free polymerization inhibition can make up the defect of free radicals, and is more suitable for curing the low-viscosity thin-coating LED;
in the existing UV-LED high-speed ink-jet technology, a free radical system is used for overcoming oxygen polymerization inhibition, the consumption of an initiator is greatly increased, the problems of resource waste, cost rise and safety and environmental protection are caused, the chemical resistance of a cured product is poor, the existing cation system can overcome the oxygen polymerization inhibition problem and the chemical resistance is improved, but most of the technology is mainly used for reducing the viscosity by taking alicyclic epoxy 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylmethyl formate, and a large amount of diluents such as glycidyl ether epoxy, oxetane and vinyl ether are required to be matched, so that the performances of the cured product such as the chemical resistance, the heat resistance and the adhesive force are lost, and the curing speed is still slower than that of the free radical; therefore, it is desirable to provide a low viscosity, fast UV-LED curing cationic composition that combines excellent cured properties.
Disclosure of Invention
The invention aims to solve the problems, and designs a low-viscosity rapid UV-LED curing cationic composition and a preparation method thereof.
The technical scheme of the invention for achieving the purpose is that a low-viscosity rapid UV-LED curing cationic composition comprises the following components in percentage by weight, based on 100% of the total mass of the composition: 30% -70% of alicyclic epoxy compound; 10% -70% of reactive diluent; 1-8% of a photoinitiator; 0.1-2% of a sense enhancing agent; 10% -30% of color paste; 2-5% of auxiliary agent.
Further supplementing the technical scheme, the alicyclic epoxy compound is one or more selected from TTA21, TTA20, TTA22, TTA28 and TTA800 of Jiangsu Taier New Material technology Co.
Further supplementing the technical scheme, the reactive diluent is one or more of glycidyl ether type epoxy, glycidyl ester type epoxy, oxetane structure epoxy and vinyl ether.
Further to the technical scheme, the photoinitiator is one or more of aryl diazonium salt, diaryl iodonium salt, triarylsulfonium salt and aryl ferrocenium salt.
Further supplementing the technical scheme, the sensitizer is one or more of anthracene, coumarin and thioxanthone compounds.
According to the technical scheme, the color paste is self-made cationic color paste, and the total mass of the color paste is 100%, and the color paste comprises the following components in percentage by weight: 30-70% of alicyclic epoxy compound, 10-70% of oxetane epoxy, 10-50% of pigment, 1-10% of wetting dispersant and 0.1-0.5% of defoamer.
Further supplementing the technical scheme, the auxiliary agent comprises a leveling agent and a defoaming agent.
The technical proposal is further supplemented, and the leveling agent is one or more of BYK373, BYK315, BYK325, BYK331, BYK333, BYK310, BYK307 and BYK 300; the defoaming agent is one or more of polyether defoaming agent, organic silicon defoaming agent and polyether modified organic silicon defoaming agent.
A method of preparing a low viscosity rapid UV-LED curing cationic composition comprising the steps of:
step one: mixing the alicyclic epoxy compound, the reactive diluent, the initiator, the inductance increasing agent and the auxiliary agent in a light-proof or yellow light environment at room temperature and normal pressure, and stirring until the solid compound is completely dissolved;
step two: and (3) filtering the product obtained in the step (A), and obtaining the UV-LED curing cationic composition which is gloss oil and can be used in ink jet, and forming a curing film through spraying the gloss oil onto a material and curing by illumination, so that a good protection effect is achieved.
According to the technical scheme, the UV-LED curing cationic composition further comprises color paste, the color paste is added into the gloss oil obtained in the second step, stirring, high-speed dispersion and filtering are carried out, and the UV-LED curing cationic composition ink can be used for ink jet and is colored in a mode of being sprayed to the surface of a printing material without an intermediate medium.
The cationic composition has the beneficial effects that the viscosity can be reduced, the UV-LED curing speed can be further improved, the cured product has better adhesive force, chemical resistance and heat resistance, the cationic composition absorbs energy under the radiation of an LED light source, excited sensitizer molecules are complexed with ground state photoinitiator molecules to form an excited state compound, the excited state compound is subjected to internal electron transfer, the sensitizer molecules are transited back to the ground state, and the photoinitiator molecules reach the excited state, so that the carbon cation active center is generated by decomposition, the epoxy resin and the monomer are initiated to carry out ring-opening polymerization, and the cured film is formed by crosslinking; compared with the existing cationic system, the curing speed can be further improved, the consumption of the diluent is reduced, the adhesive force and the chemical resistance of the cured product are improved, and the glass transition temperature (Tg) of the cured product is not influenced; thus, the cationic composition described above can be used as a UV ink, meeting the application requirements of high-speed UV-LED inkjet.
Detailed Description
The process equipment and conditions not identified in the following examples and comparative examples are those conventional in the art. Unless otherwise indicated, all materials and the like used in the examples of the present invention were commercially available. All technical means in the examples are, if specifically indicated, conventional means well known to those skilled in the art.
In order to make the technical solution more clear to the person skilled in the art, the following details of the technical solution of the present invention are described:
a low viscosity fast UV-LED curing cationic composition consisting of, based on 100% of the total mass of the composition, the following weight percentages: 30% -70% of alicyclic epoxy compound; 10% -70% of reactive diluent; 1-8% of a photoinitiator; 0.1-2% of a sense enhancing agent; 10% -30% of color paste; 2-5% of auxiliary agent.
Further supplementing the technical scheme, the alicyclic epoxy compound is one or more selected from TTA21, TTA20, TTA22, TTA28 and TTA800 of Jiangsu Taier New Material technology Co.
Further supplementing the technical scheme, the reactive diluent is one or more of glycidyl ether type epoxy, glycidyl ester type epoxy, oxetane structure epoxy and vinyl ether.
Further to the technical scheme, the photoinitiator is one or more of aryl diazonium salt, diaryl iodonium salt, triarylsulfonium salt and aryl ferrocenium salt.
Further supplementing the technical scheme, the sensitizer is one or more of anthracene, coumarin and thioxanthone compounds.
According to the technical scheme, the color paste is self-made cationic color paste, and the total mass of the color paste is 100%, and the color paste comprises the following components in percentage by weight: 30-70% of alicyclic epoxy compound, 10-70% of oxetane epoxy, 10-50% of pigment, 1-10% of wetting dispersant and 0.1-0.5% of defoamer.
Further supplementing the technical scheme, the auxiliary agent comprises a leveling agent and a defoaming agent.
The technical proposal is further supplemented, and the leveling agent is one or more of BYK373, BYK315, BYK325, BYK331, BYK333, BYK310, BYK307 and BYK 300; the defoaming agent is one or more of polyether defoaming agent, organic silicon defoaming agent and polyether modified organic silicon defoaming agent.
A method of preparing a low viscosity rapid UV-LED curing cationic composition comprising the steps of:
step one: mixing the alicyclic epoxy compound, the reactive diluent, the initiator, the inductance increasing agent and the auxiliary agent in a light-proof or yellow light environment at room temperature and normal pressure, and stirring until the solid compound is completely dissolved;
step two: and (3) filtering the product obtained in the step (A), and obtaining the UV-LED curing cationic composition which is gloss oil and can be used in ink jet, and forming a curing film through spraying the gloss oil onto a material and curing by illumination, so that a good protection effect is achieved.
The UV-LED curing cationic composition further comprises color paste, the color paste is added into the gloss oil obtained in the second step, stirring is carried out, high-speed dispersion is carried out, filtering is carried out, and the UV-LED curing cationic composition ink can be used for ink jet and is used for coloring in a mode of being sprayed onto the surface of a printing material, and an intermediate medium is not needed.
Examples 1 to 9
The cationic compositions of examples 1 to 9 were formulated with the mass percent compositions shown in table 1 below.
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| TTA21 | / | / | / | / | / | 20 | 20 | 20 | / |
| TTA22 | 46 | / | / | / | / | / | / | 26 | / |
| TTA28 | / | 46 | 25 | / | / | / | 26 | / | 20 |
| TTA800 | / | / | / | 46 | 46 | 35 | / | / | 48.6 |
| TR-TCM201 | 30 | 30 | 41 | 20 | 30 | 21 | 30 | 30 | 20 |
| XY-692 | / | / | 10 | 10 | / | / | / | / | / |
| TR-PAG20102P | 8 | 8 | 8 | 8 | / | 8 | 8 | 8 | 10 |
| TR-PAG30301 | / | / | / | / | 4 | / | / | / | / |
| TR-PSS306 | 0.6 | 0.6 | 0.6 | 0.6 | / | 0.6 | 0.6 | 0.6 | 1 |
| ITX | / | / | / | / | 0.6 | / | / | / | / |
| Black color paste | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | / |
| BYK333 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| BYK055 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Comparative examples 1 to 4
Cationic compositions of comparative examples 1 to 4 were formulated with the mass percent compositions shown in Table 2 below
The preparation method of the cationic composition in the above examples and comparative examples is the same, and includes the following steps
Step one: and under the conditions of light shielding or yellow light and normal pressure at room temperature, mixing the alicyclic epoxy compound, the reactive diluent, the initiator, the sense enhancing agent and the auxiliary agent, stirring until the solid compound is completely dissolved, and filtering the product to obtain the composition gloss oil.
Step two: if the pigment is needed to be added, the gloss oil obtained in the step one is added with color paste, stirred, dispersed at high speed and filtered to obtain the UV-LED curing cationic composition ink.
The cationic compositions prepared in the above examples and comparative examples were subjected to a viscosity, a curing speed, an adhesion, a chemical resistance test, and a heat resistance test.
1. Viscosity test
The testing method comprises the following steps: the viscosity of the compositions of examples and comparative examples was measured at 25℃using a rotational viscometer.
2. Curing speed
The testing method comprises the following steps: the coating is coated on a PET film by adopting a 5um bar roller, and is exposed under a curing machine with a 395nm LED light source, and the minimum energy required by the surface drying of the coating is compared.
Evaluation criteria: the lower the energy required for the coating to set up, the faster the cure speed.
3. Adhesion force
The testing method comprises the following steps: the PET film is coated with a 5um bar roller, exposed under a curing machine with 395nm LED light source (5000 mJ/cm < 2 >), fully cured, placed at room temperature for 24 hours, and subjected to a cross-cut test according to the specification of GB/T9286-2021.
Evaluation criteria: judging the adhesion level according to the surface falling condition, wherein the level 0 is that the scribing edge is smooth, and no marks fall off at the scribing edge and the intersection point; the level 1 is that the small piece falls off at the cross point of the scribing line, and the total falling area cannot be obviously more than 5%; the level 2 is that the edges of the scribing lines and the crossing points are provided with small pieces to fall off, and the total falling-off area is between 5 and 15 percent; the level 3 is that the edges and the intersections of the scribing lines are provided with flaking falling off, and the falling off area is between 15 and 35 percent; the level 4 is that the edges and the intersections of the scribing lines are provided with flaking falling off, and the falling off area is between 35 and 65 percent; grade 5 is a degree of shedding exceeding grade 4.
4. Resistance to chemical transformation
The testing method comprises the following steps: the PET film is coated with a 5um coil bar roller, exposed under a curing machine with a 395nm LED light source (5000 mJ/cm < 2 >), fully cured, placed at room temperature for 24 hours, subjected to a 95% ethanol-resistant wiping test according to the specification of GB/T23989-2009, and subjected to a solvent-resistant wiping instrument load of 1kg at a rotating speed of 60rpm.
Evaluation criteria: the number of wiping times is 100, the coating is qualified without fading and bottomless, and is represented by OK, otherwise, the coating is unqualified, and is represented by NG.
5. Heat resistance
The testing method comprises the following steps: the glass transition temperature (Tg) of the cured product is tested by a DMA film stretching method by adopting a20 um bar roller coating on a release film, placing the release film under a curing machine with a 395nm LED light source for exposure (5000 mJ/cm < 2 >), standing the release film at room temperature for 24 hours after complete curing, cutting the release film into 10mm long strips with 50 mm.
Evaluation criteria: the higher the Tg, the better the heat resistance.
The test results of the examples and comparative examples were obtained according to the above test methods and determination criteria as follows.
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Viscosity (25 ℃ C.) | 15 | 18 | 16 | 20 | 19 | 24 | 21 | 20 | 23 |
| Energy of surface drying (mJ/cm) 2 ) | 1400 | 950 | 700 | 500 | 350 | 1200 | 1250 | 1550 | 25 |
| Tg(℃) | 94 | 106 | 101 | 112 | 113 | 108 | 105 | 98 | 121 |
| Adhesion force | 0 | 0 | 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| Resistance to chemical transformation | OK | OK | OK | OK | OK | OK | OK | OK | OK |
Examples 1, 2, 4, and 5 have lower viscosity, faster cure speed, while maintaining a higher glass transition temperature (Tg), and better resistance to chemicals and adhesion than the comparative examples, with example 5 having the fastest cure speed, highest Tg, and the best combination of properties. Example 3 further improved the curing speed but reduced the adhesion as compared with example 2. Examples 6, 7, 8 are faster in curing speed than the comparative examples, and the low-viscosity alicyclic epoxy compound is not reduced in cured product properties, particularly heat resistance, than the other reactive diluents. In addition, example 9 is a gloss oil composition with faster UV-LED cure speed.
| Comparative example 1 | Comparative example 2 | Comparative example 2 | Comparative example 3 | |
| Viscosity (25 ℃ C.) | 55 | 19 | 20 | 17 |
| Energy of surface drying (mJ/cm) 2 ) | 3200 | 1500 | 1800 | 1650 |
| Tg(℃) | 101 | 91 | 75 | 81 |
| Adhesion force | 0 | 3 | 0 | 3 |
| Resistance to chemical transformation | OK | OK | NG | NG |
Comparative examples 2, 3,4, compared to comparative example 1, have more reactive diluent added to reduce viscosity, resulting in undesirable overall properties, particularly a reduction in glass transition temperature (Tg). The oxetane and alicyclic epoxy compound curing speed is high, but the adhesive force is reduced; the cationic reactivity of the glycidyl ether is low, the curing is insufficient, the chemical resistance is poor, and the dosage is not easy to be excessive; the vinyl ether monomer in the above combination affects the adhesion and chemical resistance of the cured product.
The sources of cycloaliphatic epoxy compounds and diluents used in the examples and comparative examples are shown below in Table 5:
the alicyclic epoxy compounds are all from Jiangsu Taier New Material Co., ltd; oxetane diluents are all available from Changzhou powerful electronic New materials Co., ltd; the glycidyl ether diluents were all from Anhui New and remote technologies Inc.; vinyl ether diluents were all from Hebei Kairei chemical Co.
The sources of photoinitiators and extenders used for the examples and comparative examples are as follows, table 6:
the photoinitiator, coumarin and anthracene type sensitizer are all from Changzhou powerful electronic new material Co., ltd; thioxanthones are available from Zhejiang Sail New Material Co.
The defoamer, the leveling agent and the dispersing agent are all selected from Pick in Germany, and the pigment is selected from inorganic pigment or organic pigment, which are all conventional commercial products in the field.
The above technical solution only represents the preferred technical solution of the present invention, and some changes that may be made by those skilled in the art to some parts of the technical solution represent the principles of the present invention, and the technical solution falls within the scope of the present invention.
Claims (10)
1. A low viscosity fast UV-LED curing cationic composition characterized in that it consists of, based on 100% of the total mass of the composition, the following weight percentages: 30% -70% of alicyclic epoxy compound; 10% -70% of reactive diluent; 1-8% of a photoinitiator; 0.1-2% of a sense enhancing agent; 10% -30% of color paste; 2-5% of auxiliary agent.
2. The low viscosity fast UV-LED curing cationic composition according to claim 1, wherein said cycloaliphatic epoxy compound is selected from one or more of TTA21, TTA20, TTA22, TTA28, TTA800, new materials science and technology limited, stachattel.
3. The low viscosity fast UV-LED curing cationic composition according to claim 1, wherein said reactive diluent is one or more of a glycidyl ether type epoxy, a glycidyl ester type epoxy, an oxetane structure epoxy, a vinyl ether.
4. The low viscosity fast UV-LED curing cationic composition according to claim 1, wherein said photoinitiator is one or more of aryl diazonium salts, diaryl iodonium salts, triarylsulfonium salts, and aryl ferrocenium salts.
5. The low viscosity rapid UV-LED curing cationic composition of claim 1, wherein said sensitizer is one or more of anthracene, coumarin, thioxanthone compounds.
6. The low-viscosity rapid UV-LED curing cationic composition according to claim 1, wherein the color paste is a self-made cationic color paste, the color paste is composed of the following components in percentage by weight, based on 100% of the total mass: 30-70% of alicyclic epoxy compound, 10-70% of oxetane epoxy, 10-50% of pigment, 1-10% of wetting dispersant and 0.1-0.5% of defoamer.
7. A low viscosity fast UV-LED curing cationic composition according to claim 1, wherein said adjuvant comprises a leveling agent, an antifoaming agent.
8. The low viscosity fast UV-LED curing cationic composition according to claim 7, wherein said leveling agent is one or more of BYK373, BYK315, BYK325, BYK331, BYK333, BYK310, BYK307, BYK 300; the defoaming agent is one or more of polyether defoaming agent, organic silicon defoaming agent and polyether modified organic silicon defoaming agent.
9. A method of preparing a low viscosity fast UV-LED curing cationic composition according to any of claims 1-8, comprising the steps of:
step one: mixing the alicyclic epoxy compound, the reactive diluent, the initiator, the inductance increasing agent and the auxiliary agent in a light-proof or yellow light environment at room temperature and normal pressure, and stirring until the solid compound is completely dissolved;
step two: and (3) filtering the product obtained in the step (A), and obtaining the UV-LED curing cationic composition which is gloss oil and can be used in ink jet, and forming a curing film through spraying the gloss oil onto a material and curing by illumination, so that a good protection effect is achieved.
10. The method for preparing the low-viscosity rapid UV-LED curing cationic composition according to claim 9, wherein the UV-LED curing cationic composition further comprises color paste, wherein the color paste is added into the gloss oil obtained in the second step, and the gloss oil is stirred, dispersed at a high speed and filtered to obtain the UV-LED curing cationic composition ink which can be used for inkjet and is colored by spraying on the surface of a printing material without an intermediate medium.
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| CN102492330A (en) * | 2011-12-02 | 2012-06-13 | 中山大学 | Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink |
| CN116009356A (en) * | 2022-12-15 | 2023-04-25 | 珠海天威新材料股份有限公司 | Ultraviolet radiation curing cationic composition, preparation method thereof and digital ink-jet printing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492330A (en) * | 2011-12-02 | 2012-06-13 | 中山大学 | Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink |
| CN116009356A (en) * | 2022-12-15 | 2023-04-25 | 珠海天威新材料股份有限公司 | Ultraviolet radiation curing cationic composition, preparation method thereof and digital ink-jet printing method |
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