UV glass ink – UV Monomer
Glass and ceramics both contain silicates as the main ingredient. They are hard and brittle materials with polar surfaces. Therefore, they do not require the flexibility of UV ink. The key is to solve the adhesion problem with the substrate.
The main purpose of printing inks on glass surfaces is decoration and beautification. Glass printed with bright, colorful artistic patterns is often used to decorate building doors and windows, curtain walls and ceilings. The glass material is dense, and UV inks cannot penetrate, affecting adhesion. However, the glass surface has a rich silanol structure, so the adhesion between UV inks and glass can be improved by adding a silane coupling agent. A commonly used silane coupling agent is KH570, which is methacryloxy-γ-propyltrimethoxysilane and has a low surface energy (28×10-5N/cm). The methacryloxy group can participate in polymerization and cross-linking to become part of the cross-linked network, and the siloxane group can easily condense with the silanol groups on the glass surface to form a strong Si–O–Si structure, which improves the adhesion of the ink to the glass.
Glass inks and UV glass inks
are increasingly being used in printing on glass products. In everyday life, there are many glass products such as sliding doors, tea sets, photo frames, disinfection cabinets, refrigerator doors, furniture, etc., which have been decorated with screen printing or inkjet printing processes to become beautiful and colorful. Not only does it add value to the product, but it also beautifies our lives. But how are these colorful effects achieved? The main player is, of course, the ink. In screen printing on glass products, the inks currently used can be broadly divided into five categories: solvent-based one-component low-temperature baking inks, water-based low-temperature baking inks, two-component self-drying inks, high-temperature sintering (tempering) inks and UV-curable inks. Among the above five types of inks, UV-curable glass inks are a new type of ink that has been successfully developed in China in recent years. They have significant advantages over other types of inks in terms of energy saving, environmental protection, efficiency and operability, and are therefore increasingly popular with users (see Table 3-45).
Table 3-45 Comparison of UV glass inks and solvent-based glass inks
Decorating glass using the inkjet printing process has the advantages of not requiring plate making, digital printing, and personalization, and in particular the use of environmentally friendly UV inkjet inks and more energy-saving and environmentally friendly UV-LED inkjet inks (see Table 3-46), which have received attention and been promoted for use.
Table 3-46 Advantages of UV inkjet printing glass inks in glass printing
There are many types of UV glass inks, the most common being UV glass color inks, special effect UV glass inks, special function UV glass inks, functional UV glass varnishes, etc. There are UV screen printing glass inks, UV pad printing glass inks, UV waterless offset printing glass inks, water transfer printing UV glass inks, UV glass inkjet printing inks, UV-LED glass inkjet printing inks, etc., depending on the printing process; there are photopolymerization UV glass inks, high-temperature sintering UV glass inks, dual-curing UV glass inks, etc., depending on the curing method.
Preparation of UV glass inks
The properties of screen-printed UV glass inks are shown in Table 3-47.
Table 3-47 Properties of screen-printed UV glass inks
UV glass inks also consist of oligomers, reactive diluents, photoinitiators, pigments and additives. Commonly used oligomers are epoxy acrylates or urethane acrylates, reactive diluents are commonly used monomers such as TMPTA and TPGDA, and photoinitiators are mainly ITX and 907. When preparing UV glass inks, the following conditions should be given priority:
① UV Monomer: Choose reactive diluents with low surface tension (≤28dyn/cm) to achieve the goal of wetting and affinizing the glass surface.
② Photoinitiators: According to the light transmittance performance of ≥85% for glass, choose a photoinitiator with an absorption peak of 320–380 nm to achieve the best photoinitiation efficiency.
③ Oligomers: Silicone-modified acrylic resins are selected, as the silicone component can undergo a condensation reaction with the silicate component in the glass, and the acrylic component can undergo a photopolymerization reaction.
④ Pigments: Environmentally friendly pigments that are weather-resistant, non-migratory, non-discoloring, and have good heat resistance (200°C x 60 min) are selected based on the various process requirements of glass printing, such as heating and light curing.
⑤ Adhesion promoter: As the glass surface is dense and the ink cannot penetrate, it is necessary to add an appropriate additive or adhesion promoter to the ink to improve adhesion. The most common method is to add 0.5% to 1% of the organosilane coupling agent KH570. This is a silane coupling agent with a methacryloxy group, which can participate in photopolymerization and cross-linking polymerization, and the silane coupling agent can condense with the glass. In addition, the addition of the trifunctional ester CD9051 (5% to 7%) can also significantly improve the adhesion of the coating film to the glass. Some pure acrylic resins also have an effect on improving adhesion to glass.
UV glass ink reference formula
(1) UV white glass screen printing ink reference formula
Low-viscosity PUA (CN987) 27.75
Low-viscosity monoacrylate oligomer (CN131) 10.00
POEA 30.00
Non-migrating, non-yellowing photoinitiator (SR1113) 6.00
Wetting agent (SR022) 0.25
Non-silicone leveling agent (SR012) 1.00
(2) Reference formula for UV black glass screen printing ink
Aromatic acid acrylate copolymer (SB520E35) 46.0
Low-viscosity monoacrylate oligomer (CN131) 22.0
POEA 20.0
907 4.5
ITX 0.5
BP 2.0
Carbon black (Raven 450) 4.0
Non-silicone leveling agent (SR012) 1.0
(3) Reference formula for UV pad printing white glass ink
Trifunctional PEA 20
ACMO 8
LA 5
907 3
DETX 0.3
TPO 2
Co-initiator EHA 2
Titanium dioxide R-706 20
Titanium dioxide R-900 25
Defoamer S43 0.5
Defoamer Arix920 2
Leveling agent RAD2200 0.3
(4) Reference formula for UV pad printing black glass ink
Trifunctional PEA 25
Bifunctional PEA 15
ACMO 8
LA 10
907 3
DETX 1
TPO 2
Accelerator EDAB 1
Accelerator DMBI 1
Carbon black 8
Defoamer Arix920 3
Leveling agent RAD2300 0.3
(5) Reference formula for UV pad printing red glass ink
Trifunctional PEA 25
Bis-functional PEA 15
ACMO 7
LA 10
907 3
DETX 1
184 3
Accelerator EDAB 1
Accelerator EHA 1
Magenta (57:1) 12
Defoamer EFKA-4050 1
Defoamer KS66 0.5
Leveling agent BYK306 0.3
(6) Reference formulation for UV pad printing blue glass ink
Trifunctional PEA 20
Bifunctional PEA 10
ACMO 10
LA 10
907 4
DETX 0.3
TPO 2
Accelerator EHA 1
Phthalocyanine blue 15
Defoamer Arix920 0.5
Leveling agent BYK163 0.3
Ink properties:
Light curing speed (80W/cm2) 3–6s
Adhesion (cross-hatch method) 100/100
Ethanol resistance (95% ethanol) 100 times
Acetone resistance 50 times
Acid resistance (5% sulfuric acid) 16h
Alkaline resistance (5% NaOH) 12h
Boiling water resistance (100°C boiling water) 1h No shedding
(7) UV screen printing red glass ink reference formula
Trifunctional PEA 25
Bifunctional PEA 15
ACMO 27
LA 10
907 3
DETX 1
184 3
Initiator EDAB 1
Initiator EHA 1
Magenta (57:1) 12
Defoamer EFKA-4050 1
Defoamer KS66 0.5
Leveling agent BYK306 0.3
(8) Reference formula for UV screen printing white glass ink
Trifunctional PEA 20
ACMO 23
LA 5
907 3
DETX 0.3
TPO 2
Co-initiator EHA 2
Titanium dioxide R-706 20
Titanium dioxide R-900 25
Defoamer S43 0.5
Defoamer Arix920 2
Leveling agent RAD2200 0.3
(9) Reference formula for UV screen printing black glass ink
Trifunctional PEA 25
Bifunctional PEA 15
ACMO 28
LA 10
907 3
DETX 1
TPO 2
Accelerator EDAB 1
Accelerator DMBI 1
Carbon black 8
Defoamer Arix920 3
Leveling agent RAD2300 0.3
(10) Reference formula for UV screen printing blue glass ink
Tri-functional PEA 20
Bis-functional PEA 10
ACMO 32
LA 10
907 4
DETX 0.3
TPO 2
Accelerator EHA 1
Phthalocyanine blue 15
Leveling agent BYK-163 0.3
Defoamer Arix920 0.5
Ink properties: Light curing speed (80W/cm2) 3–6s
Adhesion (cross-hatch method) 100/100
Ethanol resistance (95% ethanol) 100 times
Acetone resistance 50 times
Acid resistance (5% sulfuric acid) 16h
Alkaline resistance (5% NaOH) 12h
Boiling water resistance (100°C boiling water) 1h No shedding
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| Polythiol/Polymercaptan | ||
| DMES Monomer | Bis(2-mercaptoethyl) sulfide | 3570-55-6 |
| DMPT Monomer | THIOCURE DMPT | 131538-00-6 |
| PETMP Monomer | 7575-23-7 | |
| PM839 Monomer | Polyoxy(methyl-1,2-ethanediyl) | 72244-98-5 |
| Monofunctional Monomer | ||
| HEMA Monomer | 2-hydroxyethyl methacrylate | 868-77-9 |
| HPMA Monomer | 2-Hydroxypropyl methacrylate | 27813-02-1 |
| THFA Monomer | Tetrahydrofurfuryl acrylate | 2399-48-6 |
| HDCPA Monomer | Hydrogenated dicyclopentenyl acrylate | 79637-74-4 |
| DCPMA Monomer | Dihydrodicyclopentadienyl methacrylate | 30798-39-1 |
| DCPA Monomer | Dihydrodicyclopentadienyl Acrylate | 12542-30-2 |
| DCPEMA Monomer | Dicyclopentenyloxyethyl Methacrylate | 68586-19-6 |
| DCPEOA Monomer | Dicyclopentenyloxyethyl Acrylate | 65983-31-5 |
| NP-4EA Monomer | (4) ethoxylated nonylphenol | 50974-47-5 |
| LA Monomer | Lauryl acrylate / Dodecyl acrylate | 2156-97-0 |
| THFMA Monomer | Tetrahydrofurfuryl methacrylate | 2455-24-5 |
| PHEA Monomer | 2-PHENOXYETHYL ACRYLATE | 48145-04-6 |
| LMA Monomer | Lauryl methacrylate | 142-90-5 |
| IDA Monomer | Isodecyl acrylate | 1330-61-6 |
| IBOMA Monomer | Isobornyl methacrylate | 7534-94-3 |
| IBOA Monomer | Isobornyl acrylate | 5888-33-5 |
| EOEOEA Monomer | 2-(2-Ethoxyethoxy)ethyl acrylate | 7328-17-8 |
| Multifunctional monomer | ||
| DPHA Monomer | 29570-58-9 | |
| DI-TMPTA Monomer | DI(TRIMETHYLOLPROPANE) TETRAACRYLATE | 94108-97-1 |
| Acrylamide monomer | ||
| ACMO Monomer | 4-acryloylmorpholine | 5117-12-4 |
| Di-functional Monomer | ||
| PEGDMA Monomer | Poly(ethylene glycol) dimethacrylate | 25852-47-5 |
| TPGDA Monomer | Tripropylene glycol diacrylate | 42978-66-5 |
| TEGDMA Monomer | Triethylene glycol dimethacrylate | 109-16-0 |
| PO2-NPGDA Monomer | Propoxylate neopentylene glycol diacrylate | 84170-74-1 |
| PEGDA Monomer | Polyethylene Glycol Diacrylate | 26570-48-9 |
| PDDA Monomer | Phthalate diethylene glycol diacrylate | |
| NPGDA Monomer | Neopentyl glycol diacrylate | 2223-82-7 |
| HDDA Monomer | Hexamethylene Diacrylate | 13048-33-4 |
| EO4-BPADA Monomer | ETHOXYLATED (4) BISPHENOL A DIACRYLATE | 64401-02-1 |
| EO10-BPADA Monomer | ETHOXYLATED (10) BISPHENOL A DIACRYLATE | 64401-02-1 |
| EGDMA Monomer | Ethylene glycol dimethacrylate | 97-90-5 |
| DPGDA Monomer | Dipropylene Glycol Dienoate | 57472-68-1 |
| Bis-GMA Monomer | Bisphenol A Glycidyl Methacrylate | 1565-94-2 |
| Trifunctional Monomer | ||
| TMPTMA Monomer | Trimethylolpropane trimethacrylate | 3290-92-4 |
| TMPTA Monomer | Trimethylolpropane triacrylate | 15625-89-5 |
| PETA Monomer | 3524-68-3 | |
| GPTA ( G3POTA ) Monomer | GLYCERYL PROPOXY TRIACRYLATE | 52408-84-1 |
| EO3-TMPTA Monomer | Ethoxylated trimethylolpropane triacrylate | 28961-43-5 |
| Photoresist Monomer | ||
| IPAMA Monomer | 2-isopropyl-2-adamantyl methacrylate | 297156-50-4 |
| ECPMA Monomer | 1-Ethylcyclopentyl Methacrylate | 266308-58-1 |
| ADAMA Monomer | 1-Adamantyl Methacrylate | 16887-36-8 |
| Methacrylates monomer | ||
| TBAEMA Monomer | 2-(Tert-butylamino)ethyl methacrylate | 3775-90-4 |
| NBMA Monomer | n-Butyl methacrylate | 97-88-1 |
| MEMA Monomer | 2-Methoxyethyl Methacrylate | 6976-93-8 |
| i-BMA Monomer | Isobutyl methacrylate | 97-86-9 |
| EHMA Monomer | 2-Ethylhexyl methacrylate | 688-84-6 |
| EGDMP Monomer | Ethylene glycol Bis(3-mercaptopropionate) | 22504-50-3 |
| EEMA Monomer | 2-ethoxyethyl 2-methylprop-2-enoate | 2370-63-0 |
| DMAEMA Monomer | N,M-Dimethylaminoethyl methacrylate | 2867-47-2 |
| DEAM Monomer | Diethylaminoethyl methacrylate | 105-16-8 |
| CHMA Monomer | Cyclohexyl methacrylate | 101-43-9 |
| BZMA Monomer | Benzyl methacrylate | 2495-37-6 |
| BDDMP Monomer | 1,4-Butanediol Di(3-mercaptopropionate) | 92140-97-1 |
| BDDMA Monomer | 1,4-Butanedioldimethacrylate | 2082-81-7 |
| AMA Monomer | Allyl methacrylate | 96-05-9 |
| AAEM Monomer | Acetylacetoxyethyl methacrylate | 21282-97-3 |
| Acrylates Monomer | ||
| IBA Monomer | Isobutyl acrylate | 106-63-8 |
| EMA Monomer | Ethyl methacrylate | 97-63-2 |
| DMAEA Monomer | Dimethylaminoethyl acrylate | 2439-35-2 |
| DEAEA Monomer | 2-(diethylamino)ethyl prop-2-enoate | 2426-54-2 |
| CHA Monomer | cyclohexyl prop-2-enoate | 3066-71-5 |
| BZA Monomer | benzyl prop-2-enoate | 2495-35-4 |