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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| 聚硫醇/聚硫醇 | ||
| DMES 单体 | 双（2-巯基乙基）硫醚 | 3570-55-6 |
| DMPT 单体 | THIOCURE DMPT | 131538-00-6 |
| PETMP 单体 | 7575-23-7 | |
| PM839 单体 | 聚氧（甲基-1,2-乙二基） | 72244-98-5 |
| 单官能团单体 | ||
| HEMA 单体 | 甲基丙烯酸 2-羟乙基酯 | 868-77-9 |
| HPMA 单体 | 甲基丙烯酸羟丙酯 | 27813-02-1 |
| THFA 单体 | 丙烯酸四氢糠酯 | 2399-48-6 |
| HDCPA 单体 | 氢化双环戊烯丙烯酸酯 | 79637-74-4 |
| DCPMA 单体 | 甲基丙烯酸二氢双环戊二烯酯 | 30798-39-1 |
| DCPA 单体 | 丙烯酸二氢双环戊二烯酯 | 12542-30-2 |
| 二氯丙烯酰亚胺单体 | 甲基丙烯酸二环戊氧基乙酯 | 68586-19-6 |
| DCPEOA 单体 | 丙烯酸二环戊烯基氧基乙基酯 | 65983-31-5 |
| NP-4EA 单体 | (4) 乙氧基化壬基酚 | 50974-47-5 |
| LA 单体 | 丙烯酸十二烷基酯/丙烯酸十二烷基酯 | 2156-97-0 |
| THFMA 单体 | 甲基丙烯酸四氢糠酯 | 2455-24-5 |
| PHEA 单体 | 2-苯氧基乙基丙烯酸酯 | 48145-04-6 |
| LMA 单体 | 甲基丙烯酸月桂酯 | 142-90-5 |
| IDA 单体 | 丙烯酸异癸酯 | 1330-61-6 |
| IBOMA 单体 | 甲基丙烯酸异冰片酯 | 7534-94-3 |
| IBOA 单体 | 丙烯酸异冰片酯 | 5888-33-5 |
| EOEOEA 单体 | 2-(2-乙氧基乙氧基)丙烯酸乙酯 | 7328-17-8 |
| 多功能单体 | ||
| DPHA 单体 | 29570-58-9 | |
| DI-TMPTA 单体 | 二（三羟甲基丙烷）四丙烯酸酯 | 94108-97-1 |
| 丙烯酰胺单体 | ||
| ACMO 单体 | 4-丙烯酰基吗啉 | 5117-12-4 |
| 双功能单体 | ||
| PEGDMA 单体 | 聚乙二醇二甲基丙烯酸酯 | 25852-47-5 |
| TPGDA 单体 | 三丙二醇二丙烯酸酯 | 42978-66-5 |
| TEGDMA 单体 | 三乙二醇二甲基丙烯酸酯 | 109-16-0 |
| PO2-NPGDA 单体 | 丙氧基新戊二醇二丙烯酸酯 | 84170-74-1 |
| PEGDA 单体 | 聚乙二醇二丙烯酸酯 | 26570-48-9 |
| PDDA 单体 | 邻苯二甲酸二乙二醇二丙烯酸酯 | |
| NPGDA 单体 | 新戊二醇二丙烯酸酯 | 2223-82-7 |
| HDDA 单体 | 二丙烯酸六亚甲基酯 | 13048-33-4 |
| EO4-BPADA 单体 | 乙氧基化 (4) 双酚 A 二丙烯酸酯 | 64401-02-1 |
| EO10-BPADA 单体 | 乙氧基化 (10) 双酚 A 二丙烯酸酯 | 64401-02-1 |
| EGDMA 单体 | 乙二醇二甲基丙烯酸酯 | 97-90-5 |
| DPGDA 单体 | 二丙二醇二烯酸酯 | 57472-68-1 |
| 双-GMA 单体 | 双酚 A 甲基丙烯酸缩水甘油酯 | 1565-94-2 |
| 三官能单体 | ||
| TMPTMA 单体 | 三羟甲基丙烷三甲基丙烯酸酯 | 3290-92-4 |
| TMPTA 单体 | 三羟甲基丙烷三丙烯酸酯 | 15625-89-5 |
| PETA 单体 | 3524-68-3 | |
| GPTA ( G3POTA ) 单体 | 丙氧基三丙烯酸甘油酯 | 52408-84-1 |
| EO3-TMPTA 单体 | 三羟甲基丙烷三丙烯酸乙氧基化物 | 28961-43-5 |
| 光阻单体 | ||
| IPAMA 单体 | 2-异丙基-2-金刚烷基甲基丙烯酸酯 | 297156-50-4 |
| ECPMA 单体 | 1-乙基环戊基甲基丙烯酸酯 | 266308-58-1 |
| ADAMA 单体 | 1-金刚烷基甲基丙烯酸酯 | 16887-36-8 |
| 甲基丙烯酸酯单体 | ||
| TBAEMA 单体 | 2-(叔丁基氨基)乙基甲基丙烯酸酯 | 3775-90-4 |
| NBMA 单体 | 甲基丙烯酸正丁酯 | 97-88-1 |
| MEMA 单体 | 甲基丙烯酸 2-甲氧基乙酯 | 6976-93-8 |
| i-BMA 单体 | 甲基丙烯酸异丁酯 | 97-86-9 |
| EHMA 单体 | 甲基丙烯酸 2-乙基己酯 | 688-84-6 |
| EGDMP 单体 | 乙二醇双(3-巯基丙酸酯) | 22504-50-3 |
| EEMA 单体 | 2-甲基丙-2-烯酸 2-乙氧基乙酯 | 2370-63-0 |
| DMAEMA 单体 | 甲基丙烯酸 N,M-二甲基氨基乙酯 | 2867-47-2 |
| DEAM 单体 | 甲基丙烯酸二乙氨基乙酯 | 105-16-8 |
| CHMA 单体 | 甲基丙烯酸环己基酯 | 101-43-9 |
| BZMA 单体 | 甲基丙烯酸苄酯 | 2495-37-6 |
| BDDMP 单体 | 1,4-丁二醇二（3-巯基丙酸酯） | 92140-97-1 |
| BDDMA 单体 | 1,4-丁二醇二甲基丙烯酸酯 | 2082-81-7 |
| AMA 单体 | 甲基丙烯酸烯丙酯 | 96-05-9 |
| AAEM 单体 | 甲基丙烯酸乙酰乙酰氧基乙基酯 | 21282-97-3 |
| 丙烯酸酯单体 | ||
| IBA 单体 | 丙烯酸异丁酯 | 106-63-8 |
| EMA 单体 | 甲基丙烯酸乙酯 | 97-63-2 |
| DMAEA 单体 | 丙烯酸二甲胺基乙酯 | 2439-35-2 |
| DEAEA 单体 | 2-(二乙基氨基)乙基丙-2-烯酸酯 | 2426-54-2 |
| CHA 单体 | 丙-2-烯酸环己基酯 | 3066-71-5 |
| BZA 单体 | 丙-2-烯酸苄酯 | 2495-35-4 |