CN117089241A - Soft UV ink resistant to dry and wet wiping and preparation method and application thereof - Google Patents

Soft UV ink resistant to dry and wet wiping and preparation method and application thereof Download PDF

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Publication number
CN117089241A
CN117089241A CN202310966007.8A CN202310966007A CN117089241A CN 117089241 A CN117089241 A CN 117089241A CN 202310966007 A CN202310966007 A CN 202310966007A CN 117089241 A CN117089241 A CN 117089241A
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photoinitiator
acrylate
monomer
soft
ink
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刘明辉
刘白桦
林昭宁
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Zhuhai Chuanmeixun New Materials Co ltd
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Zhuhai Chuanmeixun New Materials Co ltd
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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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention belongs to the technical field of ink, and provides a dry-wet-wiping-resistant soft UV ink, and a preparation method and application thereof. The invention adopts a monofunctional monomer, a photoinitiator and color paste as main components of the soft UV ink, wherein the monofunctional monomer comprises that the light energy is less than or equal to 0.5J/cm 2 The cured monomer A and the light energy of the monomer A is less than or equal to 1.5J/cm 2 The mass of the solidified monomer B is more than 50 percent of the total mass of the monofunctional monomer, the photoinitiator comprises a photoinitiator A and a photoinitiator B, the photoinitiator A is selected from Norrish II type intramolecular hydrogen abstraction type photoinitiators and/or amine synergists, the photoinitiator B is selected from Norrish I type free radical cleavage type photoinitiators, and the mass of the photoinitiator A is the photoinitiationThe total mass of the agent is more than 40 percent. The invention improves the problem of sticky coating surface, and has the advantages of good surface dryness, good dry and wet rubbing resistance, good folding resistance, excellent ductility and strong adhesive force.

Description

Soft UV ink resistant to dry and wet wiping and preparation method and application thereof
Technical Field
The invention relates to the technical field of ink, in particular to dry and wet wiping-resistant soft UV ink, and a preparation method and application thereof.
Background
The UV ink-jet printing has the advantages of strong digital editing capability, high efficiency, high resolution and low cost, and the used UV ink has the advantages of solvent-free volatilization, energy conservation, carbon reduction, green environmental protection and the like, and is increasingly favored by people. The drying of the UV ink is a photochemical curing process, and the energy of the UV light is absorbed by a photoinitiator in the UV ink, so that free radicals are excited to form and polymerize with monomers or oligomers and the like into solid macromolecules. However, the photoinitiator and the reactive monomer in the ink cannot completely participate in the reaction, especially the surface layer is interfered by oxygen, the problem of oxygen inhibition easily occurs, the photoinitiator and the monomer can be inhibited from reacting, the surface is not dry, the adhesion is generated, the surface pigment is not well fixed, and the defects of dry and wet wiping resistance and the like of the coating are caused. Especially when printing on the surfaces of the base materials such as wallpaper, car stickers, advertisement posters, lamp boxes and the like which need to be cleaned, the coating is cleaned and faded, so that the appearance is affected, the base materials are polluted, and the dyeing problem is caused.
Oxygen inhibition means that oxygen in the coating reacts preferentially with the photoinitiator, preventing the photoinitiator from reacting with the monomer normally. Oxygen inhibition severely affects the efficiency of ink photocuring. The problem has a slight effect on the hard ink, and the hard ink adopts a polyfunctional monomer, so that the reaction speed is high, and the reaction can be carried out with oxygen in a competing way, so that the oxygen polymerization inhibition effect is small. However, the soft ink is used for printing soft materials, such as soft films, canvas, EVA, leather, and the like, and the printed coating is required to have stretchability and not to be easily broken, so the problem of folding resistance of the coating is also required to be considered, most of the soft ink uses monofunctional monomers, the reaction speed is low, and the problem of oxygen polymerization inhibition is serious.
Therefore, development of a soft UV ink is needed to ensure not only excellent folding endurance of the coating, but also to suppress the poor fixation of the coating due to oxygen inhibition, thereby improving the problem of dry and wet wiping resistance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a dry and wet wiping resistant soft UV ink, and a preparation method and application thereof. The soft UV ink provided by the invention has good surface dryness and is resistant to dry and wet wiping (the dry wiping can reach 5 levels and the wet wiping can reach 4-5 levels), and the folding endurance is good (no cracking in folding endurance test).
A first aspect of the present invention provides a soft UV ink that is dry and wet rub resistant.
Specifically, the soft UV ink resistant to dry and wet wiping comprises the following components:
a monofunctional monomer, a photoinitiator and color paste;
the monofunctional monomer comprises a monomer A and a monomer B;
the monomer A can be used for light energy of less than or equal to 0.5J/cm 2 A cured monofunctional monomer, said monomer B being capable of exhibiting a luminous energy of > 0.5J/cm 2 And is less than or equal to 1.5J/cm 2 A cured monofunctional monomer;
the mass of the monomer A accounts for more than 50% of the total mass of the monofunctional monomers;
the photoinitiator comprises a photoinitiator A and a photoinitiator B;
the photoinitiator A is Norrish (also known as Norrish photochemical reaction, roche reaction and Norrish reaction) II type intramolecular hydrogen-abstraction type photoinitiator and/or amine synergist; the photoinitiator B is Norrish I type free radical cleavage type photoinitiator;
the mass of the photoinitiator A accounts for more than 40% of the total mass of the photoinitiator.
The monomer A adopted by the invention is a low-energy curing monofunctional monomer, has low curing energy requirement, and can be used in the condition that the light energy is less than or equal to 0.5J/cm 2 Curing, so that effective photo-curing can still be performed under the interference of oxygen inhibition. Compared with the monomer A cured by low energy, the monomer B belongs to the monomer cured by low energy, and can be cured by light energy of more than 0.5J/cm 2 And is less than or equal to 1.5J/cm 2 Photo curing occurs. The invention adopts the monomer A with low curing energy which accounts for more than 50 percent of the total mass of the monomer with single functional group, can quickly generate photo-curing reaction, reduce the influence of oxygen polymerization inhibition, simultaneously, the monomer B with secondary low curing energy is added to be matched with the monomer A, thus improving the adhesive force, folding endurance and ductility of the ink and simultaneously controlling the cost of the ink. In addition, the invention also adopts the photoinitiator A which accounts for more than 40 percent of the total mass of the photoinitiator and is hardly influenced by oxygen polymerization inhibition, thereby effectively accelerating the photocuring rate, avoiding the occurrence of oxygen polymerization inhibition caused by too slow curing rate and improving the problems of sticky coating surface and no dry and wet wiping resistance. The invention is realized byThe addition proportion of the monomer A and the photoinitiator A is controlled, the curing rate is effectively accelerated, the oxygen polymerization inhibition is avoided, the problems of tackiness and dry and wet wiping intolerance of the surface of the coating are improved, and meanwhile, the cost is controlled, so that the performance of the coating is optimal.
The "dry skin" refers to: the surface of the coating is dried.
The "monofunctional monomer" means: each monomer molecule contains only one group which can participate in the photocuring reaction.
Preferably, the monomer A is a monomer which can be used at a light energy of 0.3J/cm or less 2 A cured monofunctional monomer.
Further preferably, the monomer A is a monomer capable of reacting at an optical energy of 0.2J/cm or less 2 A cured monofunctional monomer.
If the curing energy of the monomer A is more than 0.5J/cm 2 Then suffers from oxygen inhibition; if the curing energy of the monomer A is lower than 0.2J/cm 2 The reactivity is too high, it is not easy to preserve, and it is expensive.
Preferably, the monomer a comprises at least one of N, N-dimethylacrylamide (No. DMAA), N-acryloylmorpholine (No. ACMO), N-vinylpyrrolidone (No. NVP), o-phenylphenoxyethyl acrylate (No. OPPEA), 4 (ethoxy) nonylphenol acrylate (No. 4 EONPA), ethyl 2-ethyleneoxyethoxyacrylate (No. VEEA), N-vinylcaprolactam (No. NVC), trimethylol cyclohexyl acrylate (No. TMCHA), 4-t-butylcyclohexyl acrylate (No. TBCHA), hydroxyethyl acrylamide (No. HEAA), dicyclopentenyl acrylate (No. DCPA), 3-phenoxybenzyl acrylate (No. BPA), 2- (1, 2-cyclohexanedicarboxyimine) ethyl acrylate (No. CHDCIEA).
Preferably, the monomers B are those which can be used at a light energy of > 0.5J/cm 2 And is less than or equal to 1.0J/cm 2 A cured monofunctional monomer.
Further preferably, the monomers B are those which can be used at a luminous energy of > 0.5J/cm 2 And is less than or equal to 0.6J/cm 2 A cured monofunctional monomer.
The second-lowest energy curing monomer B is disturbed by oxygen inhibition to some extent, but its adhesion, folding endurance and elongationThe functionality such as the functionality is better, and can be selected from various types with low cost, so the method is still selected. If the curing energy of the monomer B is more than 1.5J/cm 2 The interference of oxygen inhibition is serious; if the curing energy of the monomer B is less than 0.5J/cm 2 The cost increases significantly.
Preferably, the monomer B includes at least one of tetrahydrofuran acrylate (No. THFA), hydroxyethyl acrylate (No. HEA), hydroxypropyl acrylate (No. HPA), hydroxybutyl acrylate (No. HBA), methyl acrylate (No. MA), ethyl acrylate (No. EA), propyl acrylate (No. PA), butyl acrylate (No. BA), isooctyl acrylate (No. IOA), phenoxyethyl acrylate (No. PHEA), poly (ethylene glycol) phenyl ether acrylic acid (No. EO-PHEA), cyclotrimethylol propane formal acrylate (No. CTFA), benzyl acrylate (No. BZA), ethoxyethoxyethyl acrylate (No. eoea), isobornyl acrylate (No. IBOA), dicyclopentenyl (ethoxy) acrylate (No. EO-DCPA), caprolactone acrylate (No. CA).
Preferably, the photoinitiator A is a Norrish type II intramolecular hydrogen abstraction type photoinitiator, or the photoinitiator A is a combination of a Norrish type II intramolecular hydrogen abstraction type photoinitiator and an amine synergist.
Preferably, the mass ratio of the Norrish type II intramolecular hydrogen abstraction photoinitiator to the amine synergist is 1: (0.5-6).
Further preferably, the mass ratio of the Norrish type II intramolecular hydrogen abstraction photoinitiator to the amine synergist is 1: (0.7-4).
More preferably, the mass ratio of the Norrish type II intramolecular hydrogen abstraction photoinitiator to the amine synergist is 1: (1-2).
Preferably, the Norrish type II intramolecular hydrogen abstraction type photoinitiator comprises a benzophenone type photoinitiator and/or a heterocyclic aromatic type photoinitiator.
Preferably, the heterocyclic aromatic ketone photoinitiator comprises a thioxanthone photoinitiator and/or an anthraquinone photoinitiator.
Preferably, the Norrish type II intramolecular hydrogen abstraction type photoinitiator includes at least one of Michler's ketone (numbered MK), tetraethylMichler's ketone (numbered DEMK), methylethylMichler's ketone (numbered MEMK), 2, 4-diethylthiazolone (numbered DETX), 2-isopropylthioxanthone (numbered ITX), 2-chlorothioxanthone (numbered CTX), and 1-chloro-4-propoxythioxanthone (numbered CPTX).
Preferably, the amine synergist comprises a tertiary amine compound.
Preferably, the tertiary amine compound includes at least one of aliphatic tertiary amine, ethanolamines tertiary amine, benzoate tertiary amine, active amine (acrylamide), and acrylate tertiary amine.
Further preferably, the amine synergist comprises at least one of triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, ethyl 4-dimethylaminobenzoate (No. EDB), 2-ethylhexyl 4-dimethylaminobenzoate (No. EHA), isoamyl p-dimethylaminobenzoate (No. IADB), dimethylaminoethyl benzoate (No. DMB), N-dimethylaminobenzamide, acrylate amine.
Preferably, the photoinitiator B comprises at least one of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (No. 819), 2,4, 6-trimethylbenzoyl diphenylphosphine oxide (No. TPO), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (No. 369), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (No. 379), and 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone (No. 907), hydroxycyclohexyl benzophenone (No. 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (No. 1173), 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] (No. 127).
Preferably, the soft UV ink resistant to dry and wet wiping comprises the following components in parts by mass:
30-150 parts of monofunctional monomer,
4-30 parts of photoinitiator,
10-40 parts of color paste.
Further preferably, the dry and wet wiping resistant soft UV ink comprises the following components in parts by mass:
50-100 parts of monofunctional monomer,
8-20 parts of photoinitiator,
20-30 parts of color paste.
Preferably, the soft UV ink further comprises an auxiliary agent, the auxiliary agent comprising at least one of a wetting agent, a stabilizer, and an adhesion promoter.
Preferably, the soft UV ink resistant to dry and wet wiping further comprises 0.1-10 parts of an auxiliary agent in parts by mass.
Further preferably, the soft UV ink resistant to dry and wet wiping further comprises 0.5-5 parts of an auxiliary agent in parts by mass.
Preferably, the mass of the monomer A accounts for more than 55% of the total mass of the monofunctional monomers.
Further preferably, the mass of the monomer a accounts for 60% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a is 65% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a is 70% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a accounts for 75% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a is 80% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a accounts for 85% or more of the total mass of the monofunctional monomers.
More preferably, the mass of the monomer a accounts for 90% or more of the total mass of the monofunctional monomers.
When the amount of the monomer A added is too small, the inhibition of the interference of oxygen inhibition is insufficient, the surface layer is easy to be sticky and the wet and dry wiping is not resisted; when the amount of the monomer A added is too large, the ink stability becomes poor (reactivity is high) and the cost becomes high.
Preferably, the mass of the photoinitiator A accounts for more than 50% of the total mass of the photoinitiator.
Further preferably, the mass of the photoinitiator a is more than 60% of the total mass of the photoinitiator.
More preferably, the mass of the photoinitiator a accounts for 65% or more of the total mass of the photoinitiator.
More preferably, the mass of the photoinitiator a is more than 70% of the total mass of the photoinitiator.
More preferably, the mass of the photoinitiator a accounts for more than 75% of the total mass of the photoinitiator.
More preferably, the mass of the photoinitiator a is 80% or more of the total mass of the photoinitiator.
When the addition amount of the photoinitiator A is too small, the interference of oxygen polymerization inhibition on the photo-curing of the ink is avoided, the surface layer is easy to be sticky and not resistant to wet wiping; when the amount of the photoinitiator A added is too large, the ink tends to yellow and the deep curing becomes poor.
Preferably, the wetting agent is at least one of BYK-371, BYK-377, BYK-378, BYK-337, BYK-3500, BYK-3505 and BYK-361.
Preferably, the stabilizer is at least one of 2, 6-di-t-butyl-4-methylphenol (numbered BHT), 4-methoxyphenol (numbered MEHQ), RAHN GENORAD 16, RAHN GENORAD 18, RAHN GENORAD 20, RAHN GENORAD 22, RAHN GENORAD 23, cyante S100, cyante 110, cyante 210, and cyante 130.
Preferably, the adhesion promoter is at least one of polyester resin, polyurethane resin, epoxy resin, vinyl chloride resin, rosin resin, acrylate resin, aldehyde ketone resin, marylic acid resin, and polyvinyl butyral resin.
Preferably, the color paste comprises the following components: color paste monomer, dispersant, pigment and stabilizer.
Preferably, the mass ratio of the color paste monomer to the dispersing agent to the pigment to the stabilizer is 40-90:5-30:10-50:0.1-5.0.
Further preferably, the mass ratio of the color paste monomer, the dispersing agent, the pigment and the stabilizer is 50-80:10-25:12-40:0.2-3.
More preferably, the mass ratio of the color paste monomer, the dispersing agent, the pigment and the stabilizer is 60-70:15-20:15-30:0.3-1.
Preferably, the color paste monomer comprises at least one of tetrahydrofuran acrylate, cyclotrimethylol propane formal acrylate, trimethylol cyclohexyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol propoxylate diacrylate, ethoxylated bisphenol A diacrylate and ethoxylated trimethylolpropane triacrylate.
Preferably, the dispersant includes at least one of winning Dispers 710, winning Dispers 685, winning Dispers 655, pick chemical BYK-168, pick chemical BYK-9130, pick chemical BYK-9131, pick chemical BYK-9132, pick chemical BYK-9150, pick chemical BYK-9151, pick chemical BYK-9152, pick chemical BYK-2100, D Pick chemical BYK-2200, pick chemical BYK-2205, road-rinse-solvent 24000, road-rinse-solvent 32000, road-rinse-solvent 32500, road-rinse-solvent 36000, road-rinse-solvent 39000, bass EFKA 4310, bass EFKA 4330, bass EFKA 4030, bass EFKA 4701.
Preferably, the pigment includes at least one of blue pigment, yellow pigment, red pigment, black pigment, white pigment.
Preferably, the blue pigment comprises at least one of PB15:1, PB15:2, PB15:3, and PB15:4.
Preferably, the yellow pigment includes at least one of PY138, PY150, PY151, PY155, PY168, PY180, PY183, PY185, PY 194.
Preferably, the red pigment comprises at least one of PV19, PR122, PR146, PR254, PR 269.
Preferably, the black pigment comprises carbon black.
Preferably, the white pigment comprises titanium dioxide.
The second aspect of the invention provides a preparation method of dry and wet wiping resistant soft UV ink.
A preparation method of dry and wet wiping resistant soft UV ink comprises the following steps:
and mixing the components to obtain the dry and wet wiping-resistant soft UV ink.
Preferably, the monofunctional monomer and the photoinitiator are mixed and dissolved to obtain a pre-solution, then the pre-solution and the color paste are mixed, solid-liquid separation is carried out, and the obtained liquid is soft UV ink.
Preferably, the auxiliary agent is added while mixing the monofunctional monomer and the photoinitiator.
Preferably, the pre-solution and the color paste are mixed in a stirring mode, the stirring speed is 500-1500rpm, and the stirring time is 1-12h.
Further preferably, the stirring speed is 800-1300rpm and the stirring time is 3-10h.
More preferably, the stirring speed is 1000-1200rpm and the stirring time is 5-8h.
Preferably, the solid-liquid separation adopts a filtering mode, and the filtering comprises a first-stage filtering and a second-stage filtering in sequence.
Preferably, the primary filtration employs a filter membrane with a media of 0.1-1 μm.
Further preferably, the primary filtration employs a filter membrane with a media of 0.5-0.7 μm.
Preferably, the primary filtration adopts a glass fiber filter membrane.
Preferably, the secondary filtration employs a filter membrane with a media of 0.1-0.8 μm.
Further preferably, the secondary filtration employs a filter membrane with a media of 0.3-0.5 μm.
Preferably, the secondary filtration employs a polypropylene (PP) filter membrane.
A third aspect of the invention provides the use of a dry and wet rub resistant soft UV ink.
Use of a dry and wet rub resistant soft UV ink in printing soft materials.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts monofunctional monomer, photoinitiator and color paste as raw materialsIs the main component of the soft UV ink, wherein the monofunctional monomer comprises a specific proportion of a monomer with the light energy less than or equal to 0.5J/cm 2 The cured monomer A and the light energy of the monomer A is less than or equal to 1.5J/cm 2 The mass of the cured monomer B is more than 50% of the total mass of the monofunctional monomer, the photoinitiator comprises a photoinitiator A and a photoinitiator B, the photoinitiator A is selected from Norrish II type intramolecular hydrogen abstraction type photoinitiators and/or amine synergists, the photoinitiator B is selected from Norrish I type free radical cleavage type photoinitiators, the mass of the photoinitiator A is more than 40% of the total mass of the photoinitiators, and the proportion of the photoinitiator A is controlled by adopting the matching of different types of monofunctional monomers and different types of photoinitiators.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The "polyfunctional monomer" means: each monomer molecule contains two or more groups which can participate in the photo-curing reaction.
Example 1
A dry and wet rub resistant soft UV ink comprising the components shown in table 1 below.
The preparation method of the dry and wet wiping resistant soft UV ink comprises the following steps:
(1) Mixing and dissolving a monomer A (CHDCIEA, NVC, DCPA), a monomer B (IBOA and BZA), a photoinitiator A (DETX, EDB), a photoinitiator B (TPO, 369), a wetting agent BYK-361 and a stabilizer MEHQ to obtain a pre-solution;
(2) Then mixing the pre-solution with color paste, and stirring at 1000rpm; wherein the color paste comprises color paste monomer PHEA, THFA, dispersant Solsperse 24000 and red pigment. Then the ink is filtered by a glass fiber filter membrane with the thickness of 0.7 mu m and a PP filter membrane with the thickness of 0.5 mu m in sequence to obtain the dry and wet resistant wiping ink.
Examples 2 to 5
Examples 2-5 provide soft UV inks that are dry and wet rub resistant, differing from example 1 in the composition and content thereof. The specific components are shown in Table 1.
Comparative examples 1 to 5
Comparative examples 1-5 provide soft UV inks differing from example 1 in the composition and content thereof. The specific components are shown in Table 1.
Table 1 Components and amounts (parts by mass) of the soft UV ink of each of examples and comparative examples
Product effect test
Using a domestic wide printer, an LED-UV curing lamp wavelength 395nm was mounted, and a five-generation industrial nozzle MH5420 was used to print swatches using the soft UV inks provided in each example and each comparative example. The printed sample is a solid color long bar 16cm x 10cm, and then cut according to the standard required sample size. And respectively performing a dry and wet wiping test, an adhesive force test, a folding endurance test and a ductility test. The base material for the dry and wet wiping test is a PVC soft film and an acrylic plate, the base material for the folding resistance and elongation test is a PVC soft film, and the base material for the adhesive force test is an acrylic plate.
(1) Dry wet wipe test: and detecting by using a rubbing fastness tester, wherein the testing standard of the national standard GBT 3920-2008 is adopted, the grade 5 is optimal, and the grade 1 is worst.
(2) The adhesion test uses the hundred grid test: the test standard of the national standard GBT 9286-1998 is used, the grade 0 is optimal and the grade 5 is worst.
(3) Folding endurance test: and (5) pressing for 1min by adopting twice folding to form a cross crease, and observing whether the ink coating of the crease is cracked.
(4) Ductility test: the elongation = (total length after stretching-sample length)/sample length was measured using a stretcher using the test standard of the industry standard HGT 4991-2016.
The test results are shown in Table 2.
TABLE 2 Performance test results of the soft UV inks of the examples and the comparative examples
As can be seen from the above table, the soft UV ink provided in examples 1-5 of the present invention has the advantages of fast curing rate, good surface drying, good dry and wet wiping resistance, good folding resistance, excellent ductility and adhesion test reaching 0-1 level. The invention can furthest reduce the influence of oxygen polymerization inhibition and improve the dry and wet rubbing resistance of the coating by regulating the types and the addition proportion of the monofunctional monomer and the photoinitiator.
The mass of the monomer a of comparative example 1 is 50% or less of the total mass of the monofunctional monomers, and the mass of the photoinitiator a is 40% or less of the total mass of the photoinitiators, so that the ink coating is not resistant to dry and wet rubbing. Comparative example 2 the mass of photoinitiator a was less than 40% of the total mass of photoinitiator, resulting in an ink coating that was not dry and wet rub resistant. Comparative example 3 the mass of monomer a was less than 50% of the total mass of monofunctional monomers, resulting in an ink coating that was not dry and wet rub resistant. Comparative example 4 added a polyfunctional monomer with a fast reaction rate, resulting in reduced coating adhesion, folding endurance, elongation, and other functionalities. Comparative example 5 contained only monomer a and no monomer B, resulting in poor adhesion and increased cost.

Claims (10)

1. The dry and wet wiping resistant soft UV ink is characterized by comprising the following components:
a monofunctional monomer, a photoinitiator and color paste;
the monofunctional monomer comprises a monomer A and a monomer B;
the monomer A can be used for light energy of less than or equal to 0.5J/cm 2 A cured monofunctional monomer, said monomer B being capable of exhibiting a luminous energy of > 0.5J/cm 2 And is less than or equal to 1.5J/cm 2 A cured monofunctional monomer;
the mass of the monomer A accounts for more than 50% of the total mass of the monofunctional monomers;
the photoinitiator comprises a photoinitiator A and a photoinitiator B;
the photoinitiator A is Norrish II type intramolecular hydrogen abstraction type photoinitiator and/or amine synergist; the photoinitiator B is Norrish I type free radical cleavage type photoinitiator;
the mass of the photoinitiator A accounts for more than 40% of the total mass of the photoinitiator.
2. A soft UV ink according to claim 1, wherein the monomer a comprises at least one of N, N-dimethylacrylamide, N-acryloylmorpholine, N-vinylpyrrolidone, o-phenylphenoxyethyl acrylate, 4 (ethoxy) nonylphenol acrylate, ethyl 2-ethyleneoxyethoxyacrylate, N-vinylcaprolactam, trimethylol cyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, hydroxyethyl acrylamide, dicyclopentenyl acrylate, 3-phenoxybenzyl acrylate, 2- (1, 2-cyclohexanedicarboxylic imine) ethyl acrylate.
3. A soft UV ink according to claim 1, wherein monomer B comprises at least one of tetrahydrofuranyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isooctyl acrylate, phenoxyethyl acrylate, poly (ethylene glycol) phenyl ether acrylic acid, cyclotrimethyolpropane formal acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, isobornyl acrylate, dicyclopentenyl (ethoxy) acrylate, caprolactone acrylate.
4. A soft UV ink according to claim 1, wherein the photoinitiator a is a Norrish type ii intramolecular hydrogen abstraction type photoinitiator or the photoinitiator a is a combination of a Norrish type ii intramolecular hydrogen abstraction type photoinitiator and an amine synergist.
5. A soft UV ink according to claim 1, wherein the photoinitiator B comprises at least one of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ].
6. A soft UV ink according to claim 1, comprising the following components in parts by mass:
30-150 parts of monofunctional monomer,
4-30 parts of photoinitiator,
10-40 parts of color paste.
7. A soft UV ink according to claim 1, further comprising an auxiliary agent comprising at least one of a wetting agent, a stabilizer, an adhesion promoter.
8. A method for preparing a dry and wet rub resistant soft UV ink according to any one of claims 1 to 7 comprising the steps of:
and mixing the components to obtain the dry and wet wiping-resistant soft UV ink.
9. The preparation method according to claim 8, wherein the monofunctional monomer and the photoinitiator are mixed and dissolved to obtain a pre-solution, the pre-solution and the color paste are mixed, and solid-liquid separation is performed, wherein the obtained liquid is soft UV ink.
10. Use of the soft UV ink according to any one of claims 1-7 for printing soft materials.
CN202310966007.8A 2023-08-02 2023-08-02 Soft UV ink resistant to dry and wet wiping and preparation method and application thereof Pending CN117089241A (en)

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Applications Claiming Priority (1)

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CN202310966007.8A CN117089241A (en) 2023-08-02 2023-08-02 Soft UV ink resistant to dry and wet wiping and preparation method and application thereof

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CN117089241A true CN117089241A (en) 2023-11-21

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