A UV inkjet ink containing hybrid unsaturated bond monomer and preparation method thereof

Abstract

The present invention provides a UV inkjet ink containing a hybrid unsaturated bond monomer and a preparation method thereof, which contains a monomer, an initiator system, and a color paste; the monomer includes a monofunctional monomer and a bifunctional monomer, and the bifunctional monomer includes a hybrid unsaturated bond monomer, and one end of the hybrid unsaturated bond monomer contains an acrylate group that can undergo a free radical reaction, and the other end contains an allyl ether group or a vinyl ether group that can undergo a cationic reaction. The oxygen inhibition phenomenon can be effectively reduced and the speed of photo-crosslinking can be increased. That is, the oxygen inhibition phenomenon can be effectively reduced, and the incomplete and incomplete curing caused by the oxygen inhibition of free radical polymerization, the sticky surface or the dry surface and sticky inside, etc. can be avoided, and the UV curable ink composition is suitable for inkjet printing. At the same time, it can also be used in all photocuring fields.

Description

Technical Field

[0001] The invention relates to UV inkjet ink, in particular to a UV inkjet ink containing a hybrid unsaturated bond monomer and a preparation method thereof. Background Art

[0002] UV light curing technology is applied in various fields due to its environmental protection and fast curing speed, especially in the field of UV curing inkjet. Of course, it is not limited to the field of inkjet. Any photocuring reaction can be used for free radical photopolymerization, such as infrared photopolymerization in printing plates, violet laser photopolymerization, etc. As long as free radical polymerization occurs, oxygen inhibition will occur. UV inkjet ink has become a new trend in the current inkjet printing market due to its solvent-free volatilization and instant curing. UV inkjet printing has the characteristics of on-demand printing, high speed, high quality, simple operation, high efficiency, and no pollution. It has quickly occupied the market and has had a great impact on the previous water-based ink and solvent inkjet printing. However, UV inkjet ink undergoes free radical polymerization under UV light. Although free radical polymerization is fast, it usually causes some problems due to oxygen inhibition, which is not satisfactory. First, the surface curing is poor. In addition, it is particularly dependent on the effect of light. Once the light is lost, the polymerization reaction stops immediately. Therefore, the curing thickness is limited, especially for darker colors, especially black ink, there is a phenomenon of incomplete curing. Incomplete curing, sticky surface, or dry surface and sticky inside often occur. For the problem of incomplete reaction and incomplete cross-linking, the market has also improved it from other aspects. For example, the development of monomers with multiple reactive functional groups, but the addition of these monomers will cause wrinkling. The specific reason may be the inconsistent curing speed of the surface and the inner layer. Among them, oxygen inhibition is an important factor.

[0003] In addition, inkjet printing often faces the problem of bonding on different substrates due to the different printing substrates. It is well known that polyurethane resin has excellent bonding properties, and has strong bonding properties for metals, glass, and many substrates including PVC, PET, and PMMA. However, the polyurethane acrylates purchased on the market are difficult to operate due to their high viscosity and cannot be added to the system in large quantities. In addition, in typical UV inks, the energy reaching the surface due to absorption by pigments, photosensitive initiators, etc. is far greater than the energy of UV absorbed in the deep layer, and curing cannot achieve the desired effect. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a UV inkjet ink containing a hybrid unsaturated bond monomer and a preparation method thereof, which can effectively reduce the oxygen inhibition phenomenon and increase the speed of photo-crosslinking. That is, it can effectively reduce the oxygen inhibition phenomenon and avoid the phenomenon of incomplete and incomplete curing of free radical polymerization due to oxygen inhibition, sticky surface or dry surface and sticky inside, etc., which is suitable for UV curable ink composition for inkjet printing. At the same time, it can also be used in all fields of photocuring.

[0005] The objective of the present invention is achieved in the following manner: a UV inkjet ink containing hybrid unsaturated bond monomers, comprising monomers, an initiator system, and a color paste; the monomers include monofunctional monomers and bifunctional monomers, the bifunctional monomers include hybrid unsaturated bond monomers, one end of the hybrid unsaturated bond monomer contains an acrylate group that can undergo a free radical reaction, and the other end contains an allyl ether group or a vinyl ether group that can undergo a cationic reaction.

[0006] The weight of the hybrid unsaturated bond monomer is 10% to 60% of the content of the UV inkjet ink; the weight content of the acrylic acid group that can undergo free radical reaction in the hybrid unsaturated bond monomer is 20% to 40%, and the weight content of the allyl or vinyl group that can undergo cationic polymerization is 20% to 40%.

[0007] The acrylate group that can undergo a radical reaction in the hybrid unsaturated bond monomer is an acrylate group having a urethane group.

[0008] The hybrid unsaturated bond monomer is prepared by reacting ethylene glycol monoallyl ether or 4-hydroxybutyl vinyl ether with isocyanate acrylate.

[0009] The weight of the initiator system is 2%-10% of the content of the UV inkjet ink, the weight of the monofunctional monomer is 10-65% of the content of the UV inkjet ink, the color paste content is 15%-35%; the monomer content is 20%-80%.

[0010] The weight of the hybrid unsaturated bond monomer is 15%-50% of the content of the UV inkjet ink; the weight of the initiator system is 5%-10% of the content of the UV inkjet ink; and the weight of the monofunctional monomer is 20%-40% of the content of the UV inkjet ink.

[0011] Initiator system, the initiator includes a cationic initiator and a free radical initiator.

[0012] The initiator system also includes a co-initiator, which may be an active amine co-initiator, such as Changxing 641 tertiary amine acrylate, 6420 reactive tertiary amine co-initiator, Sartomer SARTOMER, and auxiliary agent CN371.

[0013] The monofunctional monomer is at least one of isobornyl acrylate, tert-butyl cyclohexyl acrylate, phenoxyethyl acrylate or tetrahydrofurfuryl acrylate.

[0014] The monomer includes phenoxyethyl acrylate, and the monomer further includes at least one of N-vinyl caprolactam, 4-vinyloxycyclohexyl acrylate or cyclic trimethylolpropane formal acrylate.

[0015] The UV inkjet ink also includes an auxiliary agent, which is at least one of a stabilizer, an ultraviolet absorber, a surfactant, a leveling agent, and an inhibitor. The amount of the auxiliary agent is 0.01-5% of the content of the UV inkjet ink.

[0016] The preparation method of the UV inkjet ink containing hybrid unsaturated bond monomers comprises the following steps: adding each monomer into a container, then adding each initiator under electromagnetic stirring at 500-1000 rpm, continuing stirring, and stirring for 0.8-1.2 hours after each initiator is completely dissolved, and then adding the dispersed color paste and leveling agent at the same time, and then continuing stirring for 2.5-3.5 hours at a speed of 2800-3200 rpm.

[0017] Compared with the prior art, the UV inkjet ink containing hybrid unsaturated bond monomers provided can effectively reduce oxygen inhibition and increase the speed of photo-crosslinking because hybrid unsaturated bond monomers are added, and one end of the hybrid unsaturated bond monomers contains an acrylate group that can undergo free radical reaction, and the other end contains an allyl ether (or vinyl) group that can undergo cationic reaction. That is, it can effectively reduce oxygen inhibition and avoid incomplete and incomplete curing caused by oxygen inhibition of free radical polymerization, sticky surface or dry surface and sticky inside. It increases the speed of photo-crosslinking and is suitable for UV curable ink compositions for inkjet printing.

[0018] One end of the hybrid unsaturated bond monomer contains an acrylate group with an urethane group that can undergo free radical reaction, and the other end contains an allyl ether (or vinyl) group that can undergo cationic reaction. It can not only give the system excellent adhesion, but also produce strong hydrogen bonds and van der Waals forces with materials such as metallic glass due to the strong polarity of the urethane group. It also has the ability of cationic reaction. Under the action of ultraviolet light, it can greatly improve the cross-linking speed and degree of cross-linking. It not only has strong adhesion to polar surfaces, but also shows strong adhesion to non-polar surfaces due to the presence of vinyl or allyl groups. In addition, due to the introduction of the allyl ether (or vinyl) group, the viscosity of the monomer is greatly reduced, and the amount added can be increased. DETAILED DESCRIPTION

[0019] A UV inkjet ink containing hybrid unsaturated bond monomers, comprising monomers, initiators and colorants; the monomers include monofunctional monomers and difunctional monomers, the difunctional monomers include hybrid unsaturated bond monomers, and the hybrid unsaturated bond monomers are monomers containing at least one acrylic acid group capable of free radical reaction and at least one allyl or vinyl group capable of cationic polymerization.

[0020] monomer:

[0021] The weight content of the acrylate group that can undergo free radical reaction in the hybrid unsaturated bond monomer is 20%-40%, and the weight content of the allyl or vinyl group that can undergo cationic polymerization is 20%-40%. The weight of the hybrid unsaturated bond monomer is 10%~60% of the content of UV inkjet ink. For example, the content of the hybrid unsaturated bond monomer in black ink can be relatively higher.

[0022] The acrylic acid group that can undergo free radical reaction in the hybrid unsaturated bond monomer can be an acrylate group of an urethane group, that is, one end of the hybrid unsaturated bond monomer is an acrylate group of an urethane group that can undergo free radical reaction, and the other end must contain an allyl (or vinyl) ether group that can undergo cationic polymerization. Due to the strong polarity of the urethane group, it can produce strong hydrogen bonds and van der Waals forces with materials such as metallic glass. Because the cationic reaction is not affected by oxygen inhibition, the reaction is more thorough and has better reactivity, thereby giving the system excellent adhesion and the ability of cationic reaction. Under the action of ultraviolet light, the cross-linking speed and degree of cross-linking can be greatly improved. It not only has strong adhesion to polar surfaces, but also exhibits strong adhesion to non-polar surfaces due to the presence of vinyl or allyl groups. By reacting TDI or MDI with IPDI and hydroxyethyl acrylate, the obtained bifunctional urethane acrylate has a very high viscosity, no fluidity, and is almost unusable. In the present application, due to the introduction of allyl (vinyl) groups, the viscosity of the monomer is greatly reduced, and the obtained hybrid unsaturated bifunctional monomer has a viscosity of 65 centipoise, which can be added in large quantities. This can effectively reduce the oxygen inhibition phenomenon, increase the speed of photocrosslinking, and is suitable for UV curable ink compositions for inkjet printing. At this time, preferably, the weight of the hybrid unsaturated bond monomer is 15%-50% of the content of the UV inkjet ink.

[0023] The hybrid unsaturated bond monomer can be prepared by reacting ethylene glycol monoallyl ether or 4-hydroxybutyl vinyl ether with isocyanate ethyl acrylate.

[0024] The monofunctional monomer is at least one of isobornyl acrylate, tert-butyl cyclohexyl acrylate, phenoxyethyl acrylate or tetrahydrofurfuryl acrylate.

[0025] In addition to monofunctional monomers, UV inkjet inks may also contain other difunctional monomers or trifunctional monomers or monomers with more than trifunctional groups.

[0026] At the same time, it may also contain other difunctional monomers, such as at least one of hexanediol diacrylate (HDDA), octylpentanediol diacrylate, 1,4-butanediol diacrylate or tetraethylene glycol diacrylate.

[0027] It may also contain a monomer having three or more functional groups, such as at least one of trihydroxypropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate.

[0028] The monomers may further include a soft monomer, preferably phenoxyethyl acrylate, N-vinyl caprolactam, 4-vinyloxycyclohexyl acrylate, and cyclic trimethylolpropane formal acrylate, which have a relatively low odor.

[0029] The weight of the monofunctional monomer is 10-65% of the content of the UV inkjet ink. Preferably, the weight of the monofunctional monomer is 20-40% of the content of the UV inkjet ink; the monomer content is 20%-80% of the content of the UV inkjet ink.

[0030] Photoinitiator:

[0031] Photoinitiators include cationic initiators and free radical initiators. Some photoinitiators can be used as both cationic initiators and free radical initiators, such as the photoinitiator Irgacure184. In this case, it is not necessary to add both cationic initiators and free radical initiators, as long as the initiator can act as both a cationic initiator and a free radical initiator.

[0032] The cationic initiator may be any of the disclosed cationic initiators, and may be sulfonium salts, iodonium salts, phosphonium salts, sulfone salts, diazonium salts, selenium salts, etc. In the present invention, sulfonium salts and / or iodonium salts are preferred. Such sulfonium salts and / or iodonium salts may be triphenylsulfonium p-toluenesulfonate, triphenylsulfonium chloride, eosin diphenyliodonium salt, 4,4'-dimethyldiphenyliodonium salt hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthonesulfonium hexafluorophosphate, 4,4-didodecylbenzeneiodonium hexafluoroantimonate, 3,3'-dinitrodiphenylsulfonium hexafluorophosphate, 3-nitrophenyldiphenylsulfonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, bis(p-tolyl)iodonium hexafluorophosphate, and the like; the present invention further prefers diaryl iodonium salts, triaryl sulfonium salts, alkyl sulfonium salts, such as sulfonium salt UVI-6976.

[0033] The free radical initiator can use all the disclosed free radical initiators. There are two main types of free radical initiators: Norrish I type initiators, i.e., cleavage type free radical photoinitiators, which cleave after excitation to immediately obtain initiating free radicals, and are mostly aromatic alkyl ketone derivatives. Representative ones include benzoin derivatives, benzil ketal derivatives, dialkoxyacetophenones, α-hydroxyalkyl phenones, α-aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aromatic peroxyester compounds, halogenated methyl aromatic ketones, organic sulfur-containing compounds, benzoylformate, etc.; Norrish II type initiators, which are photoinitiators activated by actinic radiation and form free radicals by abstracting hydrogen from a second compound (which becomes the actual initiating free radical). Representative hydrogen abstraction type photoinitiators include benzophenone and thioxanthone, wherein the second compound is called a polymerization synergist, a coinitiator or a co-initiator. This coinitiator is similar to Norrish II Types of co-initiators include active tertiary amines, thiols, ketones, ethers, etc., which react with aromatic ketones to produce active free radicals to promote the radiation curing process. At the same time, they have a certain degree of resistance to oxygen inhibition. Tertiary amine co-initiators are the most common.

[0034] The listed Norrish I type initiator products include DEAP, BDMM, BAPO, TPO, 184, 1173, 819, 2959 and LTM, etc.; the Norrish II type initiators include DETX, EHA and EMK, etc.; the examples of tertiary amine co-initiators include EDAB, Changxing Chemical's 641 tertiary amine acrylate, 6412 and 6420 reactive tertiary amine co-initiators, SARTOMER, auxiliary agent CN371, etc. For example, the free radical initiator of the present application can be selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-isopropylthioxanthone (ITX), diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), photoinitiator 907.

[0035] The Norrish I type initiator may specifically be 184 or 1173.

[0036] All the disclosed free radical initiators can be used in the photoinitiator system, such as aryl alkyl ketones, oxime ketones, and S-phenylthiobenzoate; and a cationic initiator such as diaryliodonium salts, triarylsulfonium salts, and alkylsulfonium salts must also be contained.

[0037] The weight of the initiator system is 2%-10% of the content of the UV inkjet ink. Preferably, the weight of the initiator system is 5%-10% of the content of the UV inkjet ink.

[0038] Color paste, color paste is the color paste commonly used in UV curing in the prior art.

[0039] The colorants used in the color paste are preferably various well-known ones such as CI Pigment Yellow 12, 13, 73, 74; CI Pigment Red 5, 7, 12, 22; CI Pigment Violet 19, 23; CI Pigment Blue 7, 23; CI Pigment White 6, 18, 21; CI Pigment Black 7.

[0040] The above pigments can be dispersed using a ball mill, and a general dispersant can be added. The dispersion medium can be a low-viscosity photocurable monomer, such as a low-molecular acrylic polymer, etc., to prepare a color paste. The particle size of the pigment in the color paste should be between 50 and 200 nm, preferably between 80 and 120 nm.

[0041] Oil-soluble dyes, preferably oil-soluble dyes from Ciba, can also be used in the system of the present invention. The pigment can be dispersed by a dispersing device, which can be a ball mill, a sand mill, or a roller mill. A dispersant can be added to disperse the pigment, and the dispersant can be hydroxycarboxylic acid ester, long-chain polyaminoamide, and high molecular weight unsaturated acid ester; the solid content in the color paste is about 30%-40%, the content of the UV monomer is 60%-70%, and the dispersant is about 1%-2%. If too much dispersant is added, it may not solidify. When an oil-soluble dye is used as a colorant, the amount of dispersant added is between 0.2% and 6%.

[0042] In order to improve the initiation efficiency and change the response wavelength by sensitizing dyes, sensitizing dyes can be added, which are dyes that absorb in the wavelength range of 350nm to 450nm. Examples include polynuclear aromatic compounds such as anthracene, pyrene, and triphenylene, thioxanthones and coumarins, thiazines such as methylene blue and toluidine blue.

[0043] A stabilizer may also be added to the stabilizer, and the stabilizer may be methoxyphenol, phenothiazine, or alkylphenol.

[0044] The color paste content is 15%-35%.

[0045] Additives

[0046] The UV inkjet ink may further include an auxiliary agent, which is at least one of a stabilizer, an ultraviolet absorber, a surfactant, a leveling agent, and an inhibitor. The amount of the auxiliary agent is 0.01-5% of the content of the UV inkjet ink.

[0047] For example, in order to improve weather resistance, an ultraviolet absorber can be added. The ultraviolet absorber includes benzotriazole compounds, benzophenone compounds, and stilbene compounds.

[0048] The ink composition may contain various surfactants, such as polyethylene oxide alkyl ether, polyethylene oxide allyl ether, and may also contain fluorine-containing surfactants.

[0049] The leveling agent may be leveling agent 432 (TEGO from Germany).

[0050] The polymerization inhibitor may be p-methoxyphenol.

[0051] The preparation method of the UV inkjet ink containing hybrid unsaturated bond monomers comprises the following steps: adding each monomer into a container, then adding each initiator under electromagnetic stirring at 500-1000 rpm, continuing stirring, and stirring for 0.8-1.2 hours after each initiator is completely dissolved, and then adding the dispersed color paste and leveling agent at the same time, and then continuing stirring for 2.5-3.5 hours at a speed of 2800-3200 rpm.

[0052] The container may be other containers besides a jar.

[0053] Inkjet recording method and printed matter

[0054] The recording method of the present invention uses an inkjet recording method: the method includes passing the above-mentioned active composition through a nozzle, which is preferably a piezoelectric nozzle, spraying the above-mentioned ink composition onto a printing medium, and curing it by irradiation with active rays.

[0055] Since the composition of the present invention contains a large amount of urethane groups, it exhibits excellent adhesion and can achieve excellent results in the following media: paper (coated paper and uncoated paper); plastic films including PET film, OPS film, OPP film, PVC film, PE film and TAC film, metal and glass.

[0056] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that this embodiment is only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Technical personnel skilled in the art can make some non-essential improvements and adjustments based on the above-mentioned contents of the present invention.

[0057] Preparation of hybrid unsaturated bond monomer compound A:

[0058] In a 500ML three-necked flask, add 150ml of ethyl acetate, 0.5mol of ethyl isocyanate acrylate, and then add a drop of dibutyltin laurate, and 0.5mol of 4-hydroxybutyl vinyl ether at room temperature of 25°C under nitrogen protection. The reaction ends after half an hour. Add 0.05g of the inhibitor p-methoxyphenol to the above mixed solution to prevent the prepared hybrid unsaturated bond monomer-compound A from continuing to polymerize, and then evaporate the ethyl acetate at 50°C using a rotary evaporator to obtain the desired hybrid unsaturated bond monomer-compound A. The viscosity of compound A is measured to be 65 centipoise.

[0059] The raw materials of UV inkjet ink containing hybrid unsaturated bond monomers are as follows:

[0060] The following examples 1, 2, and 3 correspond to the intermediate amounts of 30, 35, and 40 parts of the self-made monomers, respectively. Example 4 is the lower limit of the self-made monomers, which is only a reliable amount to ensure the reaction speed and bonding quality. It does not mean that the hybrid monomer will not work if it is less than this value. Example 5 is the upper limit of the hybrid monomer. If the amount is continued to be increased, it will still have a good effect, but the cost of the formula will be increased.

[0061] The cationic initiator used in the examples for illustration in this application is UVI-6976, which is triphenylsulfonium hexafluoroantimonate. The triphenylsulfonium hexafluoroantimonate used in this application (50% propylene carbonate solution) was synthesized and purified by Yancheng Huatai Chemical Co., Ltd.

[0062] The structural formula of UVI-6976 is as follows:

[0063]

[0064] In order to further improve the efficiency of the cationic initiator, a free radical initiator 1173 can be added. The structure is as follows:

[0065] The free radical initiator 1173 is 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone, which was synthesized and purified by Yancheng Huatai Chemical Co., Ltd. and has the following structure:

[0066]

[0067] Example 1

[0068] Pigment dispersion black color paste BlackN 30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0069] Monomer PHEA 2-phenoxyethyl acrylate (Korea Changxing EM210) 20 parts

[0070] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 12.5 parts

[0071] Monomer CTFA (Changxing, South Korea) 10 parts

[0072] Compound A 30 parts

[0073] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.0 part

[0074] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0075] Initiator 907 (Nanjing Wali Chemical Co., Ltd.) 1.9 parts

[0076] CN371 (reaction amine co-initiator SARTOMER) 1.0 part

[0077] Initiator UVI-6976 (50% propylene carbonate solution) (Yancheng Huatai Chemical Co., Ltd.) 1.5 parts

[0078] Initiator 1173 (Yancheng Huatai Chemical Co., Ltd.) 1.0 part

[0079] Leveling agent 432 (TEGO from Germany) 0.1 part

[0080] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0081] The preparation method is to first set a yellow light environment, yellow curtains, and a yellow safety light, take a brown wide-mouth bottle with an electromagnetic rotor inside, add each monomer, and then add various initiators under electromagnetic stirring at 1000 rpm, continue stirring, and after various initiators are completely dissolved, stir for another hour, then add color paste, add other additives at the same time, and then continue stirring for three hours at a speed of 3000 rpm.

[0082] Example 2

[0083] The raw materials of UV inkjet ink containing hybrid unsaturated bond monomers are as follows:

[0084] Black color paste BLACKN30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0085] Monomer PHEA 2-phenoxyethyl acrylate (Korea Changxing EM210) 20 parts

[0086] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 7.5 parts

[0087] Monomer CTFA (Changxing, South Korea) 10 parts

[0088] Compound A 35 parts

[0089] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.5 parts

[0090] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0091] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0092] Initiator UVI-6976 (50% propylene carbonate solution) (Yancheng Huatai Chemical Co., Ltd.) 1.5 parts

[0093] Initiator 1173 (Yancheng Huatai Chemical Co., Ltd.) 1.0 part

[0094] Leveling agent 432 (TEGO from Germany) 0.1 part

[0095] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0096] The preparation method is the same as Example 1.

[0097] Example 3

[0098] The raw materials of UV inkjet ink containing hybrid unsaturated bond monomers are as follows:

[0099] Black color paste BLACKN30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0100] Monomer PHEA 2-phenoxyethyl acrylate (Korea Changxing EM210) 20 parts

[0101] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 8 parts

[0102] Monomer CTFA (Changxing, South Korea) 5 parts

[0103] Compound A 40 parts

[0104] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.5 parts

[0105] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0106] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0107] Initiator UVI-6976 (50% propylene carbonate solution) (Yancheng Huatai Chemical Co., Ltd.) 1.5 parts

[0108] Initiator 1173 (Yancheng Huatai Chemical Co., Ltd.) 1.0 part

[0109] Leveling agent 432 (TEGO from Germany) 0.08 parts

[0110] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0111] The preparation method is the same as Example 1.

[0112] Embodiment 4:

[0113] The raw materials of UV inkjet ink containing hybrid unsaturated bond monomers are as follows:

[0114] Black color paste BLACKN30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0115] Monomer PHEA 2-phenoxyethyl acrylate (Korea Changxing EM210) 25 parts

[0116] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 20 parts

[0117] Monomer CTFA (Changxing, South Korea) 13 parts

[0118] Compound A 15 parts

[0119] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.5 parts

[0120] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0121] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0122] Initiator UVI-6976 (50% propylene carbonate solution) (Yancheng Huatai Chemical Co., Ltd.) 1.5 parts

[0123] Initiator 1173 (Yancheng Huatai Chemical Co., Ltd.) 1.0 part

[0124] Leveling agent 432 (TEGO from Germany) 0.08 parts

[0125] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0126] The preparation method is the same as Example 1.

[0127] Embodiment 5:

[0128] The raw materials of UV inkjet ink containing hybrid unsaturated bond monomers are as follows:

[0129] Black color paste BLACKN30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0130] Monomer PHEA 2-phenoxyethyl acrylate (Korea Changxing EM210) 5 parts

[0131] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 3 parts

[0132] Monomer CTFA (Changxing, South Korea) 10 parts

[0133] Compound A 55 parts

[0134] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.5 parts

[0135] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0136] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0137] Initiator UVI-6976 (50% propylene carbonate solution) (Yancheng Huatai Chemical Co., Ltd.) 1.5 parts

[0138] Initiator 1173 (Yancheng Huatai Chemical Co., Ltd.) 1.0 part

[0139] Leveling agent 432 (TEGO from Germany) 0.08 parts

[0140] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0141] The preparation method is the same as Example 1.

[0142] It should also be noted that the amount of color paste used is determined by the requirements for color density. There is no fixed amount. On the premise of achieving color density, try to reduce the amount of color paste to reduce the cost of ink.

[0143] Comparative Example 1

[0144] The raw materials of UV inkjet ink are as follows:

[0145] Pigment dispersion black color paste BlackN 30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0146] Monomer PHEA 2-phenoxyethyl acrylate (Korea EM210) 25 parts

[0147] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 33 parts

[0148] Monomer HDDA (Changxing, South Korea) 15 parts

[0149] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.0 part

[0150] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0151] Initiator 907 (Nanjing Wali Chemical Co., Ltd.) 1.9 parts

[0152] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0153] Leveling agent 432 (TEGO from Germany) 0.08 parts

[0154] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0155] The preparation method is to first set a yellow light environment, yellow curtains, and a yellow safety light, take a brown wide-mouth bottle with an electromagnetic rotor inside, add each monomer, and then add various initiators under electromagnetic stirring at 1000 rpm, continue stirring, and after various initiators are completely dissolved, stir for another hour, then add color paste, add other additives at the same time, and then continue stirring for three hours at a speed of 3000 rpm.

[0156] Comparative Example 2

[0157] The raw materials of UV inkjet ink are as follows:

[0158] Pigment dispersion black color paste BlackN 30 (Shanghai Kaiyin Chemical Co., Ltd.) 20 copies

[0159] Monomer PHEA 2-phenoxyethyl acrylate (Korea EM210) 25 parts

[0160] Monomer N-vinyl caprolactam (Shanghai Kaiyin Chemical Co., Ltd.) 20 parts

[0161] Monomer CTFA 13 parts

[0162] Monomer HDDA (Changxing, South Korea) 15 parts

[0163] Initiator ITX (Jiangsu Runfeng Synthetic Technology Co., Ltd.) 1.0 part

[0164] Initiator TPO (Shanghai Kaiyin Chemical Co., Ltd.) 1.0 part

[0165] Initiator 907 (Nanjing Wali Chemical Co., Ltd.) 1.9 parts

[0166] CN371 (reaction amine co-initiator SARTOMER) 1.9 parts

[0167] Leveling agent 432 (TEGO from Germany) 0.08 parts

[0168] Inhibitor p-methoxyphenol (analytical grade) 0.05 parts

[0169] The preparation method is the same as that of Comparative Example 1.

[0170] Performance testing:

[0171] Bonding with glass: Use wire rods with different properties to scrape the invention example and the comparative example onto a 5 mm thick glass plate at the same time, scrape a thin layer of 12 μm, and use a UV-LED curing machine with an irradiation of 8 W / cm 2, solidify for 5 seconds respectively. After 15 seconds, use the hundred-grid method to mark out a hundred grids, and then use transparent tape to bond. The one that is intact is A, the one that is partially bonded is B, and the one that is completely bonded is C.

[0172] Bonding with stainless steel: Use wire rods of different grades to scrape the invention embodiment and comparative example on 5 mm thick stainless steel at the same time, scrape a thin layer of 12 μm, and use a UV-LED curing machine with an irradiation of 8 W / cm 2 , solidify for 5 seconds respectively. After 15 seconds, use the hundred-grid method to mark out a hundred grids, and then use transparent tape to bond. The one that is intact is A, the one that is partially bonded is B, and the one that is completely bonded is C.

[0173] The test results are shown in Table 1:

[0174]

[0175] As can be seen from the table above, any formula that adds a certain amount of self-made hybrid monomers shows excellent reactivity, and the ink has excellent adhesion to the printing medium, while the comparative ratio is obviously inferior. For other ingredients in the formula, such as the amount of monomers used, since CTFA and PHEA are flexible monomers and N-vinyl caprolactam is a polar rigid monomer, there is no special restriction on their amount in the formula. Generally, they are adjusted to meet the requirements. If the requirements for abrasion resistance are high, the rigid monomer N-vinyl caprolactam needs to be added. Of course, other rigid monomers can also be added, such as cyclohexyl methacrylate and isobornyl methacrylate. If flexibility is required, the amount of CTFA and PHEA can be appropriately increased. Everything is adjusted for the purpose of ink research and development.

[0176] The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto. It should be pointed out that for those skilled in the art and any technician familiar with the technical field, without departing from the overall concept of the present invention, the technical solution and the inventive concept of the present invention are equivalently replaced or changed, and several changes and improvements are made, which should also be regarded as the protection scope of the present invention.

Claims

1. A UV inkjet ink containing a hybrid unsaturated bond monomer, comprising a monomer, an initiator system, and a color paste; characterized in that: The monomers include monofunctional monomers and difunctional monomers. The difunctional monomers include hybrid unsaturated monomers. The weight of the hybrid unsaturated monomers is 10% to 60% of the content of the UV inkjet ink. The monomer content is 20% to 80%. The weight of the monofunctional monomers is 10-65% of the content of the UV inkjet ink. The weight of the initiator system is 2% to 10% of the content of the UV inkjet ink. The color paste content is 15% to 35%. One end of the hybrid unsaturated bond monomer contains an acrylate group with an amino group that can undergo a free radical reaction, and the other end contains an allyl ether group or a vinyl ether group that can undergo a cationic reaction. The weight content of the acrylate group with an amino group that can undergo a free radical reaction in the hybrid unsaturated bond monomer is 20%-40%, and the weight content of the allyl ether or vinyl ether that can undergo cationic polymerization is 20%-40%. The hybrid unsaturated bond monomer is prepared by reacting ethylene glycol monoallyl ether or 4-hydroxybutyl vinyl ether with isocyanate acrylate.

2. The UV inkjet ink containing a hybrid unsaturated bond monomer according to claim 1, characterized in that: The weight of the hybrid unsaturated bond monomer is 15%-50% of the content of the UV inkjet ink, the weight of the initiator system is 5%-10% of the content of the UV inkjet ink, and the weight of the monofunctional monomer is 20%-40% of the content of the UV inkjet ink.

3. The UV inkjet ink containing a hybrid unsaturated bond monomer according to claim 1, characterized in that: The initiator system comprises a cationic initiator and a free radical initiator; the monofunctional monomer is at least one of isobornyl acrylate, tert-butyl cyclohexyl acrylate, phenoxyethyl acrylate or tetrahydrofurfuryl acrylate.

4. The UV inkjet ink containing a hybrid unsaturated bond monomer according to claim 3, characterized in that: The monomer includes phenoxyethyl acrylate, and the monomer further includes at least one of N-vinyl caprolactam, 4-vinyloxycyclohexyl acrylate or cyclic trimethylolpropane formal acrylate.

5. The UV inkjet ink containing a hybrid unsaturated bond monomer according to claim 4, characterized in that: The UV inkjet ink also includes an auxiliary agent, which is at least one of a stabilizer, an ultraviolet absorber, a surfactant, a leveling agent, and an inhibitor. The amount of the auxiliary agent is 0.01-5% of the content of the UV inkjet ink.

6. The method for preparing a UV inkjet ink containing a hybrid unsaturated bond monomer according to any one of claims 1 to 5, characterized in that: Add each monomer into the container, then add the initiator system under electromagnetic stirring at 500-1000 rpm, continue stirring, and after all initiators are completely dissolved, stir for another 0.8-1.2 hours, then add the dispersed color paste and leveling agent at the same time, and then continue stirring at a speed of 2800-3200 rpm for 2.5-3.5 hours.

Images