CN113150614A - Radiation-curable ink-jet fluid, spray ink and application thereof - Google Patents
Radiation-curable ink-jet fluid, spray ink and application thereof Download PDFInfo
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- CN113150614A CN113150614A CN202110593722.2A CN202110593722A CN113150614A CN 113150614 A CN113150614 A CN 113150614A CN 202110593722 A CN202110593722 A CN 202110593722A CN 113150614 A CN113150614 A CN 113150614A
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- 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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Abstract
The present examples disclose a radiation curable inkjet fluid comprising a radiation curable composition comprising an allyl ether acrylate and a polymerizable ultraviolet absorber, and a photoinitiator comprising an acylphosphine oxide, the inkjet fluid being free of volatile components. According to the invention, by matching the radiation-curable composition containing allyl ether acrylate and the polymerizable ultraviolet absorber with the photoinitiator containing acylphosphine oxide, the photoyellowing and long-term yellowing performance of the ink can be remarkably improved on the premise of ensuring that the ink has good adhesiveness, and the radiation-curable composition can be used for UV-photocuring inkjet ink.
Description
Technical Field
The embodiment of the application relates to the technical field of photocuring, in particular to a radiation-curable ink-jet fluid, a spray ink and application thereof.
Background
One reason that UV resins or monomers yellow upon curing by UV lamp or Electron Beam (EB) radiation is to limit their use in high-brightness applications. The initial yellowing is partially reversible and some bleaching occurs for the first few hours or days after radiation cure. However, it causes a change in the color of the coating, which makes color matching very difficult for a short time after irradiation, and thus also makes online quality control difficult. Reducing this photoyellowing is an important step in the development of radiation curing technology.
"photoyellowing" is also known as "cured yellowing" or "post-cure yellowing". This reduction in yellow time is referred to as "bleaching". This "photoyellowing" is distinct from "long-term yellowing," which is yellowing (for almost all coatings) that occurs during natural weathering or accelerated aging (e.g., QUV, xenon, florida exposure). Conventional stabilizers for preventing long-term yellowing are often ineffective at preventing photoyellowing, some of which even photoyellowing itself.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
To address the deficiencies of the prior art, the present invention provides a radiation curable inkjet fluid, an inkjet ink and uses thereof.
According to one aspect of the present invention, a radiation curable inkjet fluid includes a radiation curable composition including an allyl ether acrylate and a polymerizable ultraviolet absorber, and a photoinitiator including an acylphosphine oxide, the inkjet fluid being free of volatile components.
Preferably, the allyl ether acrylate has a structure represented by the general formula (1):
wherein A is any one of substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl and substituted or unsubstituted C10-C40 thick aryl;
R1represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group;
R2represents a C1-C30 substituted or unsubstituted alkylene group;
R3represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group.
Preferably, A is a C1-C8 substituted or unsubstituted alkylene, preferably C1-C4 substituted or unsubstituted alkylene, for example C2, C3 or C4 alkylene;
preferably, said R is1Hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl;
preferably, R2Is a C1-C8 substituted or unsubstituted alkylene group, preferably a C1-C4 substituted or unsubstituted alkylene group, and more preferably-CH2-；
Preferably, R3Is a C1-C8 substituted or unsubstituted alkyl group, preferably a C1-C4 substituted or unsubstituted alkyl group, and more preferably a methyl group;
preferably, the allyl ether acrylate is the product prepared by the following method:
(meth) acrylic acid is reacted with allyl glycidyl ether in a ring-opening reaction, or hydroxyethyl acrylate is reacted with allyl glycidyl ether, or tetrahydrophthalic anhydride is reacted with allyl glycidyl ether.
Preferably the polymerizable ultraviolet light absorber is an acrylated polymerizable ultraviolet light absorber.
Preferably, the polymerizable ultraviolet absorber has a structure represented by general formula (2):
R4any one selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 fused aryl;
A1is any one of C1-C30 substituted or unsubstituted alkylene, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 thick aryl;
R5represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group;
preferably, said R is5Hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl;
preferably, the polymerizable ultraviolet light absorber is a product prepared by the following method:
2, 4-dihydroxy benzophenone and 3,4-Epoxycyclohexylmethyl methacrylate are subjected to ring-opening reaction under the catalysis of sodium hydroxide, under the nitrogen atmosphere, 2, 4-dihydroxy benzophenone and sodium hydroxide are firstly added into a stirrer, 3,4-Epoxycyclohexylmethyl methacrylate is added into the stirrer, the mixture reacts for 7 to 10 hours at 80 ℃, and after the reaction is finished, the mixture is washed with water and dried in vacuum to remove water; or the like, or, alternatively,
reacting methacryloyl chloride with 2, 4-dihydroxy benzophenone for 2 hours at 50 ℃ in anhydrous pyridine, slowly pouring the mixed product into dilute hydrochloric acid under the condition of stirring to separate out a reddish brown precipitate, and recrystallizing in absolute ethyl alcohol after column chromatography treatment to obtain the product 2-hydroxy 4-methyl acrylate benzophenone.
Preferably, the photoinitiator comprises a monoacylphosphine oxide and/or a bisacylphosphine oxide;
preferably, the acylphosphine oxide includes any one or a combination of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) - (2, 4-bis-phenoxyphenyl) phosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, or 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
Preferably, the radiation curable composition comprises at least 5 wt% of allyl ether acrylate, based on the total weight of the radiation curable composition, and at least 3 wt% of a polymerizable ultraviolet absorber, based on the total weight of the radiation curable composition.
Preferably, the radiation curable composition comprises at least 5 to 10 wt% of allyl ether acrylate based on the total weight of the radiation curable composition and at least 3 to 8 wt% of a polymerizable ultraviolet absorber based on the total weight of the radiation curable composition.
Preferably, the inkjet fluid is a UV-curable inkjet fluid;
preferably, the inkjet fluid is solvent-free;
preferably, the viscosity of the inkjet fluid is 1 to 20cps at 25 ℃.
According to another aspect of the present invention, there is provided a radiation curable inkjet ink comprising a radiation curable inkjet fluid as described above.
According to a further aspect of the present invention there is provided an inkjet printing method comprising applying to a substrate a radiation curable inkjet fluid as described above or an inkjet ink as described above.
Has the advantages that: by compounding the radiation curable composition comprising allyl ether acrylate and a polymerizable ultraviolet absorber with a photoinitiator comprising acylphosphine oxide, the photoyellowing and long-term yellowing properties of the ink can be significantly improved on the premise that the ink has good adhesion.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are for purposes of illustration and not limitation.
In order to solve the defects of the prior art, the invention provides a radiation curable ink-jet fluid, a spraying ink and application thereof.
The inventors have surprisingly found that: by compounding the radiation curable composition comprising allyl ether acrylate and a polymerizable ultraviolet absorber with a photoinitiator comprising acylphosphine oxide, the photoyellowing and long-term yellowing properties of the ink can be significantly improved on the premise that the ink has good adhesion.
According to one aspect of the present invention, there is provided a radiation curable inkjet fluid comprising a radiation curable composition comprising an allyl ether acrylate and a polymerizable ultraviolet absorber, and a photoinitiator comprising an acylphosphine oxide, the inkjet fluid being free of volatile components.
According to the invention, through the coordination of the polymerizable ultraviolet absorbent capable of participating in curing, the allyl ether acrylate and the acyl phosphine oxide, the photoyellowing performance of the ink-jet ink is improved, and meanwhile, the polymerizable ultraviolet absorbent can participate in curing, so that the long-term yellowing performance of the ink-jet ink is improved.
Allyl ether acrylate
In a preferred embodiment of the present invention, the allyl ether acrylate has a structure represented by the general formula (1):
wherein A is any one of substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl and substituted or unsubstituted C10-C40 thick aryl;
R1represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group;
R2represents a C1-C30 substituted or unsubstituted alkylene group;
R3represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group.
In the present invention, the C1-C30 symbols represent the number of carbon atoms of the continuous substituents herein, and C1-C30 represent 1-30 carbon atoms.
In a preferred embodiment of the present invention, in a, the substituted or unsubstituted C1-C30 alkyl groups each independently include a substituted or unsubstituted C1-C30 linear or branched alkyl group, preferably an unsubstituted C1-C30 linear or branched alkyl group, and alternative examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-dimethylbutyl, and the like.
In a preferred embodiment of the present invention, in a, the substituted or unsubstituted C1-C30 alkoxy groups each independently include a substituted or unsubstituted C1-C30 linear or branched alkoxy group, preferably an unsubstituted C1-C30 linear or branched alkoxy group, and alternative examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, and the like.
In a preferred embodiment of the present invention, in a, the substituted or unsubstituted C6-C40 aryl group may be selected from any one of aromatic hydrocarbon groups such as phenyl, biphenylyl, 9-fluorenyl, terphenylyl, and the like. The above-mentioned C6-C40 aryl group may or may not have a substituent.
In a preferred embodiment of the present invention, in a, the substituted or unsubstituted C6-C40 fused aryl group may be selected from any one of fused aryl groups such as naphthyl, anthryl, phenanthryl, 9, 10-benzophenanthryl, 1, 2-benzophenanthryl, acenaphthenyl, perylenyl, pyrenyl, indenyl, and the like. The condensed aryl group having C6 to C40 may or may not have a substituent.
The same should be understood with respect to substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C10-C40 fused aryl, as mentioned elsewhere in this invention.
In a preferred embodiment of the present invention, a is a C1 to C8 substituted or unsubstituted alkylene, preferably C1 to C4 substituted or unsubstituted alkylene, for example C2, C3 or C4 alkylene.
In a preferred embodiment of the present invention, R is1Is hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl.
In a preferred embodiment of the invention, R2Is a C1-C8 substituted or unsubstituted alkylene group, preferably a C1-C4 substituted or unsubstituted alkylene group, and more preferably-CH2-。
In a preferred embodiment of the invention, R3Is a C1 to C8 substituted or unsubstituted alkyl group, preferably a C1 to C4 substituted or unsubstituted alkyl group, and more preferably a methyl group.
Allyl ether acrylates can be prepared by those skilled in the art with the knowledge of their own organic synthesis, and in a preferred embodiment of the invention, typical but non-limiting examples of such allyl ether acrylates can be prepared as follows:
(meth) acrylic acid is reacted with allyl glycidyl ether in a ring-opening reaction, or hydroxyethyl acrylate is reacted with allyl glycidyl ether, or tetrahydrophthalic anhydride is reacted with allyl glycidyl ether.
In the present invention, a single allyl ether acrylate may be used, or a mixture of different types of allyl ether acrylates may be used, which is not limited by the present invention.
Polymerizable ultraviolet absorber
In a preferred embodiment of the present invention, the polymerizable ultraviolet absorber is an acrylated polymerizable ultraviolet absorber.
In a preferred embodiment of the present invention, the polymerizable ultraviolet absorber has a structure represented by general formula (2):
R4any one selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 fused aryl;
A1is any one of C1-C30 substituted or unsubstituted alkylene, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 thick aryl;
R5represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group.
In the general formula (2), substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C6-C40 aryl group, and substituted or unsubstituted C10-C40 condensed aryl group are the same as those in the aforementioned general formula (1).
In a preferred embodiment of the present invention, R is5Is hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl.
The polymerizable ultraviolet absorber can be prepared by a person skilled in the art according to his own knowledge in the field of organic synthesis, and in a preferred embodiment of the invention, said polymerizable ultraviolet absorber can be typically, but not exclusively, prepared as follows:
2, 4-dihydroxy benzophenone and 3,4-Epoxycyclohexylmethyl methacrylate are subjected to ring-opening reaction under the catalysis of sodium hydroxide, under the nitrogen atmosphere, 2, 4-dihydroxy benzophenone and sodium hydroxide are firstly added into a stirrer, 3,4-Epoxycyclohexylmethyl methacrylate is added into the stirrer, the mixture reacts for 7 to 10 hours at 80 ℃, and after the reaction is finished, the mixture is washed with water and dried in vacuum to remove water; or the like, or, alternatively,
reacting methacryloyl chloride with 2, 4-dihydroxy benzophenone for 2 hours at 50 ℃ in anhydrous pyridine, slowly pouring the mixed product into dilute hydrochloric acid under the condition of stirring to separate out a reddish brown precipitate, and recrystallizing in absolute ethyl alcohol after column chromatography treatment to obtain the product 2-hydroxy 4-methyl acrylate benzophenone.
Photoinitiator
According to the invention, the photoinitiator comprises at least one acylphosphine oxide.
The acyl phosphine oxide is used as a high-light-sensitive initiator, and is subjected to intramolecular photolysis after being irradiated by light, carbonyl and phosphonyl are subjected to bond breaking, and the generated phosphonyl radical has extremely high initiated polymerization activity on unsaturated monomers.
In a preferred embodiment of the present invention, the photoinitiator comprises a monoacylphosphine oxide and/or a bisacylphosphine oxide. Both monoacylphosphine oxides and bisacylphosphine oxides are commercially available. Furthermore, the preparation of monoacylphosphine oxides and bisacylphosphine oxides is also well known to the person skilled in the art.
Typical but non-limiting acylphosphine oxides are: bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) - (2, 4-bis-phenoxyphenyl) phosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide or 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
Other photoinitiators may be used in combination with the photoinitiator.
The photoinitiator content can be determined by one skilled in the art according to his or her own general technical knowledge in the field, and the present invention is not limited thereto.
In a preferred embodiment of the present invention, the radiation curable composition comprises at least 5 wt% of allyl ether acrylate, based on the total weight of the radiation curable composition, and at least 3 wt% of a polymerizable ultraviolet absorber, based on the total weight of the radiation curable composition. In a further preferred embodiment of the present invention, the radiation curable composition comprises at least 5 to 10 wt% (less than 5% does not have a yellowing inhibition effect, and more than 10% easily causes too much double bond residue, and reduces long-term yellowing inhibition) of allyl ether acrylate based on the total weight of the radiation curable composition, and at least 3 to 8 wt% (less than 3% has a poor yellowing inhibition effect, and more than 8% obviously affects the overall curing effect) of polymerizable ultraviolet absorber based on the total weight of the radiation curable composition.
Other photopolymerisable compounds
A wide variety of photopolymerizable and photocrosslinkable compounds may be used in the radiation curable compositions of the present invention, in combination with the other components of the present invention.
Photopolymerizable and photocrosslinkable compounds capable of free radical polymerization, generally known in the art, can be used in the radiation curable inkjet fluids of the present invention, and combinations of monomers and/or oligomers can also be used.
Suitable photopolymerizable compounds include acrylate compounds such as isoamyl acrylate, octadecyl acrylate, and the like.
In a preferred embodiment of the present invention, the radiation curable inkjet fluid is a UV-curable inkjet fluid.
In a preferred embodiment of the present invention, the inkjet fluid is free of solvents, which may be either organic or inorganic.
In a preferred embodiment of the present invention, the viscosity of the inkjet fluid is 1 to 20cps (25 ℃)
According to another aspect of the present invention, there is provided a radiation curable inkjet ink comprising a radiation curable inkjet fluid as described above.
Coloring agent
The inkjet ink of the present invention preferably contains a colorant. Any colorant can be used to impart the desired color to the ink-jet ink. In a preferred embodiment of the present invention, the colorant may comprise at least one pigment or one dye or a combination thereof.
A wide variety of organic and inorganic dyes and pigments can be selected for use, alone or in combination, in the ink compositions of the present invention. The colorant particles should be small enough to allow ink to flow freely through the inkjet printing apparatus, particularly at the ejection nozzles. The colorant can be black, cyan, magenta, yellow, red, blue, green, brown, mixtures thereof, and the like. The person skilled in the art can select suitable colorants at will.
Additive agent
The inkjet ink of the present invention may include additives such as biocides, buffers, mildewcides, pH adjusters, conductivity adjusters, chelating agents, rust inhibitors, polymerization inhibitors, surfactants, light stabilizers, and the like. These additives can be included in the ink-jet inks of the present invention in any effective amount, as desired.
Equipment for radiation curing is known to those skilled in the art and is commercially available.
According to another aspect of the present invention there is provided an inkjet printing method comprising applying to a substrate a radiation curable inkjet fluid or ink as described above.
The substrate to which the inkjet fluid or inkjet ink of the present invention can be sprayed is not limited and includes, for example, paper, coated paper, polyolefin coated paper, cardboard, wood, composite board, plastic, coated plastic, canvas, textile, metal, ceramic, and the like.
Example 1
2, 4-dihydroxy benzophenone and 3,4-Epoxycyclohexylmethyl methacrylate are subjected to ring-opening reaction under the catalysis of sodium hydroxide, under the nitrogen atmosphere, 2, 4-dihydroxy benzophenone and sodium hydroxide are firstly added into a stirrer, 3,4-Epoxycyclohexylmethyl methacrylate is added into the stirrer, the mixture reacts for 7 to 10 hours at 80 ℃, and after the reaction is finished, the mixture is washed with water and dried in vacuum to remove water, so that UA-1 is obtained.
Examples 2 to 5
Carrying out esterification reaction on allyl alcohol and acrylic acid under the catalytic action of a solid activated carbon carrier, firstly adding the allyl alcohol, the acrylic acid and a catalyst into a stirrer under the nitrogen atmosphere, reacting for 7-10h at 80-100 ℃, washing with water after the reaction is finished, drying in vacuum to remove water, and purifying to obtain UB-1.
Product UB2-5 was obtained from the starting material according to table 1, with reference to the above procedure.
TABLE 1
| Numbering | Material 1 | Material 2 |
| UB-2 | Allyl alcohol | Addition product of hydroxyethyl acrylate and tetrahydrophthalic anhydride |
| UB-3 | Allyl alcohol polyoxyethylene ether | Acrylic acid |
| UB-4 | Allyl alcohol polyoxyethylene ether | Addition product of hydroxyethyl acrylate and tetrahydrophthalic anhydride |
| UB-5 | Allyl alcohol decapolyoxyethylene ether | Addition product of hydroxyethyl acrylate and tetrahydrophthalic anhydride |
2. Inkjet ink
TABLE 2
In the rightmost column of table 2, THFA, CTFA, DPHA, color paste, leveling agent, 2-functional polyurethane, etc. are: THFA15, CTFA40, DPHA5, 2-functional polyurethane B-2705, nano color paste (consisting of hyper-dispersant TEG0-685 and HDDA) 15, leveling agent BYK-21003
Comparative example 4
The procedure was as in example 1 except that allyl ether acrylate was used in place of 3-allyloxy 1, 2-propanediol.
Comparative example 5
The procedure was as in example 1 except that the polymerizable UV absorber was replaced with 2, 4-dihydroxybenzophenone.
Comparative example 6
The procedure is as in example 1, except that the photoinitiator is replaced with 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.
Performance testing
The yellowing test is carried out according to ASTM G154 standard and Q-Sun xenon lamp test box ASTM G155 standard
| Example (b) | Viscosity cps | 24h experiment E | 100h experiment E | Appearance, 100h |
| Example 1 | 10-11 | 0-1 | 1-2 | Is basically normal |
| Example 2 | 10-11 | 0-1 | 1-2 | Is basically normal |
| Example 3 | 12-13 | 1-2 | 1-2 | Is basically normal |
| Example 4 | 12-13 | 1-2 | 3-4 | Is basically normal |
| Example 5 | 15-16 | 1-2 | 3-4 | Is basically normal |
| Comparative example 1 | 10-11 | 4-5 | 5-7 | Is basically normal |
| Comparative example 2 | 10-11 | 6-8 | 7-9 | With cracking |
| Comparative example 3 | 10-11 | 4-5 | 4-5 | Is basically normal |
| Comparative example 4 | 10-11 | 4-5 | 7-9 | With cracking |
| Comparative example 5 | 10-11 | 3-4 | 5-7 | Is basically normal |
| Comparative example 6 | 10-11 | 1-2 | 3-4 | Is basically normal |
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present application and the technical principles employed. It will be understood by those skilled in the art that the present application is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the application. Therefore, although the present application has been described in more detail with reference to the above embodiments, the present application is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present application, and the scope of the present application is determined by the scope of the appended claims.
Claims (10)
1. A radiation curable inkjet fluid comprising a radiation curable composition comprising an allyl ether acrylate and a polymerizable ultraviolet absorber, and a photoinitiator comprising an acylphosphine oxide, the inkjet fluid being free of volatile components.
2. The inkjet fluid of claim 1, wherein the allyl ether acrylate has a structure according to formula (1):
wherein A is any one of substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl and substituted or unsubstituted C10-C40 thick aryl;
R1represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group;
R2represents a C1-C30 substituted or unsubstituted alkylene group;
R3represents hydrogen or substituted or unsubstituted C1-C30An alkyl group.
3. The inkjet fluid of claim 2, wherein a is a C1-C8 substituted or unsubstituted alkylene, preferably C1-C4 substituted or unsubstituted alkylene, such as C2, C3, or C4 alkylene;
preferably, said R is1Hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl;
preferably, R2Is a C1-C8 substituted or unsubstituted alkylene group, preferably a C1-C4 substituted or unsubstituted alkylene group, and more preferably-CH2-；
Preferably, R3Is a C1-C8 substituted or unsubstituted alkyl group, preferably a C1-C4 substituted or unsubstituted alkyl group, and more preferably a methyl group;
preferably, the allyl ether acrylate is the product prepared by the following method:
(meth) acrylic acid is reacted with allyl glycidyl ether in a ring-opening reaction, or hydroxyethyl acrylate is reacted with allyl glycidyl ether, or tetrahydrophthalic anhydride is reacted with allyl glycidyl ether.
4. The inkjet fluid of claim 1, wherein the polymerizable ultraviolet absorber is an acrylated polymerizable ultraviolet absorber.
5. The inkjet fluid of claim 4, wherein the polymerizable ultraviolet absorber has a structure according to formula (2):
R4selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 fused arylAny one of the above;
A1is any one of C1-C30 substituted or unsubstituted alkylene, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 heteroaryl, and substituted or unsubstituted C10-C40 thick aryl;
R5represents hydrogen or a C1-C30 substituted or unsubstituted alkyl group;
preferably, said R is5Hydrogen or a C1-C8 substituted or unsubstituted alkyl group, preferably hydrogen or a C1-C4 substituted or unsubstituted alkyl group, more preferably hydrogen or methyl;
preferably, the polymerizable ultraviolet light absorber is a product prepared by the following method:
2, 4-dihydroxy benzophenone and 3,4-Epoxycyclohexylmethyl methacrylate are subjected to ring-opening reaction under the catalysis of sodium hydroxide, under the nitrogen atmosphere, 2, 4-dihydroxy benzophenone and sodium hydroxide are firstly added into a stirrer, 3,4-Epoxycyclohexylmethyl methacrylate is added into the stirrer, the mixture reacts for 7 to 10 hours at 80 ℃, and after the reaction is finished, the mixture is washed with water and dried in vacuum to remove water; or the like, or, alternatively,
reacting methacryloyl chloride with 2, 4-dihydroxy benzophenone for 2 hours at 50 ℃ in anhydrous pyridine, slowly pouring the mixed product into dilute hydrochloric acid under the condition of stirring to separate out a reddish brown precipitate, and recrystallizing in absolute ethyl alcohol after column chromatography treatment to obtain the product 2-hydroxy 4-methyl acrylate benzophenone.
6. The inkjet fluid of claim 1, wherein the photoinitiator comprises a monoacylphosphine oxide and/or a bisacylphosphine oxide;
preferably, the acylphosphine oxide includes any one or a combination of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) - (2, 4-bis-phenoxyphenyl) phosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, or 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
7. The inkjet fluid of claim 1, wherein the radiation curable composition comprises at least 5 wt% allyl ether acrylate, based on the total weight of the radiation curable composition, and at least 3 wt% of a polymerizable ultraviolet absorber, based on the total weight of the radiation curable composition;
preferably, the radiation curable composition comprises at least 5 to 10 wt% of allyl ether acrylate based on the total weight of the radiation curable composition and at least 3 to 8 wt% of a polymerizable ultraviolet absorber based on the total weight of the radiation curable composition.
8. The inkjet fluid of claim 1, wherein the inkjet fluid is a UV-curable inkjet fluid;
preferably, the inkjet fluid is solvent-free;
preferably, the viscosity of the inkjet fluid is 1 to 20cps at 25 ℃.
9. A radiation curable inkjet ink comprising the radiation curable inkjet fluid according to any one of claims 1 to 8.
10. A method of inkjet printing comprising applying to a substrate the radiation curable inkjet fluid according to any one of claims 1 to 8 or the inkjet ink according to claim 9.
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| CN114015013A (en) * | 2021-11-16 | 2022-02-08 | 广东十辰十新材料有限公司 | Yellowing-resistant self-decoloring UV resin and application thereof in UV glue dripping |
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