Disclosure of Invention
The present disclosure provides a curable composition comprising, by weight:
epoxy compound (c): 30-70 parts (e.g., 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, or 65 parts);
polyfunctional vinyl ether compounds: 5-25 parts (e.g., 10 parts, 15 parts, or 20 parts);
oxetane compounds: 5-30 parts (e.g., 10 parts, 15 parts, 20 parts, or 25 parts);
photosensitizer: 0.1-2 parts (e.g., 0.5 parts, 1 part, or 1.5 parts);
cationic photoinitiator: 1-12 parts (e.g., 2 parts, 5 parts, 8 parts, or 10 parts).
In some embodiments, the curable composition further comprises: and (3) a fluorinated resin in a weight content interval of (0,15 parts).
In some embodiments, the curable composition further comprises: and (5) a pigment, wherein the content interval by weight of the pigment is (0,45 parts).
In some embodiments, the epoxy compound is a compound containing an epoxy group (e.g., a cationically photocurable epoxy group). The epoxy compound has at least one epoxy group, preferably two epoxy groups, in the molecule.
In some embodiments, the parts by weight of epoxy compound in the curable composition is from 35 to 70 parts, particularly preferably from 40 to 60 parts.
In some embodiments, the epoxy compound comprises a cycloaliphatic epoxy resin, divinylbenzene dioxide, limonene dioxide, epoxidized soybean oil, epoxidized polybutadiene, or combinations thereof.
In some embodiments, the epoxy compound comprises a cycloaliphatic epoxy resin, divinylbenzene dioxide, limonene dioxide, or combinations thereof.
In some embodiments, the curable composition contains a first type of epoxy compound and a second type of epoxy compound in a ratio of 10:1 to 2:1, preferably 8:1 to 3: 1. Wherein the first type of epoxy compound comprises a cycloaliphatic epoxy resin, divinylbenzene dioxide, limonene dioxide, or combinations thereof; the second epoxy compound includes epoxidized soybean oil, epoxidized polybutadiene, or a combination thereof. Based on the above, the curable composition has the advantages of high curing speed, excellent physical and chemical resistance and excellent flexibility. (e.g., example F1-2, F2-4).
In some embodiments, the cycloaliphatic epoxy resin comprises bis (3, 4-epoxycyclohexylmethyl) adipate, (3, 4-epoxy) cyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexanecarboxylate-3 ', 4' -epoxy-6-methylcyclohexanemethyl, liquid dicyclopentenyl ether dioxide, bis (2, 3-epoxycyclohexyl) ether, 3, 4-epoxy-6-methylcyclohexylmethyl carboxylate,
1, 2-bis (3, 4-epoxycyclohexylmethoxy) alkane:
1, 2-bis (3, 4-epoxycyclohexylmethoxy) p-xylene:
epoxidized polybutadiene (e.g., polyBD-605E from Sartomer
PolyBD-600E), or a combination thereof.
In some embodiments, the epoxy compound further comprises a bisphenol A epoxy resin, a novolac epoxy resin, or a combination thereof in an amount ranging from (0,30 weight percent) based on the total weight of the epoxy compound.
In some embodiments, the oxetane compound is a four-membered ring ether compound, can be subjected to cationic ring-opening polymerization, and has the characteristics of low viscosity, low curing shrinkage, high polymerization speed and the like.
In some embodiments, the reactive group of the oxetane compound is an oxetane having at least one oxetane, and preferably two oxetanes, in one molecule.
In some embodiments, the oxetane compound is a monofunctional oxetane, including, for example, 3-ethyl-3-hydroxymethyl-oxetane (TMPO OXT101), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT-212)
Or a combination thereof.
In some embodiments, the oxetane compound is a multifunctional oxetane, including, for example, 3' - (oxybispenemethylene) -bis- (3-ethyl) oxetane (OXP OXT221)
1,4 bis [ (3-ethyl-3-oxymethyleneoxetanyl) methyl ] benzene (OXT121)
3, 3' - [1, 4-butylbis (oxymethylene) ] -bis- (3-ethyl) oxetane
Or a combination thereof.
In some embodiments, the multifunctional vinyl ether compound contains a first reactive functional group and a second reactive functional group, the first reactive functional group being a vinyl ether group or a propenyl ether group, and the second reactive functional group being a radical reactive functional group or a cationic reactive functional group.
In some embodiments, both vinyl ether groups and propenyl ether groups are among the cationically active functional groups.
In some embodiments, the second reactive functional group in the multifunctional vinyl ether compound is a vinyl ether group or a propenyl ether group (e.g., F1-1, F1-2, F1-3, F2-1, F2-4, F3-2, F3-3, G1-1, G1-3 of examples). Alternative polyfunctional vinyl ether compounds include triethylene glycol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, 1, 4-butanediol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, or combinations thereof. Based on the method, the requirement of the curing rate of the system can be met, a certain degree of crosslinking is achieved, and the solvent resistance of the printed product is improved.
In some embodiments, the first reactive functional group is a vinyl ether group or a propenyl ether group and the second reactive functional group is a free radical reactive functional group or a cationic reactive functional group other than the vinyl ether group and the propenyl ether group (e.g., examples F1-5, F2-5, F3-4, G1-2). Based on this, the photocuring rate can be further accelerated, and the conversion rate can be improved.
In some embodiments, the polyfunctional vinyl ether compounds include
3-ethyl-3-allylmethoxyoxetane:
2- [2- (ethyleneoxy) ethoxy ] ethyl 2-acrylate:
(3, 4-epoxycyclohexylmethoxy) propene:
or a combination thereof.
In 3-ethyl-3-allylmethoxyoxetane, the first reactive functional group is a propenyl ether group and the second reactive functional group is an oxetane group.
In 2- [2- (vinyloxy) ethoxy ] ethyl 2-acrylate, the first reactive functional group is a vinyl ether group and the second reactive functional group is a (meth) acrylate group.
In the (3, 4-epoxycyclohexylmethoxy) propene, the first reactive functional group is a propenyl ether group and the second reactive functional group is an alicyclic epoxy group.
In some embodiments, the second functional group is an oxetane group, an acrylate group (e.g., a methacrylate group), or an alicyclic epoxy group.
The inventors have found that a specific amount of a polyfunctional vinyl ether compound is effective for accelerating the curing reaction of oxetane and an epoxy compound, and improving the photocuring rate of the entire curable composition and the solvent resistance of a printed product. When the content is less than a certain value, the photocuring rate of the curable composition is lowered, and when the content is too high, the solvent resistance of the curable composition is lowered.
In some embodiments, the curable composition may further comprise 0.5 to 10 parts of a fluorinated resin. The fluorinated resin may include a perfluoropolyether, a fluorinated urethane acrylate, a fluorinated epoxy, or a combination thereof. Based on this, the surface energy of the coating of the curable composition can be further reduced, enhancing its anti-smudge and anti-fingerprint properties.
In some embodiments, the curable composition further comprises 5 to 25 parts of a hydroxy compound. The hydroxyl compound may include a polyester polyol, a polyether polyol, cellulose acetate butyrate, polycaprolactone, castor oil, or a combination thereof.
In some embodiments, the curable composition further comprises 1 to 20 parts of an acrylate compound containing a free radical reactive group. Thereby forming a free radical-cationic hybrid polymerization system. In some embodiments, the free radical reactive group-containing acrylate compound comprises bisphenol a epoxy acrylate (e.g., F1-3 of example 1), trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerol triacrylate, propoxylated glycerol triacrylate, or combinations thereof.
The free radical photocuring has the advantages of high curing speed, excellent physical and chemical resistance, rich resin varieties and the like, but has the defects of oxygen inhibition, large polymerization volume shrinkage, poor adhesion and the like. The cation photocuring has the advantages of small volume shrinkage, small oxygen resistance, good adhesive force and the like, and has the defects of low curing speed and the like. Under certain conditions, the free radical-cation hybrid ultraviolet curing system can simultaneously carry out free radical and cation photocuring reactions, fully exerts the respective advantages of the free radical and cation photocuring systems, generates good synergistic effect, accelerates the curing speed, effectively shortens the surface drying time, and simultaneously does not affect the adhesive force and the physicochemical resistance. The inventors found experimentally that acrylate compounds containing free radical reactive groups are complex to influence the curing process of the hybrid system and do not necessarily form good synergistic effects. For example, when 15 parts of a urethane acrylate having the model number CN996 or a polyester acrylate having the model number CN2264 was added to the curing system of the curable composition of the present disclosure, the hybrid system rather failed to cure completely, and even had a sticky surface.
In some embodiments, the curable composition includes 2 to 20 parts, such as 5, 10, or 15 parts, of filler.
In some embodiments, the filler comprises calcium carbonate, kaolin, aluminum silicate salts, wax powder, and silica matting powder, or a combination thereof.
In some embodiments, the cationic photoinitiator comprises a diaryliodonium salt, a triarylsulfonium salt, an arylferrocenium salt, or a combination thereof. The photosensitizer which can be matched with the photoinitiator and is selected by the invention can generate strong absorption in a long-wave spectral region emitted by a UVLED light source, firstly absorb UV light energy to be excited, and then transfer electrons to the initiator, thereby generating super acid to initiate cationic photocuring.
In some embodiments, the photosensitizer comprises a thioxanthone derivative, an anthraquinone derivative, or a combination thereof. As the absorption peak of the onium salt photoinitiator is mostly concentrated at 250-300nm, the emission spectrum of the long-wave UVLED light source is not matched. The photosensitizer which can be matched with the photoinitiator and is selected by the invention can generate strong absorption in a long-wave spectral region emitted by a UVLED light source, firstly absorb UV light energy to be excited, and then transfer electrons to the initiator, thereby generating super acid to initiate cationic photocuring.
In some embodiments, the curable composition further contains 2 to 45 parts of a pigment, such as 5 to 25, 10 to 35, or 15 to 30 parts of a pigment.
In some embodiments, the pigments are organic pigments, which are azo pigments, phthalocyanine blues, phthalocyanine greens, quinacridones, and the like, and inorganic pigments, which are titanium white, carbon black, and the like.
In some embodiments, the pigment is a pigment refinery, which is the product of coating a pigment with a carrier resin. It has the advantages of excellent transparency, high color development, small particle size, etc.
In some embodiments, the pigment comprises an effect pigment, an optically variable pigment, or a combination thereof. Alternatively, optically variable pigments are multilayer thin film interference pigments that exhibit color change when viewed at two different angles, front and glancing. Alternatively, the effect pigment is a metallic pigment or a pearlescent pigment having a certain luster, such as a metal, a metal oxide, or a pigment obtained by coating a substrate with a multilayer oxide of mica, alumina or the like. Optionally, the effect pigments are pigments prepared by wet chemical or Chemical Vapour Deposition (CVD), the flaky substrate or core material being coated alternately with a metal oxide or a mixture of metal oxides of the high and low refractive index layers. The material of the substrate may include mica, alumina, silica, glass, metal, etc., and the material of the high refractive index metal oxide layer or metal oxide mixture layer may include TiO2、Fe2O3、ZrO2ZnO or other compound having a high refractive index, and the material of the low refractive index metal oxide layer or metal oxide mixture layer may include SiO2、Al2O3And the like. When the glasses are observed at two different angles of front view and glancing view, color change can be presented.
In some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some embodiments, the curable composition has the following formulation:
in some aspects, there is provided the use of the above curable composition as a photocurable ink, photocurable coating, or photocurable adhesive under ultraviolet light.
In some embodiments, a mercury lamp may be used as the light source for the ultraviolet light.
In some embodiments, a UVLED may be employed as a source of ultraviolet light. The ultraviolet light generated by the UVLED light source is typically a single band ultraviolet light.
In some embodiments, the ultraviolet light is a single band of ultraviolet light or a mixture of multiple (e.g., 2-10) single band ultraviolet lights. The peak wavelength of the single-band ultraviolet light can be within the range of 360-410 nm, and the peak wavelength of the single-band ultraviolet light can be within the range of 360-365 nm, 365-370 nm, 370-375 nm, 375-380 nm, 380-385 nm, 385-390 nm, 390-395 nm, 395-400 nm, 400-405 nm or 405-410 nm.
In some aspects, a method for curing the curable composition is provided, which comprises irradiating the curable composition with ultraviolet light, wherein the ultraviolet light refers to a single-band ultraviolet light or a mixture of several (for example, 2 to 10) single-band ultraviolet lights.
In some embodiments, the method of the present disclosure includes printing the curable composition on a substrate, which may be flexo or rotogravure printing, etc., and when applied to a protective coating on the surface of a banknote, it is preferably flexo printing, and the substrate may be paper-based or plastic, and the plastic substrate includes biaxially oriented polypropylene (BOPP), polycarbonate, polyethylene terephthalate (PET), etc. The printing ink can also be printed by adopting a photogravure gravure or rotogravure mode, the base material can also be a paper base or plastic base material, and particularly when the printing ink is printed on a BOPP film, the printing ink can show good adhesive force and physical and chemical resistance.
The term "multifunctional vinyl ether-based compound" refers to a multifunctional compound having a vinyl ether or propenyl ether structure, which may be a monomer, an oligomer and/or a polymer.
The term "oxetane compound" refers to a compound having an oxetane, which is monofunctional and/or polyfunctional, which may be monomeric, oligomeric and/or polymeric.
The term "epoxy compound" is an aliphatic and/or aromatic compound having an epoxy group, which is monofunctional and/or polyfunctional, which may be monomeric, oligomeric and/or polymeric.
The term "acrylate compound containing a free radical reactive group" is monofunctional and/or multifunctional, and may be a monomer, oligomer and/or polymer.
The term "free radical reactive functional group" refers to a functional group that can undergo a free radical type UV curing reaction.
The term "cationically active functional group" is a functional group that is capable of sending cationic UV curing reactions.
The term "epoxy compound" does not include the vinyl ether-based compounds described above.
The term "epoxy compound" does not include the oxetane compounds described above.
The term "epoxy compound does not include the above-mentioned" acrylate compounds containing free radical reactive groups ", for example bisphenol a epoxy acrylate.
The term "oxetane compound" does not include the above vinyl ether compounds.
The term "single band ultraviolet light" refers to ultraviolet light having a full width at half maximum (FWHM) of the spectrum below 10nm, for example below 5 nm.
The term "comprising" means in an amount of 10 to 100% by weight, for example 20%, 40%, 60%, 80% or 100%.
Advantageous effects
The curable compositions of the present invention have one or more of the following advantages:
(1) the curing speed is high, for example, the curing speed is more than or equal to 60 m/min;
(2) the solvent resistance is good, for example, the butanone resistance is more than or equal to 4 grade;
(3) the kneading resistance is good, for example, the kneading resistance is more than or equal to grade 4.
(4) Has better curing performance under single-waveband ultraviolet light.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and can be obtained by commercial or self-synthesis.
The ink set performance test and rating methods of the following examples are as follows:
curing rate: the fingers can enable the UV ink to be cured to reach the maximum speed of the conveyor belt of the ultraviolet curing machine when the surface is dry, the ink film is pressed by the fingers after the UV ink is cured, the ink film is free from sticky feeling, and the surface is dry when no trace is left on the fingers.
Butanone resistance wiping: the testing of the butanone wiping resistance was carried out with reference to the standard GB/T23989-2009 (determination of the solvent wiping resistance of the coating), and the evaluation was carried out according to the ink falling condition after wiping.
Kneading resistance: the rub resistance was tested according to the standard ASTM F392 and the prints were rated according to ink drop after rubbing.
Grading: after the test, the ink is classified into 5 grades according to the ink falling condition, wherein the non-falling is classified into 5 grades, the basically non-falling is classified into 4 grades, the slight falling is classified into 3 grades, the obvious falling is classified into 2 grades, and the serious falling is classified into 1 grade.
The three test methods are well known in the field and used for evaluating the curing performance and the physical and chemical resistance of the ink, the resistance to butanone wiping reflects the quality of the solvent resistance of the ink, the resistance to kneading reflects the quality of the flexibility of the ink, the flexibility of the ink is better, and the kneading resistance grade is higher.
Example 1
According to the formulation shown in Table 1, a vinyl ether-based compound and an oxetane compound were first mixed with a matting powder, stirred for 20min at a rotation speed of 1000 rpm by a high-speed disperser, then other components were gradually added, and finally stirred for 15 min.
The inks were each coated onto a paper substrate to a thickness of about 2 microns using a flexographic coater with an anilox roll of 400 lines/inch. Then the power is 8W/cm2Curing is carried out under a UVLED light source with the wavelength of 365 nm. Physicochemical resistance test was performed after 24 hours, and the curing properties and the test results are shown in Table 1.
Experimental conclusion of table 1:
(1) as can be seen from the data in Table 1, the inks (F1-1 to F1-3) of the present invention have improved curing properties, and the inks (F1-4) beyond the range of the formula have poor curing properties;
(2) f1-5 in the ink system, 3-ethyl-3-allyl methoxy oxetane is further adopted as a diluent, based on the component system, the curing speed of the ink of more than or equal to 100m/min is obtained (the maximum speed of a conveyor belt of an ultraviolet curing machine is 100m/min, and more than or equal to 100m/min means that the ink can be fully cured at the maximum speed), and meanwhile, the rubbing resistance and the butanone wiping resistance of the ink are also particularly excellent.
(3) F1-2 uses a combination of adipic acid bis (3, 4-epoxycyclohexylmethyl ester) and epoxidized polybutadiene, PolyBD-605E, the curing rate can reach 60m/min, and the kneading resistance and the butanone wiping resistance are both 5 grades.
(4) The formulation of comparative example F1-4, which is outside the scope of the inventive formulation, did not cure effectively under a single band of UV light.
Example 2
According to the formulation shown in Table 2, a vinyl ether-based compound and an oxetane compound were first mixed with a matting powder, stirred for 20min at a rotation speed of 1000 rpm by a high-speed disperser, then other components were gradually added, and finally stirred for 15 min.
The inks were each coated onto a paper substrate to a thickness of about 2 microns using a flexographic coater with an anilox roll of 400 lines/inch. Then the power is 8W/cm2Curing is carried out under a UVLED light source with the wavelength of 365 nm. And after 24h, physicochemical resistance detection is carried out, and the curing performance and the detection result are shown in Table 2.
Experimental conclusion of table 2:
(1) f2-4 uses the combination of (3, 4-epoxy group) cyclohexyl methyl ester cyclohexyl formic acid (3, 4-epoxy group) and epoxidized soybean oil, based on the component system, the curing speed can reach 60m/min, and the kneading resistance and the butanone wiping resistance are both 5 grades.
(2) F2-5 used "(3, 4-epoxycyclohexylmethoxy) propene" as a reactive diluent, and based on the component system, a curing rate of 100m/min or more was obtained.
(3) The formulation of comparative example F2-2 is outside the inventive formulation and exhibits poor butanone rub resistance after curing under a single band UV light.
(4) The formulation of comparative example F2-3, which is outside the scope of the inventive formulation, did not cure effectively under a single band of UV light.
Example 3
According to the formula shown in Table 3, the epoxy compound, vinyl ether, oxetane, polyester, dispersant and carbon black or phthalocyanine blue are mixed, stirred uniformly, ground by a sand mill until the fineness is less than 5 microns, added with photosensitizer and initiator, and stirred for 15 min. The ink was coated on a PET film using a flexographic coater with an anilox roll of 200 lines/inch. Then the power is 16W/cm2Curing is carried out under a UVLED light source with the wavelength of 385 nm. Physicochemical resistance test was performed after 24 hours, and the curing properties and the test results are shown in Table 3.
Experimental conclusion of table 3:
(1) the inks F3-1 and F3-4 used "2- [2- (vinyloxy) ethoxy ] ethyl 2-acrylate" as the reactive diluent, based on the component system, obtained curing rates of 100m/min or more, and were both 5 grades resistant to rubbing and to butanone wiping.
(2) Ink F3-2 used diethylene glycol divinyl ether as the reactive diluent, and based on this component system, a cure rate of 80m/min, a rub resistance of grade 4, and a methyl ethyl ketone rub resistance of grade 5 were obtained.
Example 4
According to the formula shown in Table 4, the components except the photosensitizer and the initiator are firstly mixed by a high-speed dispersion machine under the stirring condition, stirred for 20min at the rotating speed of 1000 r/min, then the photosensitizer and the initiator are added, and stirred for 15 min. The ink can be printed on a BOPP film or a BOPP-based plastic substrate by a photogravure press with an anilox roller of 180 lines/inch. Then the power is 16W/cm2Curing is carried out under a UVLED light source with the wavelength of 385 nm. Physicochemical resistance test was performed after 24 hours, and the curing properties and the test results are shown in Table 4.
Experimental conclusion of table 4:
(1) inks G1-1 through G1-3 all had improved curing properties. The ink G1-2 adopts 3-ethyl-3-allylmethoxyoxetane as a reactive diluent, and based on the component system, the curing rate of more than or equal to 100m/min is obtained.
(2) G1-2 in the ink system of the invention, 3-ethyl-3-allyl methoxy oxetane is further adopted as a diluent, based on the component system, the curing rate of the ink is faster, and the ink is particularly excellent in the rolling resistance and the butanone wiping resistance.
(3) Ink G1-1 contains a Huayangtao photochromic pigment
A color change effect is exhibited. Ink G1-2 contained Merck Iriododin 9201, which exhibited an interference gold pearlescence effect. G1-1 and G1-2 can be printed on the see-through window of a printable plastic substrate, i.e. directly on a BOPP film. Or on an opaque treated printable plastic substrate. Or printing a part of the transparent window on the plastic base material, and printing the other part of the transparent window on the plastic base material after the opaque treatment.
While specific embodiments of the invention have been described in detail, those skilled in the art will understand that: various modifications and changes in detail can be made in light of the overall teachings of the disclosure, and such changes are intended to be within the scope of the present invention. The full scope of the invention is given by the appended claims and any equivalents thereof.