CN112062675A - Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink - Google Patents

Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink Download PDF

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CN112062675A
CN112062675A CN202010969710.0A CN202010969710A CN112062675A CN 112062675 A CN112062675 A CN 112062675A CN 202010969710 A CN202010969710 A CN 202010969710A CN 112062675 A CN112062675 A CN 112062675A
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monomer
curing
gravure ink
main material
functional
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杨爱军
周宏波
常国庆
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Changzhou Solid New Photographic Materials Co ltd
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Changzhou Solid New Photographic Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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Abstract

The invention provides a monomer with a free radical and cation dual curing function, a preparation method and radiation curing gravure ink, and relates to the technical field of ink. The monomer with the free radical and cation dual curing functions has the structural formula of R1-A-R2, A is polyester, polyether, polyurethane or hydrocarbon, R1 comprises at least one acrylate group, and R2 comprises at least one vinyl ether group or epoxy group. The radiation curing gravure ink comprises the functional main material I and the functional main material I, wherein the functional main material I is a monomer or resin at least containing two acrylic groups. The ink prepared by using the monomer has dual curing functions of free radical curing and cation curing, has the advantages of free radical curing and cation curing, is high in curing speed, small in adhesion to a film, small in smell and resistant to migration, avoids the defects of a free radical curing system and a cation curing system, is low in cost and can be popularized in a large area.

Description

Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink
Technical Field
The invention relates to the technical field of printing ink, in particular to a monomer with a free radical and cation dual curing function, a preparation method and radiation curing gravure printing ink.
Background
Most of the ink used in the gravure industry at present is solvent-based ink and water-based ink, and the radiation curing ink is rarely used. The conventional free radical curing ink has the advantage of high curing speed, but has the defects of high viscosity, poor adhesion to a film, strong smell, easy migration of residual initiator and monomer and the like. The gravure ink of the cationic curing system has low viscosity, small smell, migration resistance and good adhesion to a film, but has high cost and low curing speed, and is not beneficial to large-scale popularization.
Therefore, there is an urgent need to develop a product that can overcome the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to provide a monomer with a radical and cation dual curing function, which contains a functional group capable of polymerizing with a radical and a functional group capable of polymerizing with a cation, and a product prepared by utilizing the monomer has the radical and cation dual curing function.
Another object of the present invention is to provide a radiation curable gravure ink containing the aforementioned monomer, which has advantages of radical curing and cationic curing, and has a fast curing speed, adhesion to a film, a small odor, and migration resistance.
The invention also aims to provide a preparation method of the monomer, which has the advantages of simple operation, simple reaction conditions and good performance of the prepared monomer.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
In one aspect, the embodiments provide a monomer having dual curing functions of radical and cation, the monomer has a structural formula of R1-a-R2, the a is polyester, polyether, polyurethane or hydrocarbon, the R1 includes at least one acrylate group, and the R2 includes at least one vinyl ether group or epoxy group.
In another aspect, the present invention also provides a radiation curing gravure ink containing the monomer, which includes the monomer and a first functional main material, wherein the first functional main material is a monomer or a resin containing at least two acrylic groups.
In another aspect, an embodiment of the present invention provides a method for preparing the foregoing monomer, including the following steps: mixing a monomer containing an R1 group, a monomer containing an R2 group and a reaction auxiliary agent, reacting for 1.5-2.5 h, adding the monomer containing A, refluxing for 4.5-5.5 h at 110-120 ℃, removing a water phase, washing, and removing toluene to obtain the monomer.
Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:
the ink prepared by the monomer provided by the invention has dual curing functions of free radical curing and cation curing, has the advantages of free radical curing and cation curing, is high in curing speed, small in smell and migration-resistant, has high adhesion to a film, avoids the defects of a free radical curing system and a cation curing system, is low in cost and can be popularized in a large area.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 are all conventional products available commercially.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.
In one aspect, the embodiments provide a monomer having dual curing functions of radical and cation, the monomer has a structural formula of R1-a-R2, the a is polyester, polyether, polyurethane or hydrocarbon, the R1 includes at least one acrylate group, and the R2 includes at least one vinyl ether group or epoxy group.
In some embodiments of the present invention, the monomer with dual curing functions of radical and cation, wherein R1 is a graft of acrylic functional group, and R1 contains at least one acrylate functional group and is capable of polymerizing with radical.
In some embodiments of the present invention, in the above monomer having dual curing functions of radical and cation, the R2 is a graft polymer containing vinyl ether, epoxy group or oxetane group, and the R2 contains at least one of the above functional groups and can be polymerized with cation.
In another aspect, the present invention also provides a radiation curing gravure ink containing the monomer, which includes the monomer and a first functional main material, wherein the first functional main material is a monomer or a resin containing at least two acrylic groups.
In some embodiments of the present invention, the functional primary material in the radiation curable gravure ink includes di-functional propionate, tri-functional acrylate, and higher functional acrylate.
In some embodiments of the present invention, the radiation curable gravure ink described above comprises one or more of difunctional propionate bicyclodecane diacrylate, 1,6 hexanediol diacrylate, hexanediol ethoxy diacrylate, butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol a diacrylate homologues, and alkoxylated hexanediol diacrylate.
In some embodiments of the present invention, the trifunctional acrylate in the radiation curable gravure ink includes one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and glycerol propoxyl triacrylate.
In some embodiments of the present invention, the higher functionality acrylate in the radiation curable gravure ink described above is one or more of pentaerythritol tetraacrylate, pentaerythritol ethoxy tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
In some embodiments of the present invention, the radiation curable gravure ink further includes a second functional main material, where the second functional main material is a monomer or resin containing at least one epoxy group, or a monomer or resin containing at least one oxetanyl group, or a vinyl monomer or resin.
In some embodiments of the present invention, the vinyl monomer or resin in the radiation curable gravure ink includes one or more of diethylene glycol divinyl ether, triethylene glycol divinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, N-vinyl pyrrolidone, and N-vinyl carbazole and polyethylene glycol divinyl ether.
In some embodiments of the present invention, the epoxy group-containing monomer or resin in the radiation curable gravure ink includes 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 2-epoxy-4-vinylcyclohexane, tetrahydrodiglycidyl phthalate, diglycidyl cyclohexane-1, 2-dicarboxylate, 4-vinyl-1-cyclohexene diepoxide, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, N, -tetracyclooxypropyl-4, 4-diaminodiphenylmethane, and the epoxy group-containing monomer or resin further includes 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylformate and caprolactone in a molar quantity ratio of 1:1, and the epoxy group-containing monomer or resin further comprises a polymerization product obtained by reacting 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate and caprolactone in a molar quantity ratio of 1: 3.
In some embodiments of the present invention, the oxetane-containing monomer or resin in the radiation curable gravure ink includes 3-hydroxymethyl-3-ethyl oxetane, 3-ethyl-3- [ (oxyethylene-2-methoxy) methyl ] oxetane, bis (1- (3-methoxy-3-ethyl oxetanyl) -3-methoxypropyl-2-) methoxyethylene oxide, 3'- (4, 15-bis (oxyethylene-2-methoxy) -2,6,13, 17-tetraoxy-n-octadecyl-1, 18) bis (3-ethyl oxetane), 3' - (7,10, 13-trimethyl-4, 17-bis (2-methyl-oxyethylene) -2,6,9,12,15, 19-hexaoxoeicosane-1, 20-) bis (3-ethyloxetane), 3' - [ oxybis-methylene ] bis [ 3-ethyl ] oxetane, 3-ethyl-3- [4- [ (3-ethyloxetan-3-yl) methoxy ] butoxymethyl ] oxetane, 1- (3-ethyloxetan-3-methoxy) -3-methoxypropyl-2-methacrylate and 1, 18-bis (3-ethyloxetan-methoxyoctadecanoxy-tetra-2, 6,13,17-) yl-4, 15-bis (2-methacrylate).
In some embodiments of the present invention, the radiation curable gravure ink further includes a radical initiator and a cationic initiator.
In some embodiments of the present invention, the free radical initiator in the above radiation curable gravure ink comprises one or more of an α -hydroxy ketone, an α -amino ketone, a benzoyl formate, a mixture of acyl phosphines, and a bisacyl phosphine.
In some embodiments of the present invention, the cationic initiator in the above radiation curable gravure ink comprises one or more of a diazonium salt, a diaryliodonium salt, a triarylthionium salt, an alkylthionium salt, an iron aryl salt, a sulfonyloxy ketone, and a triarylsiloxy ether.
In some embodiments of the present invention, the radiation curable gravure ink further includes a pigment, a filler, and an auxiliary agent.
In some embodiments of the present invention, the radiation curable gravure ink includes the following raw materials in percentage by weight: 10-80% of monomer, 0-50% of first functional main material, 0-80% of second functional main material, 1-8% of free radical initiator, 1-8% of cationic initiator, 5-15% of functional auxiliary agent and 0-10% of filler.
In some embodiments of the present invention, the radiation curable gravure ink includes the following raw materials in percentage by weight: 30-60% of monomer, 10-30% of first functional main material, 20-50% of second functional main material, 2-4% of free radical initiator, 3-6% of cationic initiator, 5-15% of functional auxiliary agent and 0-10% of filler.
In some embodiments of the present invention, the particle size of the radiation curable gravure ink is 4 to 6 micrometers, and preferably 5 micrometers.
In another aspect, an embodiment of the present invention provides a method for preparing the foregoing monomer, including the following steps: mixing a monomer containing an R1 group, a monomer containing an R2 group and a reaction auxiliary agent, reacting for 1.5-2.5 h, adding the monomer containing A, refluxing for 4.5-5.5 h at 110-120 ℃, removing a water phase, washing, and removing toluene to obtain the monomer.
In some embodiments of the present invention, in the preparation method of the monomer, the monomer containing the R1 group, the monomer containing the R2 group and the reaction assistant are mixed and reacted for 2 hours, and the reflux time is 5 hours.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The present example aims to provide a monomer with dual curing functions of free radical and cation, which comprises the following preparation steps:
58 g of raw material I, 51.45 g of raw material V, 300 g of toluene, 0.1 g of sodium hypophosphite, 0.1 g of copper sulfate, 0.1 g of p-methoxyphenol and 5 g of sodium methyl benzenesulfonate are added into a three-neck flask with a thermometer, a stirrer and a reflux device, the temperature is heated and controlled to react for 1.5 to 2.5 hours, preferably 2 hours, then 121 g of raw material IV is added, the mixture is refluxed for 4.5 to 5.5 hours at the temperature of 110 ℃ and 120 ℃, preferably 5 hours, the water yield exceeds 9 g, the temperature is reduced to room temperature, 60 g of 10 percent sodium hydroxide solution is added, the lower-layer water phase is separated, 100 g of 10 percent sodium chloride solution is used for washing for 2 times, and the residual part is subjected to vacuum toluene removal to obtain about 219 g of reactant monomer.
In this example, the structural formula of the first raw material is as follows:
CH2＝CH-O-CH2-CH2-CH2-CH2-OH
the structural formula of the raw material V is as follows:
Figure BDA0002683659340000071
the structural formula of the raw material IV is as follows:
Figure BDA0002683659340000072
the structural formula of the monomer I is as follows:
Figure BDA0002683659340000073
example 2
The present example aims to provide a monomer with dual curing functions of free radical and cation, which comprises the following preparation steps:
51 g of raw material bis 3-ethyl-3-oxetanylcarbinol (CAS: 3047-32-3), 51.45 g of raw material five, 300 g of toluene, 0.1 g of sodium hypophosphite, 0.1 g of copper sulfate, 0.1 g of p-methoxyphenol and 5 g of sodium methyl benzenesulfonate are added into a three-neck flask with a thermometer, a stirrer and a reflux device, the temperature is heated and controlled for reaction for 2 hours, then 121 g of raw material four, 110 and 120 ℃ are added for reflux for 5 hours, the water yield exceeds 9 g, the temperature is reduced to room temperature, 60 g of 10 percent sodium hydroxide solution is added, the lower-layer water phase is separated, 100 g of 10 percent sodium chloride solution is used for washing for 2 times, and the residual part is subjected to vacuum toluene removal to obtain about 212 g of reactant monomer two.
In this example, the structural formula of the second raw material is as follows:
Figure BDA0002683659340000081
the structural formula of the raw material V is as follows:
Figure BDA0002683659340000082
the structural formula of the raw material IV is as follows:
Figure BDA0002683659340000083
the structural formula of the monomer II is as follows:
Figure BDA0002683659340000091
example 3
The present example aims to provide a monomer with dual curing functions of free radical and cation, which comprises the following preparation steps:
57 g of raw material III, 51.45 g of raw material V, 300 g of toluene, 0.1 g of sodium hypophosphite, 0.1 g of copper sulfate, 0.1 g of p-methoxyphenol and 5 g of sodium methyl benzenesulfonate are added into a three-neck flask with a thermometer, a stirrer and a reflux device, the temperature is heated and controlled for reaction for 2 hours, then 121 g of raw material IV is added, the temperature is reduced to room temperature after reflux is carried out for 5 hours at 120 ℃ with the water yield exceeding 9 g, 60 g of 10% sodium hydroxide solution is added, the lower-layer water phase is separated, the 100 g of 10% sodium chloride solution is used for washing for 2 times, the rest is removed in vacuum, and about 218 g of reactant monomer is obtained.
In this example, the structural formula of the raw material three is as follows:
Figure BDA0002683659340000092
the structural formula of the raw material V is as follows:
Figure BDA0002683659340000093
the structural formula of the raw material IV is as follows:
Figure BDA0002683659340000101
the structural formula of monomer III is as follows:
Figure BDA0002683659340000102
it should be noted that the monomer with the radical and cation dual curing function of the present invention is not limited to the preparation of the raw materials provided in examples 1 to 3, as long as the raw materials with the structural formula of R1-a-R2 of the obtained monomer can be used for preparing the monomer with the radical and cation dual curing function, as long as the generated monomer satisfies the following conditions, a is polyester, polyether, polyurethane or hydrocarbon, R1 includes at least one acrylate group, and R2 includes at least one vinyl ether group or epoxy group. In particular, R1 is a graft of acrylic functional groups, containing at least one acrylic functional group and capable of polymerizing with free radicals. R2 is a graft containing vinyl ether, epoxy or oxetane groups, containing at least one of the above-mentioned functional groups and capable of polymerizing with cations.
Example 4
The present embodiment aims to provide several types of radiation curable gravure inks with different ratios of monomers having dual curing functions of free radicals and cations, which are specifically as follows:
TABLE 1
Figure BDA0002683659340000103
Figure BDA0002683659340000111
Specifically, the raw materials used in table 1 are:
TCM101, Qiangli corporation, hydroxymethyl-3-ethyloxetane;
the TCM 104: power company, 3-ethyl-3- [ (benzyloxy) methyl ] oxetane;
2021P: xylonite, 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester;
dispersing agent: lubriun Solsperse 24000;
polymerization inhibitor: MEHQ;
carbon black: mitsubishi MA 11;
DPGDA and DPHA: is a product of Taiwan Changxing company; (ii) a
An agent for enhancing the sensation of cold: Tu-Kagaku TR-PSS-303;
leveling agent: BYK-331, BYK, Germany;
defoaming agent: BYK-055, BYK, Germany.
The radiation curing gravure ink provided by the present invention is not limited to the raw materials described in table 1, and specifically:
the first functional main material is a monomer or resin containing at least two acrylic groups, and the monomer or resin contains acrylic monomers or resins which are commonly available in the market, such as: difunctional propionate, selected from the group consisting of dicyclodecane diacrylate, 1,6 hexanediol diacrylate (HDDA), hexanediol ethoxy diacrylate, butanediol diacrylate (BDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), tricyclodecane diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A diacrylate homologues, alkoxylated hexanediol diacrylate; trifunctional acrylate selected from trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate (TMPTA), Glycerol Propoxylate Triacrylate (GPTA); higher functionality acrylates may be selected from pentaerythritol tetraacrylate, pentaerythritol ethoxy tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.
The second functional main material is a monomer or resin at least containing one epoxy group, or a monomer or resin at least containing one oxetanyl group, or a vinyl monomer or resin. The mass percentage of the ink in the whole ink is 0-80%, and preferably 30-50%.
Specifically, the vinyl monomer or resin comprises one or more of diethylene glycol divinyl ether, triethylene glycol divinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, N-vinyl pyrrolidone, and N-vinyl carbazole and polyethylene glycol divinyl ether.
Specifically, the epoxy group-containing monomer or resin includes 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 2-epoxy-4-vinylcyclohexane, diglycidyl tetrahydrophthalate, diglycidyl cyclohexane-1, 2-dicarboxylate, 4-vinyl-1-cyclohexene diepoxide, 4- (2, 3-epoxypropoxy) -N, N-bis (2, 3-epoxypropyl) aniline, N, N, N, -tetracyclooxypropyl-4, 4-diaminodiphenylmethane, and the epoxy group-containing monomer or resin also includes 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxy cyclohexyl formate and caprolactone according to the molar quantity ratio of 1:1, and the epoxy group-containing monomer or resin also comprises a polymerization product obtained by reacting 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate and caprolactone according to the molar quantity ratio of 1: 3.
Specifically, the oxetane-containing monomer or resin includes 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- [ (oxyethylene-2-methoxy) methyl ] oxetane, bis (1- (3-methoxy-3-ethyloxetanyl) -3-methoxypropyl-2-) methoxyoxyethylene, 3'- (4, 15-bis (oxyethylene-2-methoxy) -2,6,13, 17-tetraoxy-n-octadecyl-1, 18) bis (3-ethyloxetane), 3' - (7,10, 13-trimethyl-4, 17-bis (2-methyl-oxyethylene) -2,6,9,12,15, 19-hexaoxoeicosane-1, 20-) bis (3-ethyloxetane), 3' - [ oxybis-methylene ] bis [ 3-ethyl ] oxetane, 3-ethyl-3- [4- [ (3-ethyloxetan-3-yl) methoxy ] butoxymethyl ] oxetane, 1- (3-ethyloxetan-3-methoxy) -3-methoxypropyl-2-methacrylate and 1, 18-bis (3-ethyloxetan-methoxyoctadecanoxy-tetra-2, 6,13,17-) yl-4, 15-bis (2-methacrylate).
In addition, the radical initiator in the radiation curing gravure ink provided by the invention comprises one or more of alpha-hydroxy ketone, alpha-amino ketone, benzoyl formate, acyl phosphine mixture and diacyl phosphine, the mass percentage of the radical initiator in the whole ink is 1-8%, preferably 2-4%, and the radical initiator mainly provides curing speed and enhances deep curing degree. The cationic initiator comprises one or more of diazonium salt, diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron aryl salt, sulfonyloxy ketone and triaryl siloxy ether, the mass percent of the cationic initiator in the whole ink is 1-8%, preferably 3-6%, and the cationic initiator mainly provides surface layer curing speed and enhances later-stage curing degree.
The pigment in the radiation curable gravure ink provided by the invention can be various pigments commonly found in the market, such as black pigment carbon black, red pigments 57:1, 53:1, 146, 122, 184, 176, 254, and the like; yellow pigments 12, 13, 14, 74, 150, 151, 180 and the like, blue pigments 15:3, 15:4 and the like, white pigments such as titanium dioxide, barium sulfate and the like, wherein the pigments comprise calcium carbonate, talcum powder, kaolin, silicon dioxide and the like, and the using amount of the pigments is 5-15% of the mass of the ink; the filler is common filler on the market, and the using amount of the filler is 0-10% of the mass of the ink; the functional assistant comprises a dispersant, a flatting agent, a wetting agent, a defoaming agent, a polymerization inhibitor and the like, and is added according to the requirement.
Examples of effects
The purpose of this effect example is to verify the performance of the radiation curable gravure inks of different formulation ratios in example 4.
Test items and test methods:
adhesion force: the detection is carried out by referring to the ink layer combination fastness standard in GB/T7705-2008 planographic decoration printed matter, GB/T7706-2008 relief decoration printed matter and GB/T7707-2008 intaglio decoration printed matter, and the falling area of the ink layer is less than 1.0 percent;
alcohol resistance: wrapping cotton gauze with 500 g valve, dipping alcohol, rubbing on the printed matter, and counting once for each round trip until the ink drops to expose the printed substrate;
flexibility: cutting the substrate into 6cm by 6cm, testing by adopting an IGT wrinkle-resistant device, respectively performing 3 times on the front and back sides of the four sides, and comparing the ink layer before unfolding and testing, wherein the angle-dependent dynamic optical effect is good;
migration resistance: reference is made to the use of EN 1186-1, -3, -14: 2002 migration test method.
The inks obtained from the formulations of example 4 were printed on a BOPP film using 94 lines, according to a 24 micron deep gravure plate, using 38 linesIrradiating with 5 nm LED light at an irradiation energy of 500mJ/cm2After printing for 48h, the test performance was tested, and the results are shown in table two.
TABLE 2
Formulation 1 Formulation 2 Formulation 3 Comparative formulation 1 Comparative formulation 2
Adhesion force 5 5 5 5 1
Alcohol resistance (times) 100 100 100 60 50
Flexibility Good taste Good taste Good taste It is preferable that Difference (D)
Migration resistance By passing By passing By passing By passing Can not pass through
As can be seen from Table 2, the adhesion, alcohol resistance, flexibility and migration resistance of the radiation curing gravure ink prepared according to the formulas 1 to 3 can reach the standard and have good performance, while the comparative formula 1 without the monomer described in the examples 1 to 3 has the adhesion reaching the effect of the formulas 1 to 3 but the alcohol resistance far lower than the formulas 1 to 3, and meanwhile, the comparative formula 3 without the monomer described in the examples 1 to 3 has the alcohol resistance far lower than the formulas 1 to 3, the flexibility is also poor, and the migration resistance fails to be tested.
In conclusion, the monomer provided by the invention can obviously improve the fixed line speed of a product prepared by using the monomer and reduce the cost, after the monomer is prepared into ink, functional main materials are added to improve the adhesive force, flexibility and curing performance of the ink, a free radical initiator is used for providing the curing speed and enhancing the deep curing degree, a cationic initiator is used for providing the surface curing speed and enhancing the later curing degree, and finally, the performance of the ink is properly improved by pigments, fillers and various auxiliaries, so that the finally prepared ink has the dual curing functions of free radical curing and cationic curing, has the advantages of free radical curing and cationic curing, is high in curing speed, small in adhesive force and smell on film and resistant to migration, avoids the defects of a free radical curing system and a cationic curing system, is low in cost and can be popularized in a large area.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. A monomer with a radical and cation dual curing function is characterized in that the monomer has a structural formula of R1-A-R2, A is polyester, polyether, polyurethane or hydrocarbon, R1 comprises at least one acrylate group, and R2 comprises at least one vinyl ether group or epoxy group.
2. The monomer having a radical and cation dual curing function according to claim 1, characterized in that: r1 is a graft of acrylic functional groups, R1 contains at least one acrylic functional group and is capable of polymerizing with free radicals; r2 is a graft containing vinyl ether, epoxy or oxetane group, R2 contains at least one of the above functional groups and is capable of polymerizing with cation.
3. A radiation curable gravure ink comprising the monomer of claim 1 or 2, characterized in that: the acrylic resin comprises a monomer and a first functional main material, wherein the first functional main material is a monomer or resin at least containing two acrylic groups.
4. The radiation curable gravure ink according to claim 3, wherein: the functional main material comprises one or more of bicyclodecane diacrylate, 1,6 hexanediol diacrylate, hexanediol ethoxy diacrylate, butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A diacrylate homologues, alkoxylated hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, glycerol propoxy triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxy tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
5. The radiation curable gravure ink according to claim 3, wherein: the epoxy resin composition also comprises a functional main material II, wherein the functional main material II is a monomer or resin at least containing one epoxy group, or a monomer or resin at least containing one oxetanyl group, or a vinyl monomer or resin.
6. The radiation curable gravure ink according to claim 5, wherein: also included are free radical initiators and cationic initiators.
7. The radiation curable gravure ink according to claim 6, wherein: also comprises pigment, filler and auxiliary agent; the radiation curing gravure ink comprises the following raw materials, by weight, 10-80% of a monomer, 0-50% of a functional main material I, 0-80% of a functional main material II, 1-8% of a free radical initiator, 1-8% of a cationic initiator, 5-15% of a functional auxiliary agent and 0-10% of a filler.
8. The radiation curable gravure ink according to claim 7, comprising the following raw materials in percentage by weight: 30-60% of monomer, 10-30% of first functional main material, 20-50% of second functional main material, 2-4% of free radical initiator, 3-6% of cationic initiator, 5-15% of functional auxiliary agent and 0-10% of filler.
9. The radiation curable gravure ink according to claim 7 or 8, wherein the particle size of the radiation curable gravure ink is 4 to 6 μm.
10. A method for preparing the monomer of claim 1 or 2, comprising the steps of: mixing a monomer containing an R1 group, a monomer containing an R2 group and a reaction auxiliary agent, reacting for 1.5-2.5 h, adding the monomer containing A, refluxing for 4.5-5.5 h at 110-120 ℃, removing a water phase, washing, and removing toluene to obtain the monomer.
CN202010969710.0A 2020-09-15 2020-09-15 Monomer with free radical and cation dual curing functions, preparation method and radiation curing gravure ink Pending CN112062675A (en)

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Application publication date: 20201211