CN109517433B - Recoatable high-coverage UV ink and preparation method and application thereof - Google Patents

Recoatable high-coverage UV ink and preparation method and application thereof Download PDF

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Publication number
CN109517433B
CN109517433B CN201811632502.0A CN201811632502A CN109517433B CN 109517433 B CN109517433 B CN 109517433B CN 201811632502 A CN201811632502 A CN 201811632502A CN 109517433 B CN109517433 B CN 109517433B
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parts
ink
acrylate resin
coverage
recoatable
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CN109517433A (en
Inventor
黄巨波
李玉良
王卫国
缪培凯
吕国强
杨波
凌云剑
伍松
符饶生
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Hunan Sokan New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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

Abstract

The invention discloses a recoatable high-coverage UV (ultraviolet) ink and a preparation method and application thereof, wherein the recoatable high-coverage UV ink comprises the following components: the coating comprises, by weight, 10-20 parts of amine modified epoxy acrylate resin, 20-50 parts of trifunctional polyurethane acrylate resin, 5-20 parts of hexafunctional or higher polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-20 parts of multifunctional reaction monomer, 5-25 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate. The recoatable high-coverage UV ink disclosed by the invention has the advantages that the amine modified epoxy acrylate resin effectively improves the curing rate of an ink system under the condition that the ink system has high coverage, and the wettability of a pigment is improved. The repairable high-covering UV ink has high covering capacity, is opaque, has an OD value larger than 5 and has zero VOC emission.

Description

Recoatable high-coverage UV ink and preparation method and application thereof
Technical Field
The invention relates to the field of UV (ultraviolet) ink, in particular to high-covering UV ink capable of being recoated. In addition, the invention also relates to a preparation method and application of the repairable high-covering UV ink.
Background
The UV (ultraviolet) curing technology is a material surface treatment technology which appears in the 60 s of the 20 th century, has the characteristics of high efficiency, environmental protection, energy conservation, high quality, low investment and the like, and is known as a new technology facing the green industry of the 21 st century. The UV ink is the most common one of the photo-curing products, and is widely applied to the printing and packaging industry and the optoelectronic industry. The UV printing ink is cured by UV irradiation at normal temperature, the energy consumption is only 10-20% of that of thermal curing, the UV printing ink is an energy-saving product, the UV printing ink has the other advantage that volatile organic compounds are not contained, the used diluents are all acrylic acid functional monomers with high boiling points, and the diluents participate in cross-linking polymerization during UV curing to form a part of a cross-linked net structure, so that no VOC is discharged, the environment is not polluted, the harm to human bodies and the possibility of fire hazard are reduced, and the UV printing ink belongs to an environment-friendly product. However, the existing high-coverage UV ink which should be recoated has many problems, the adhesion of the UV ink on a glass substrate is very poor, the coverage is weak, and the recoating cannot be performed, and in view of the above problems, the market is urgently required to develop a high-coverage UV ink which can be applied to a glass substrate.
Disclosure of Invention
The invention provides a recoatable high-coverage UV ink and a preparation method and application thereof, and aims to solve the technical problems that in the prior art, the UV ink is difficult to adhere to glass, cannot be recoated and has poor coverage.
The technical scheme adopted by the invention is as follows:
a high hiding UV ink capable of being recoated comprises the following components: the coating comprises, by weight, 10-20 parts of amine modified epoxy acrylate resin, 20-50 parts of trifunctional polyurethane acrylate resin, 5-20 parts of hexafunctional or higher functional polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-20 parts of multifunctional reaction monomer, 5-25 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate.
Further, the composition comprises the following components: the coating comprises, by weight, 10-15 parts of amine modified epoxy acrylate resin, 20-40 parts of trifunctional polyurethane acrylate resin, 5-15 parts of hexafunctional or higher polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-10 parts of multifunctional reaction monomer, 5-15 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate.
Further, the molecular weight of the thermoplastic acrylic resin was 7.5X 104～1.1×105。
Further, the polyfunctional reactive monomer is hexafunctional or higher.
Further, the photoinitiator adopts at least two of 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-acetone, isopropyl thia-nthrene, alpha, -dimethyl benzil ketal or 1-hydroxycyclohexyl benzophenone; and/or the auxiliary agent adopts at least two of a flatting agent, a defoaming agent or a wetting dispersing agent.
Further, the toner is at least one of carbon black powder, iron oxide black powder, rutile type titanium dioxide powder, benzimidazolone red toner, methylene amine metal complex yellow powder or phthalocyanine blue toner; and/or the filler adopts at least one of nano calcium carbonate, nano barium sulfate, nano alumina or wax powder.
According to another aspect of the present invention, there is also provided a method for preparing a repairable high hiding UV ink, which includes the above-mentioned repairable high hiding UV ink, including the steps of: mixing and dispersing amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional or higher polyurethane acrylate resin, thermoplastic acrylic resin, multifunctional reaction monomer and monofunctional reaction monomer to obtain mixed solution a; adding a photoinitiator and an auxiliary agent into the mixed solution a, and dispersing at a high speed to obtain mixed solution b; and grinding the mixed solution b to the fineness of less than 5 mu m, adding a silane coupling agent and acrylic acid phosphate, and dispersing to obtain the recoatable high-coverage UV ink.
According to another aspect of the present invention, there is also provided a use of a repairable high hiding UV ink on a glass substrate, comprising the above-described repairable high hiding UV ink.
Further, the method comprises the following steps: (1) screen printing the recoatable high-coverage UV ink on a glass substrate, and carrying out UV curing to form a bottom layer; (2) and (3) screen printing the repairable high-coverage UV ink on the bottom layer in the step (1) by using a screen, and carrying out UV curing to form an ink coating.
Further, the thickness of the film printed on the glass substrate in the step (1) is 5 to 7 μm; the thickness of the film printed on the bottom layer in the step (2) is 5-7 μm; the screen mesh is 300-400 meshes.
Further, the UV curing energy in the step (1) is 500mj/cm2～800mj/cm2(ii) a The UV curing energy in the step (2) is 1500mj/cm2～1800mj/cm2。
The invention has the following beneficial effects:
the repairable high-coverage UV ink disclosed by the invention has amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional or higher polyurethane acrylate resin, a multifunctional reaction monomer and a monofunctional reaction monomer as main film forming substances. The amine modified epoxy acrylate resin effectively improves the curing rate of an ink system and increases the wettability of the pigment under the condition that the ink system has high content of the pigment, and a primary amine group in the amine modified epoxy acrylate is favorable for promoting the combination of trifunctional polyurethane acrylate resin, hexafunctional or higher polyurethane acrylate resin, a multifunctional reaction monomer and a monofunctional reaction monomer with free radicals to form a cross-linked grid structure, so that the adhesive force to a glass substrate is effectively improved. The thermoplastic acrylic resin improves the recoatability of the ink system. The silane coupling agent enables the water resistance of the ink system to be excellent, and the adhesive force between the ink coating and the glass substrate is further improved. The repairable high-covering UV ink has high covering capacity, is opaque, has an OD value larger than 5 and has zero VOC emission.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention is described in further detail below.
Detailed Description
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 with reference to examples.
The repairable high hiding UV ink of this example includes the following components: the coating comprises, by weight, 10-20 parts of amine modified epoxy acrylate resin, 20-50 parts of trifunctional polyurethane acrylate resin, 5-20 parts of hexafunctional or higher polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-20 parts of multifunctional reaction monomer, 5-25 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate. The high-coverage UV ink capable of being recoated is mainly prepared from amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional or above polyurethane acrylate resin, multifunctional reaction monomer and monofunctional reaction monomer, wherein the amine modified epoxy acrylate resin effectively improves the curing rate of an ink system and increases the wettability of pigment under the condition that the ink system has high content of pigment, and a primary amine group in the amine modified epoxy acrylate is favorable for promoting the combination of the trifunctional polyurethane acrylate resin, the hexafunctional or above polyurethane acrylate resin, the multifunctional reaction monomer and the monofunctional reaction monomer with free radicals to form a cross-linked grid structure, so that the adhesive force to a glass substrate is effectively improved. The thermoplastic acrylic resin improves the recoatability of the ink system. The silane coupling agent enables the water resistance of the ink system to be excellent, and the adhesive force between the ink coating and the glass substrate is further improved. The repairable high-covering UV ink has high covering capacity, is opaque, has an OD value larger than 5 and has zero VOC emission.
Through earlier stage research tests on the UV ink, the UV light is difficult to penetrate through an ink layer when the optical density OD value is larger than 5 after the toner is added into the UV ink, so that the ink is difficult to be cured into a film, and stable adhesive force is not formed between the ink and a glass substrate. The amine modified epoxy acrylate resin is obtained by condensing primary amine and epoxy group and then esterifying the condensed primary amine and epoxy group with acrylic acid. The primary amine group contained in the amine modified epoxy acrylate resin can promote the combination of acryloxy and free radical contained in other components, increase the wetting performance to toner, and improve the penetration of UV rays through the ink layer, so that the recoatable high-coverage UV ink has good adhesive force with a glass substrate. After the trifunctional polyurethane acrylate resin is cured by acryloxy UV, the adhesive force of the recoatable high-coverage UV ink to a glass substrate is effectively improved as a film forming substance.
In the embodiment, the paint comprises the following components: the coating comprises, by weight, 10-15 parts of amine modified epoxy acrylate resin, 20-40 parts of trifunctional polyurethane acrylate resin, 5-15 parts of hexafunctional or higher polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-10 parts of multifunctional reaction monomer, 5-15 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate.
The hexafunctional or above-hexafunctional urethane acrylate resin contains at least six acryloxy groups participating in photochemical reaction, and after UV curing, the hexafunctional or above-hexafunctional urethane acrylate resin can be used as a film forming substance to effectively improve the curing rate and the crosslinking density thereof and improve the resistance and the weather resistance of the hexafunctional or above-hexafunctional urethane acrylate resin. Preferably, a hexafunctional urethane acrylate resin is used.
In this example, the molecular weight of the thermoplastic acrylic resin was 7.5X 104～1.1×105. The thermoplastic acrylic resin is linear polymer with molecular weight of 7.5 × 104～1.1×105The high-covering UV ink has no acryloyloxy group and does not participate in free radical curing of film forming substances, but the molecular chain is longer after film forming due to the large molecular weight of the thermoplastic acrylic resin, so that the high-covering UV ink capable of being recoated is softer after curing, and the recoating performance of the high-covering UV ink capable of being recoated is effectively improved.
In this embodiment, the polyfunctional reactive monomer has a hexa-functionality or higher. Preferably, the multifunctional reactive monomer is hexafunctional reactive monomer dipentaerythritol hexaacrylate (DPHA for short), each monomer molecule contains six acryloxy groups capable of participating in photochemical reaction, so that the curing rate of the recoatable high-coverage UV ink can be effectively improved, and the monomer has low viscosity, so that the viscosity of the ink is reduced to a certain extent.
In the embodiment, the monofunctional reaction monomer is tetrahydrofuran acrylate (THFA for short), each monomer molecule contains an acryloxy machine capable of participating in photochemical reaction, the diluting capability is extremely strong, the viscosity of the UV ink can be effectively reduced, no residue and no odor exist after UV curing, and the printing construction performance is improved.
In this example, at least two of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, isopropylthioxanthe, α, -dimethylbenzylketal, and 1-hydroxycyclohexylbenzophenone were used as the photoinitiator. The photoinitiator generates free radicals for cross-linking polymerization and the like, and effectively solves the problem of incomplete curing of the UV ink after the UV ink coating is added with deep color. 2,4, 6-trimethylbenzoyl diphenylphosphine oxide is abbreviated as TPO, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide is abbreviated as 819, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-propanone is abbreviated as 907, isopropylthiaanthracene is abbreviated as ITX, alpha, -dimethylbenzylketal is abbreviated as 651, and 1-hydroxycyclohexyl benzophenone is abbreviated as 184.
In this embodiment, the auxiliary agent is at least two of a leveling agent, an antifoaming agent, and a wetting dispersant. The leveling agent adopts BYK-333 or BYK-358N. The defoaming agent is TEGO FoamexN. Wetting dispersant SOLSPERSE 20000. The matching of different auxiliary agents effectively solves the problems of wetting and dispersing of toner and printing construction performance.
In this embodiment, the toner is at least one of carbon black powder, iron oxide black powder, rutile titanium dioxide powder, benzimidazolone red powder, methyleneamine metal complex yellow powder, and phthalocyanine blue powder. Different toner blends provide different color appearance effects.
In this embodiment, the filler is at least one of nano calcium carbonate, nano barium sulfate, nano alumina, or wax powder. The amine modified epoxy acrylate resin has good wetting effect on pigments and fillers, and the fillers effectively improve the printing workability of recoatable high-coverage UV ink for glass substrates and greatly reduce the cost. The nano-scale filler is added, so that the thixotropy and the leveling property of the recoatable high-coverage UV ink can be improved, the printing construction performance of the recoatable high-coverage UV ink is improved, a paint film has a nano particle surface effect after being cured, a shielding effect is formed, and the anti-ultraviolet aging effect of the film layer can be effectively improved. The wax powder may be a small particle size wax powder.
In the embodiment, the silane coupling agent is Dow Corning OFS-6030, the methacryloxy functional group alkoxy silane, the methacryloxy group at one end can be combined with a film forming substance to participate in free radical curing, and the alkoxy group at the other end is hydrolyzed and then is combined with the hydroxyl bond of the glass substrate, so that the adhesion of the recoatable high-coverage UV ink to the glass substrate is effectively improved, and the water resistance of the recoatable high-coverage UV ink is improved.
In this example, the phosphate acrylate was sartomer CD-9051, which is a high acid adhesion promoter that effectively improved the adhesion of the recoatable, high hiding UV ink to the glass substrate.
According to another aspect of the present invention, there is also provided a method for preparing a repairable high hiding UV ink, comprising the steps of: mixing and dispersing amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional or higher polyurethane acrylate resin, thermoplastic acrylic resin, multifunctional reaction monomer and monofunctional reaction monomer to obtain mixed solution a; adding a photoinitiator and an auxiliary agent into the mixed solution a, and dispersing at a high speed to obtain mixed solution b; and grinding the mixed solution b to the fineness of less than 5 mu m, adding a silane coupling agent and acrylic acid phosphate, and dispersing to obtain the recoatable high-coverage UV ink. The preparation method of the recoatable high-coverage UV ink is simple and easy to implement, high in yield, low in cost and suitable for mass production, and the prepared UV ink is suitable for surface decoration of glass substrates.
According to another aspect of the present invention, there is also provided a use of a repairable high hiding UV ink on a glass substrate, comprising the above-described repairable high hiding UV ink. The method comprises the following steps: (1) screen printing the recoatable high-coverage UV ink on a glass substrate, and carrying out UV curing to form a bottom layer; (2) and (3) screen printing the repairable high-coverage UV ink on the bottom layer in the step (1) by using a screen, and carrying out UV curing to form an ink coating. The recoatable high-coverage UV ink is directly screen-printed on a glass substrate for curing, and is fast in curing, high in yield, low in cost and suitable for mass production. Solves the problems that the traditional UV printing ink can not be recoated or the interlayer adhesive force after recoating is extremely poor. The ink coating has good adhesion with the glass substrate, can be recoated, and has high covering power and excellent water resistance.
Specifically, amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional polyurethane acrylate resin, thermoplastic acrylic resin, hexafunctional reaction monomer and monofunctional reaction monomer are sequentially added while stirring, the dispersion speed is 200 r/min-800 r/min, the dispersion time is 5 min-10 min, and mixed uniformly to obtain mixed liquid a; adding a photoinitiator and an auxiliary agent into the mixed solution a, dispersing at a high speed for 10-30 min at a rotating speed of 300-1000 r/min to obtain mixed solution b; and grinding the mixed solution b on a sand mill until the granularity is less than 5 mu m, adding a silane coupling agent and acrylic phosphate, and dispersing at the rotating speed of 200-800 r/min for 5-10 min to obtain the recoatable high-coverage UV ink.
In this example, the thickness of the film printed on the glass substrate in the step (1) was 5 μm to 7 μm. The thickness of the film printed on the bottom layer in the step (2) is 5-7 μm. The screen mesh is 300-400 meshes. The silk-screen printing adopts 300-350 meshes of silk-screen printing, so that the water-based coating is uniformly distributed and is tightly combined with the glass substrate. The ink coating adopts two-time coating, which is superior to the coating performance of only one-time coating, and the total thickness of the two films is 12-14 μm.
In this example, the UV curing energy in the step (1) was 500mj/cm2～800mj/cm2(ii) a The UV curing energy in the step (2) is 1500mj/cm2～1800mj/cm2. Curing the first ink coating, wherein energy is required during curingThe lower is 500mj/cm2～800mj/cm2So that the bonding with the glass substrate is firm, but the surface layer is not completely cured. The second time of ink coating curing, the higher UV energy is 1500mj/cm2～1800mj/cm2And the bottom layer is activated during high-temperature curing and is combined with the printing ink for the second screen printing, and the high-UV curing can increase the bonding force between two printing ink coatings, so that the two printing inks are cured more completely, and the UV curing energy is saved.
Examples
Materials and equipment used in the following examples are commercially available.
Example 1
The preferred embodiment of the present invention provides a high hiding UV ink that is repairable and has the composition shown in table 1.
The hexafunctional or above polyurethane acrylate resin is hexafunctional polyurethane acrylate resin;
the photoinitiator is a mixture of 184, ITX and 907, and the mixing mass ratio of the three is 1: 2;
the auxiliary agent is a mixture of a flatting agent, a defoaming agent and a wetting dispersant, and the mixing mass ratio of the flatting agent, the defoaming agent and the wetting dispersant is 0.3: 0.2: 2.5;
the toner adopts carbon black, and the carbon black is used in the embodiments 1 to 5, so that the color of the recoatable high-coverage UV ink is black, and the analysis and comparison are facilitated;
the filler is a mixture of nano barium sulfate and wax powder, and the mixing mass ratio of the nano barium sulfate to the wax powder is 20: 4.
The preparation method of the repairable high-hiding UV ink of this example:
adding amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, hexafunctional or higher polyurethane acrylate resin, thermoplastic acrylic resin, hexafunctional reaction monomer and monofunctional reaction monomer in sequence while stirring, wherein the dispersion speed is 500r/min, the dispersion time is 10min, and uniformly mixing to obtain a mixed solution a; adding a photoinitiator and an auxiliary agent into the mixed solution a, dispersing at a high speed for 15min at a rotating speed of 700r/min to obtain mixed solution b; and grinding the mixed solution b on a sand mill until the granularity is less than 5 mu m, adding a silane coupling agent and acrylic phosphate, and obtaining the recoatable high-coverage UV ink with the dispersion rotation speed of 500r/min and the dispersion time of 10 min.
Application of the repairable high-hiding UV ink of this example
(1) Screen printing repairable high-coverage UV ink on a clean glass substrate by using 300-mesh screen, wherein the film thickness is 6 mu m, and the UV curing is performed, and the UV curing energy is 600mj/cm2Forming a bottom layer for 5 s; (2) then, recoating high-shading UV ink is used for screen printing on the bottom layer in the step (1) by using a 300-mesh screen, the film thickness is 7 mu m, and UV curing is carried out, wherein the UV curing energy is 1700mj/cm2And the time is 6s, and an ink coating is formed.
Example 2
The preferred embodiment of the present invention provides a high hiding UV ink that is repairable and has the composition shown in table 1.
The hexafunctional or above urethane acrylate resin is an octafunctional urethane acrylate resin;
the photoinitiator is a mixture of TPO, ITX and 819, and the mixing mass ratio of the TPO, the ITX and the 819 is 1: 2;
the auxiliary agent is a mixture of a flatting agent, a defoaming agent and a wetting dispersant, and the mixing mass ratio of the flatting agent, the defoaming agent and the wetting dispersant is 0.3: 0.2: 2.5;
the filler is a mixture of nano calcium carbonate and wax powder, and the mixing mass ratio of the nano calcium carbonate to the wax powder is 20: 4.
The repairable high hiding UV ink of this example was prepared in the same manner as in example 1.
The application of the repairable high hiding UV ink of this example was the same as example 1.
Example 3
The preferred embodiment of the present invention provides a high hiding UV ink that is repairable and has the composition shown in table 1.
The hexafunctional or above urethane acrylate resin is decafunctional urethane acrylate resin;
the photoinitiator is a mixture of TPO and 651, and the mixing mass ratio of the TPO to the 651 is 1: 2;
the auxiliary agent is a mixture of a flatting agent, a defoaming agent and a wetting dispersant, and the mixing mass ratio of the flatting agent, the defoaming agent and the wetting dispersant is 0.3: 0.2: 2.5;
the filler is a mixture of nano alumina and wax powder, and the mixing mass ratio of the nano alumina to the wax powder is 20: 4.
The repairable high hiding UV ink of this example was prepared in the same manner as in example 1.
The application of the repairable high hiding UV ink of this example was the same as example 1.
Example 4
The preferred embodiment of the present invention provides a high hiding UV ink that is repairable and has the composition shown in table 1.
The hexafunctional or above polyurethane acrylate resin is hexafunctional polyurethane acrylate resin;
the photoinitiator is a mixture of 184, ITX and 907, and the mixing mass ratio of the three is 1: 2;
the auxiliary agent is a mixture of a flatting agent, a defoaming agent and a wetting dispersant, and the mixing mass ratio of the flatting agent, the defoaming agent and the wetting dispersant is 0.3: 0.2: 2.5;
the filler is a mixture of nano barium sulfate and wax powder, and the mixing mass ratio of the nano barium sulfate to the wax powder is 20: 4.
The repairable high hiding UV ink of this example was prepared in the same manner as in example 1.
The application of the repairable high hiding UV ink of this example was the same as example 1.
Example 5
The preferred embodiment of the present invention provides a high hiding UV ink that is repairable and has the composition shown in table 1.
The hexafunctional or above polyurethane acrylate resin is hexafunctional polyurethane acrylate resin;
the photoinitiator is a mixture of 651, ITX and 907, and the mixing mass ratio of the three is 1: 2;
the auxiliary agent is a mixture of a flatting agent, a defoaming agent and a wetting dispersant, and the mixing mass ratio of the flatting agent, the defoaming agent and the wetting dispersant is 0.3: 0.2: 2.5;
the filler is a mixture of nano barium sulfate and wax powder, and the mixing mass ratio of the nano barium sulfate to the wax powder is 20: 2.
The repairable high hiding UV ink of this example was prepared in the same manner as in example 1.
The application of the repairable high hiding UV ink of this example was the same as example 1.
TABLE 1 high hiding UV inks of examples 1-5 that can be recoated
Figure BDA0001929264890000071
Figure BDA0001929264890000081
Comparative example 1
Commercial black UV inks
The same applies as in example 1.
Comparative example 2
Comparative example 2 provides an ink having the composition shown in table 2.
TABLE 2 ink of comparative example 2
Figure BDA0001929264890000082
The ink of this comparative example was prepared in the same manner as in example 1.
The ink of this comparative example was used as in example 1.
Comparative example 3
Comparative example 3 provides an ink having the composition shown in table 3.
TABLE 3 ink of comparative example 3
Figure BDA0001929264890000083
Figure BDA0001929264890000091
The ink of this comparative example was prepared in the same manner as in example 1.
The ink of this comparative example was used as in example 1.
The test boards manufactured in examples 1 to 5 and the test boards manufactured in comparative examples 1 to 3 were tested, the test methods were all standard methods, and the adhesive force: GB 1720-; pencil hardness: GB/T6739-2006, 1000 g; water resistance: GB/T1733 (method B), temperature 100 deg.C, distilled water, time 30 min; covering power: GB/T1726 (method B); water contact angle: GB/T24368-.
The test results are shown in table 4:
TABLE 4 test results of the test boards manufactured in examples 1 to 5 and the test boards manufactured in comparative examples 1 to 3
Figure BDA0001929264890000092
As shown in Table 4, the recoatable high-coverage UV ink applied to the glass substrate of examples 1 to 5 had good printing workability and no significant defects such as missing teeth or jaggies; the adhesive force with the glass substrate is excellent, the covering power is high, and the OD value is more than 5; the waterproof performance is excellent, the appearance is not obviously abnormal and the adhesive force is good when the paint is boiled in water at 100 ℃ for 30 min; the surface tension is high, the water contact angle is less than 80 degrees, and the bonding of the post-processing procedure is facilitated; the hardness is excellent, the load is 1000g, and no obvious scratch is caused by 2H. The repairable high-coverage UV ink in example 4 has the advantages of optimal comprehensive performance, stable adhesion, excellent boiling resistance, high pencil hardness, high coverage, light tightness, low water contact angle, and the like, and is beneficial to the lamination of a post-processing procedure.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A high-covering UV ink capable of being recoated is characterized by comprising the following components: based on the weight portion, the weight ratio of the components,
10-20 parts of amine modified epoxy acrylate resin, 20-50 parts of trifunctional polyurethane acrylate resin, 5-20 parts of hexafunctional polyurethane acrylate resin, 3-8 parts of thermoplastic acrylic resin, 5-20 parts of multifunctional reaction monomer, 5-25 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate;
the thermoplastic acrylic resin is linear polymer with molecular weight of 7.5 × 104～1.1×105；
The silane coupling agent is methacryloxy functional group alkoxy silane;
the multifunctional reaction monomer has more than six degrees of functionality;
the photoinitiator adopts at least two of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-acetone, isopropyl thiaanthracene, alpha-dimethyl benzil ketal or 1-hydroxycyclohexyl phenyl ketone;
the auxiliary agent adopts at least two of a flatting agent, a defoaming agent or a wetting dispersant;
the toner is at least one of carbon black powder, ferric oxide black powder, rutile type titanium dioxide powder, benzimidazolone red toner, methylene amine metal complex yellow powder or phthalocyanine blue toner;
the filler is at least one of nano calcium carbonate, nano barium sulfate, nano alumina or wax powder.
2. The repairable high hiding UV ink according to claim 1, consisting of the following components: based on the weight portion, the weight ratio of the components,
10-15 parts of amine modified epoxy acrylate resin, 20-40 parts of trifunctional polyurethane acrylate resin, 5-15 parts of polyurethane acrylate resin with more than six functions, 3-8 parts of thermoplastic acrylic resin, 5-10 parts of multifunctional reaction monomer, 5-15 parts of monofunctional reaction monomer, 3-6 parts of photoinitiator, 2-5 parts of auxiliary agent, 5-8 parts of toner, 20-30 parts of filler, 1-2 parts of silane coupling agent and 1-2 parts of acrylic phosphate.
3. A method of preparing a repairable high hiding UV ink according to claim 1 or 2, comprising the steps of:
mixing and dispersing amine modified epoxy acrylate resin, trifunctional polyurethane acrylate resin, polyurethane acrylate resin with more than six functions, thermoplastic acrylic resin, multifunctional reaction monomer and monofunctional reaction monomer to obtain mixed solution a;
adding a photoinitiator and an auxiliary agent into the mixed solution a, and dispersing at a high speed to obtain a mixed solution b;
and grinding the mixed solution b to a fineness of less than 5 mu m, adding a silane coupling agent and acrylic acid phosphate, and dispersing to obtain the recoatable high-coverage UV ink.
4. Use of a repairable high-hiding UV ink on a glass substrate, characterized in that a repairable high-hiding UV ink according to claim 1 or 2 is used.
5. Use of a recoatable high hiding UV ink according to claim 4 on a glass substrate comprising the steps of:
(1) screen printing the recoatable high-coverage UV ink on a glass substrate, and carrying out UV curing to form a bottom layer;
(2) and (3) screen printing the repairable high-coverage UV ink on the bottom layer in the step (1) by using a screen, and carrying out UV curing to form an ink coating.
6. Use of a repairable high hiding UV ink according to claim 5 on a glass substrate,
the thickness of the film printed on the glass substrate in the step (1) is 5-7 μm; the thickness of the film printed on the bottom layer in the step (2) is 5-7 μm;
the silk screen is 300-400 meshes;
the UV curing energy in the step (1) is 500mj/cm2～800mj/cm2(ii) a The UV curing energy in the step (2) is 1500mj/cm2～1800mj/cm2。
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