High-strength uv ink and method for preparing the same

Abstract

The application relates to a high-strength UV ink and a preparation method thereof, and belongs to the technical field of the UV ink. The high-strength UV ink comprises the following components: modified acrylic ester emulsion, reaction monomer, photoinitiator, pigment, defoaming agent and solvent; wherein the preparation of the modified acrylic ester emulsion comprises the following steps: stirring and uniformly mixing emulsifier, sodium bicarbonate, deionized water and 2 / 3 of composite monomers in a reaction kettle to obtain a mixture; slowly heating the mixture, adding 1 / 3 of an initiator, slowly adding the remaining composite monomers and the remaining initiator and carrying out constant-temperature water bath reaction, and cooling to obtain the product. The application changes the surface activity of the pigment, increases the dispersibility of the pigment in a resin system, improves the interfacial bonding force between the pigment and the resin, and improves the adhesion firmness and mechanical strength of the composite ink.

Description

Technical Field

[0001] This invention belongs to the technical field of UV inks, and relates to a high-strength UV ink and its preparation method. Background Technology

[0002] Among resins used in UV inks, acrylic resins have become one of the best choices for UV ink binders due to their versatility and excellent physical and chemical properties. The participation of comonomers carrying different functional groups in the polymerization reaction can improve some properties of the polymer, such as hydrophilicity / hydrophobicity, resistance to low and high temperatures, acid and alkali resistance, and corrosion resistance. In emulsion polymerization systems, monomers are the most important components. Acrylic monomers are generally composed of hard monomers, soft monomers, and functional monomers. The type and amount of monomers determine the chemical properties, mechanical properties, adhesion properties, stain resistance, antibacterial properties, and application properties of the polymer emulsion.

[0003] Another key aspect of UV ink preparation lies in pigment dispersion, stability, and viscosity control. To obtain high-quality UV ink, its dispersion stability needs to be improved. Currently, domestic research on pigment dispersion in UV inks mainly employs ball mills to prepare color pastes from pigments, monomers, and dispersants, followed by the addition of oligomers, monomers, and ink additives. However, inks prepared using this method exhibit low stability, limited improvement in pigment dispersibility, insufficient binding force with resins, and low ink film strength. Furthermore, partial pigment agglomeration also leads to low ink adhesion to the substrate. Summary of the Invention

[0004] The purpose of this invention is to provide a high-strength UV ink and its preparation method. This invention improves the adhesion and mechanical strength of the composite ink by changing the surface activity of the pigment, increasing its dispersibility in the resin system, enhancing the interfacial bonding force between the pigment and the resin.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-strength UV ink comprises the following components by weight:

[0007] 20-30 parts modified acrylate emulsion, 50-70 parts reactive monomer, 2-4 parts photoinitiator, 14-20 parts pigment, 2-3 parts defoamer and 20-30 parts solvent;

[0008] As a preferred embodiment of the present invention, the reaction monomer is composed of isobornyl methacrylate and triethylene glycol diacrylate in a mass ratio of 12-13:20-25.

[0009] As a preferred embodiment of the present invention, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin diethyl ether, and 1-hydroxycyclohexylphenyl ketone.

[0010] As a preferred embodiment of the present invention, the pigment is one or more of titanium dioxide, carbon black and aluminum silver paste.

[0011] In a preferred embodiment of the present invention, the defoamer is polydimethylsiloxane. The solvent is one or both of an organic solvent and deionized water.

[0012] As a preferred embodiment of the present invention, the modified acrylate emulsion comprises the following components by weight: 60-70 parts of composite monomer, 2-5 parts of emulsifier, 2-3 parts of initiator, 1.8-2.4 parts of sodium bicarbonate, and 40-60 parts of deionized water.

[0013] As a preferred embodiment of the present invention, the composite monomer is composed of methyl methacrylate, ethyl acrylate and functional monomer in a mass ratio of 35-45:17-21:5-8; the emulsifier is one or two of emulsifier OP-10 and sodium dodecyl sulfate; and the initiator is ammonium persulfate.

[0014] As a preferred embodiment of the present invention, the method for preparing the modified acrylate emulsion includes the following steps:

[0015] S1. Place the emulsifier, sodium bicarbonate, deionized water and 2 / 3 of the composite monomer in a reaction vessel and stir to mix well to obtain a mixture;

[0016] S2. Slowly heat the mixture, add 1 / 3 of the initiator, slowly add the remaining composite monomer and the remaining initiator, and react in a constant temperature water bath. Cool to obtain the final product.

[0017] As a preferred technical solution of the present invention, in step S1, the stirring and mixing is carried out at 200-300 r / min for 20-30 min.

[0018] As a preferred embodiment of the present invention, in step S2, the slow heating is to raise the temperature to 70-80°C; the constant temperature water bath reaction is to react at 80-90°C for 3-5 hours; and the cooling is to cool to room temperature.

[0019] As a preferred embodiment of the present invention, the method for preparing the functional monomer includes the following steps:

[0020] Step 1: Under a nitrogen atmosphere, diethylenetriaminepropyltrimethoxysilane and anhydrous ethanol are placed in a dry reaction vessel and stirred. After adding triethylamine, glycidyl ether is slowly added dropwise while stirring under controlled temperature. The solvent is removed by vacuum distillation to obtain the intermediate.

[0021] Step 2: Mix the intermediate, glacial acetic acid and anhydrous ethanol, add the benzaldehyde derivative, stir at a constant temperature, and centrifuge to obtain the final product.

[0022] As a preferred embodiment of the present invention, in step one, the stirring and mixing is carried out at 120-160 r / min for 10-15 min; the temperature-controlled stirring is carried out at 50-60℃ for 2-3 h; the continued stirring is carried out at 50-60℃ for 4-6 h; and the ratio of the amounts of diethylenetriaminepropyltrimethoxysilane, anhydrous ethanol, glycidyl ether, and triethylamine is 100-110 g: 30-34 g: 200-230 mL: 1.0-1.2 g.

[0023] As a preferred embodiment of the present invention, in step two, the constant temperature stirring is carried out at 55-60℃ for 4-6 hours; the ratio of the intermediate, glacial acetic acid, anhydrous ethanol and benzaldehyde derivative is 12-15g: 0.02-0.03g: 22-25mL: 3.4-3.8g; the benzaldehyde derivative is an aromatic aldehyde compound with multiple oxygen-containing functional groups, such as syringaldehyde and vanillin.

[0024] This invention discloses a method for preparing a high-strength UV ink, the method comprising the following steps: stirring the reactive monomer, photoinitiator, pigment, defoamer and solvent at 300-800 r / min for 5-10 min, adding modified acrylate emulsion and stirring for 10-20 min to obtain the ink.

[0025] The beneficial effects of this invention are:

[0026] This invention prepares a high-strength UV ink comprising modified acrylate emulsion, reactive monomers, photoinitiators, pigments, defoamers, and solvents. The functional monomers in the modified acrylate emulsion impart excellent adhesion and mechanical strength to the ink film. The combination of diethylenetriaminepropyltrimethoxysilane, glycidyl ether, and benzaldehyde derivatives alters the surface activity of the pigment, increases its dispersibility in the resin system, enhances its interfacial bonding with the resin, and improves the adhesion and mechanical strength of the composite ink.

[0027] The acrylic water-based ink involved in this invention has excellent mechanical strength properties, is not easily deformed, and also has very strong adhesion, enabling it to bond firmly to various substrates. Detailed Implementation

[0028] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0029] Example 1

[0030] A high-strength UV ink comprises the following components by weight:

[0031] The mixture comprises 20 parts modified acrylate emulsion, 50 parts reactive monomer, 2 parts photoinitiator, 14 parts pigment, 2 parts defoamer, and 20 parts solvent; the reactive monomer is composed of isobornyl methacrylate and triethylene glycol diacrylate in a mass ratio of 12:20; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone; the pigment is titanium dioxide; the defoamer is polydimethylsiloxane; and the solvent is composed of isopropanol and deionized water in a mass ratio of 1:4.

[0032] The modified acrylate emulsion comprises the following components by weight: 60 parts of composite monomer, 2 parts of emulsifier, 2 parts of initiator, 1.8 parts of sodium bicarbonate, and 40 parts of deionized water.

[0033] The composite monomer is composed of methyl methacrylate, ethyl acrylate and functional monomers in a mass ratio of 35:17:5; the emulsifier is composed of emulsifier OP-10 and sodium dodecyl sulfate in a mass ratio of 1.0:1; the initiator is ammonium persulfate.

[0034] The method for preparing the modified acrylate emulsion includes the following steps:

[0035] S1. Place the emulsifier, sodium bicarbonate, deionized water and 2 / 3 of the composite monomer in a reaction vessel and stir at 200 r / min for 20 min to obtain a mixture;

[0036] S2. Slowly heat the mixture to 70°C, add 1 / 3 of the initiator, slowly add the remaining composite monomer and the remaining initiator, react at 80°C for 3 hours, and cool to room temperature to obtain the final product.

[0037] The preparation method of the functional monomer includes the following steps:

[0038] Step 1: Under a nitrogen atmosphere, diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol are placed in a dry reaction vessel and stirred at 120 r / min for 10 min. After adding triethylamine, glycidyl ether is slowly added dropwise and stirred at 50°C for 2 h. The solvent is removed by vacuum distillation to obtain the intermediate. The ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, glycidyl ether, and triethylamine is 100 g: 30 g: 200 mL: 1.0 g.

[0039] Step 2: Mix the intermediate, glacial acetic acid and anhydrous ethanol, add eugenol and stir at 55°C for 4 hours. Centrifuge and collect the yellow viscous liquid to obtain the product. The ratio of the amount of intermediate, glacial acetic acid, anhydrous ethanol and eugenol is 12g:0.02g:22mL:3.4g.

[0040] A method for preparing a high-strength UV ink includes the following steps: stirring the reactive monomer, photoinitiator, pigment, defoamer and solvent at 300 r / min for 5 min, adding modified acrylate emulsion and stirring for 10 min to obtain the ink.

[0041] Example 2

[0042] A high-strength UV ink comprises the following components by weight:

[0043] The mixture comprises 25 parts modified acrylate emulsion, 60 parts reactive monomer, 3 parts photoinitiator, 17 parts pigment, 2.5 parts defoamer, and 25 parts solvent; the reactive monomer is composed of isobornyl methacrylate and triethylene glycol diacrylate in a mass ratio of 12.5:22; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone; the pigment is titanium dioxide; the defoamer is polydimethylsiloxane; and the solvent is composed of isopropanol and deionized water in a mass ratio of 1:4.

[0044] The modified acrylate emulsion comprises the following components by weight: 65 parts of composite monomer, 4 parts of emulsifier, 2.5 parts of initiator, 2.1 parts of sodium bicarbonate, and 50 parts of deionized water.

[0045] The composite monomer is composed of methyl methacrylate, ethyl acrylate, and functional monomers in a mass ratio of 40:19:6; the emulsifier is composed of emulsifier OP-10 and sodium dodecyl sulfate in a mass ratio of 1.2:1; and the initiator is ammonium persulfate.

[0046] The method for preparing the modified acrylate emulsion includes the following steps:

[0047] S1. Place the emulsifier, sodium bicarbonate, deionized water and 2 / 3 of the composite monomer in a reaction vessel and stir at 250 r / min for 25 min to obtain a mixture;

[0048] S2. Slowly heat the mixture to 75°C, add 1 / 3 of the initiator, slowly add the remaining composite monomer and the remaining initiator, react at 85°C for 4 hours, and cool to room temperature to obtain the final product.

[0049] The preparation method of the functional monomer includes the following steps:

[0050] Step 1: Under a nitrogen atmosphere, diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol are placed in a dry reaction vessel and stirred at 140 r / min for 12 min. After adding triethylamine, glycidyl ether is slowly added dropwise and stirred at 55°C for 2.5 h. The solvent is removed by vacuum distillation to obtain the intermediate. The ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, glycidyl ether, and triethylamine is 105 g: 32 g: 215 mL: 1.1 g.

[0051] Step 2: Mix the intermediate, glacial acetic acid and anhydrous ethanol, add eugenol and stir at 58°C for 5 hours. Centrifuge and collect the yellow viscous liquid to obtain the product. The ratio of the amount of intermediate, glacial acetic acid, anhydrous ethanol and eugenol is 14g:0.025g:24mL:3.6g.

[0052] A method for preparing a high-strength UV ink includes the following steps: stirring the reactive monomer, photoinitiator, pigment, defoamer and solvent at 550 r / min for 8 min, adding modified acrylate emulsion and stirring for 15 min to obtain the ink.

[0053] Example 3

[0054] A high-strength UV ink comprises the following components in parts by weight:

[0055] The mixture comprises 30 parts modified acrylate emulsion, 70 parts reactive monomer, 4 parts photoinitiator, 20 parts pigment, 3 parts defoamer, and 30 parts solvent; the reactive monomer is composed of isobornyl methacrylate and triethylene glycol diacrylate in a mass ratio of 13:25; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone; the pigment is titanium dioxide; the defoamer is polydimethylsiloxane; and the solvent is composed of isopropanol and deionized water in a mass ratio of 1:4.

[0056] The modified acrylate emulsion comprises the following components by weight: 70 parts of composite monomer, 5 parts of emulsifier, 3 parts of initiator, 2.4 parts of sodium bicarbonate, and 60 parts of deionized water.

[0057] The composite monomer is composed of methyl methacrylate, ethyl acrylate and functional monomers in a mass ratio of 45:21:8; the emulsifier is composed of emulsifier OP-10 and sodium dodecyl sulfate in a mass ratio of 1.5:1; the initiator is ammonium persulfate.

[0058] The method for preparing the modified acrylate emulsion includes the following steps:

[0059] S1. Place the emulsifier, sodium bicarbonate, deionized water and 2 / 3 of the composite monomer in a reaction vessel and stir at 300 r / min for 30 min to obtain a mixture;

[0060] S2. Slowly heat the mixture to 80°C, add 1 / 3 of the initiator, slowly add the remaining composite monomer and the remaining initiator, react at 90°C for 5 hours, and cool to room temperature to obtain the final product.

[0061] The preparation method of the functional monomer includes the following steps:

[0062] Step 1: Under a nitrogen atmosphere, diethylenetriaminopropyltrimethoxysilane and anhydrous ethanol are placed in a dry reaction vessel and stirred at 160 r / min for 15 min. After adding triethylamine, glycidyl ether is slowly added dropwise and stirred at 60℃ for 3 h. The solvent is removed by vacuum distillation to obtain the intermediate. The ratio of diethylenetriaminopropyltrimethoxysilane, anhydrous ethanol, glycidyl ether, and triethylamine is 110 g: 34 g: 230 mL: 1.2 g.

[0063] Step 2: Mix the intermediate, glacial acetic acid and anhydrous ethanol, add eugenol and stir at 60°C for 6 hours. Centrifuge and collect the yellow viscous liquid to obtain the product. The ratio of the amount of the intermediate, glacial acetic acid, anhydrous ethanol and eugenol is 15g:0.03g:25mL:3.8g.

[0064] A method for preparing a high-strength UV ink includes the following steps: stirring the reactive monomer, photoinitiator, pigment, defoamer and solvent at 800 r / min for 10 min, adding modified acrylate emulsion and stirring for 20 min to obtain the ink.

[0065] Comparative Example 1

[0066] Compared with Example 3, Comparative Example 1 differs in that glycidol is not used, while the other components, preparation steps and parameters are the same.

[0067] Comparative Example 2

[0068] Compared with Example 3, Comparative Example 2 differs in that syringaldehyde is not used, while the other components, preparation steps and parameters are the same.

[0069] Comparative Example 3

[0070] Compared with Example 3, Comparative Example 3 differs in that it uses silane coupling agent KH550 instead of diethylenetriaminepropyltrimethoxysilane, while the other components, preparation steps and parameters are the same.

[0071] Comparative Example 4

[0072] Compared with Example 3, Comparative Example 4 differs in that silane coupling agent KH570 is used instead of diethylenetriaminepropyltrimethoxysilane, while the other components, preparation steps and parameters are the same.

[0073] Comparative Example 5

[0074] Compared with Example 3, Comparative Example 5 differs in that ethyl acrylate is used instead of the functional monomer, while the other components, preparation steps and parameters are the same.

[0075] The inks prepared in Examples 1-3 and Comparative Examples 1-5 were tested as follows, and the test results are shown in Table 1.

[0076] Adhesion strength test: According to GB / T13217.7-2009, PET film is used as the substrate and 3M tape is selected;

[0077] Tensile strength test: GB / T1040.1-2018;

[0078] Table 1

[0079]

[0080]

[0081] As shown in Table 1, compared with Comparative Examples 1-5, Examples 1-3, through the use of diethylenetriaminepropyltrimethoxysilane, can form Si-O-Ti chemical bonds with the surface of inorganic pigments (titanium dioxide), enhancing the interfacial bonding between the resin and the pigment. The terminal amino groups react with the carboxyl groups in the acrylate and the epoxy groups of glycidyl, promoting chemical bonding between the organic and inorganic phases and reducing interfacial defects. Simultaneously, the flexible long chain of silane can moderately improve the toughness of the ink film, enhance the cross-linking effect, increase network density, and improve tensile strength. The highly polar epoxy groups of glycidyl can improve the ink... The wettability of the film to the substrate enhances physical adsorption; the epoxy groups participate in curing and crosslinking, increasing the crosslinking density of the polymer, making the ink film structure denser and significantly enhancing mechanical strength; the aldehyde group of the benzaldehyde derivative forms a Schiff base structure with the amino group in diethylenetriaminepropyltrimethoxysilane, and its oxygen-containing functional groups can provide additional crosslinking points, strengthening the chemical anchoring of the ink film to the substrate. The oxygen-containing functional groups and the Schiff base structure can also adsorb pigments through hydrogen bonding, electrostatic adsorption and other forces, increasing the dispersibility of pigments and reducing their aggregation; the rigid benzene ring structure of the benzaldehyde derivative increases the network rigidity and improves tensile strength.

[0082] This invention constructs a multi-layered network structure by forming a main crosslinking backbone with diethylenetriaminepropyltrimethoxysilane and glycidol, and introducing secondary crosslinking points with eugenol, thereby improving the mechanical strength and adhesion of the ink film. Furthermore, by bridging inorganic pigments and resin with silane, and enhancing the cohesive energy of the resin with glycidol and eugenol, the overall performance is improved by reducing interfacial stress.

[0083] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A high-strength UV ink, characterized by, The modified acrylic emulsion comprises the following components by weight parts: 20-30 parts of modified acrylic emulsion, 50-70 parts of reaction monomer, 2-4 parts of photoinitiator, 14-20 parts of pigment, 2-3 parts of defoaming agent and 20-30 parts of solvent; the reaction monomer is composed of isobornyl methacrylate and triethylene glycol dimethacrylate in a mass ratio of 12-13:20-25; The preparation method of the modified acrylic emulsion comprises the following steps: S1, the emulsifier, sodium bicarbonate, deionized water and 2 / 3 of the composite monomer are placed in the reaction kettle and stirred and mixed uniformly to obtain a mixture; the composite monomer is composed of methyl methacrylate, ethyl acrylate and functional monomer in a mass ratio of 35-45:17-21:5-8; S2, slowly warm the mixture, add 1 / 3 of the initiator, slowly add the remaining composite monomer and the remaining initiator and react in a constant temperature water bath, cool down, and obtain the product; The preparation method of the functional monomer comprises the following steps: Step one, under a nitrogen atmosphere, diethylenetriamine propyl trimethoxysilane and anhydrous ethanol are placed in a dry reaction kettle and stirred and mixed, then triethylamine is added, glycidol is slowly added dropwise under temperature control and stirring, and the solvent is removed by reduced pressure distillation to obtain an intermediate; Step two, the intermediate, glacial acetic acid and anhydrous ethanol are mixed, a benzaldehyde derivative is added under constant temperature stirring, and centrifugation is performed to obtain the product; the benzaldehyde derivative is syringaldehyde. The photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin diethyl ether and 1-hydroxycyclohexyl phenyl ketone.

2. The high strength UV ink according to claim 1, wherein: The pigment is one or more of titanium dioxide, carbon black and aluminum paste; the solvent is one or both of an organic solvent and deionized water.

3. The high strength UV ink of claim 1, wherein: The modified acrylic emulsion comprises the following components by weight parts: 20-30 parts of modified acrylic emulsion, 50-70 parts of reaction monomer, 2-4 parts of photoinitiator, 14-20 parts of pigment, 2-3 parts of defoaming agent and 20-30 parts of solvent; the reaction monomer is composed of isobornyl methacrylate and triethylene glycol dimethacrylate in a mass ratio of 12-13:20-25; 4. The high strength UV ink of claim 1, wherein: The emulsifier is one or both of emulsifier OP-10 and sodium dodecyl sulfate.

5. The high strength UV ink of claim 1, wherein: In step S1, the stirring and mixing is performed at 200-300 r / min for 20-30 min; in step S2, the slow warming is performed to 70-80℃; the constant temperature water bath reaction is performed at 80-90℃ for 3-5 h; and the cooling is performed to room temperature.

6. The high strength UV ink of claim 1, wherein: In step one, the stirring and mixing is performed at 120-160 r / min for 10-15 min; the temperature control stirring is performed at 50-60℃ for 2-3 h; and the amounts of diethylenetriamine propyl trimethoxysilane, anhydrous ethanol, glycidol and triethylamine are 100-110 g:30-34 g:200-230 mL:1.0-1.2 g.

7. The high strength UV ink of claim 1, wherein: In step two, the constant temperature stirring is performed at 55-60℃ for 4-6 h; and the amounts of the intermediate, glacial acetic acid, anhydrous ethanol and benzaldehyde derivative are 12-15 g:0.02-0.03 g:22-25 mL:3.4-3.8 g.

8. The high strength UV ink of claim 1, wherein: ​ 9. A method of preparing a high-strength UV ink according to any one of claims 1 to 8, characterized in that, The preparation method comprises the following steps: stirring and mixing reaction monomers, a photoinitiator, a pigment, a defoaming agent and a solvent, adding a modified acrylate emulsion and continuously stirring, and thus the pigment emulsion is obtained.

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