LED curing ink capable of automatically shrinking to form textures and preparation method of LED curing ink

Abstract

The invention belongs to the technical field of printing ink, and particularly relates to LED curing printing ink capable of automatically shrinking to form textures and a preparation method of the LED curing printing ink. The LED curing ink capable of automatically shrinking to form the texture is prepared from the following components in percentage by weight: 5 to 9 percent of photoinitiator, 27 to 32 percent of tripropylene glycol diacrylate, 18 to 24 percent of trimethylolpropane triacrylate, 3 to 7 percent of organosilicone acrylate, 8 to 13 percent of regulator, 3 to 7 percent of pigment, 5 to 8 percent of modified nano material and the balance of polymer, and the polymer comprises epoxy acrylate, polyurethane acrylate and a four-functional acrylate oligomer. According to the printing ink prepared by the preparation method disclosed by the invention, by adding the organosilicone acrylate, a shrinkage effect can be generated, a specific texture effect can be spontaneously formed, and the printing ink is more resistant to a harsh environment and has an excellent effect when being used as a coated paper packaging material.

Description

Technical Field

[0001] The present invention belongs to the technical field of inks, and particularly relates to an LED-curable ink capable of autonomously shrinking to form textures and a preparation method thereof. Background Art

[0002] An LED-curable ink capable of autonomously shrinking to form textures is an advanced functional ink that can be rapidly cured under specific conditions (such as irradiation by a UV LED light source) and spontaneously forms specific texture effects during the curing process through the action of internal stress or special additives.

[0003] UV LED-curable inks have a wide range of applications in the field of packaging printing, and are particularly suitable for high-end product packaging and personalized customized packaging. They can be used for the packaging boxes and labels of high-end products such as luxury goods, cosmetics, and electronic products, significantly enhancing the brand image and product attractiveness through unique texture effects. In addition, it can also meet the needs of small-batch customization, such as limited-edition product packaging and festival special-edition packaging, providing a flexible and cost-effective solution, thereby enhancing market competitiveness and customer satisfaction. However, traditional UV inks require two sets of inks to be used in combination to produce a shrinking effect. Such printing processes have the disadvantages of high plate-making costs and expensive printing machines, and are only applicable to large-scale printing. The printing cost is expensive for small-batch printing.

[0004] Art paper is one of the commonly used materials in high-end packaging and is widely popular due to its excellent printing performance and appearance effects. However, due to the positioning standards of high-end brands, the inks used for high-end art paper have higher requirements for properties such as adhesion, gloss, resistance to high and low temperatures, and alcohol resistance, because these characteristics directly affect the performance of the packaging material in actual use and the overall quality of the product. For example: 1. Adhesion: Adhesion refers to the firmness of the ink on the art paper. If the adhesion is insufficient, the ink may fall off during transportation, storage, or use, resulting in defects on the packaging surface, affecting the aesthetics and brand image. Good adhesion ensures that the ink can remain stable under various environmental conditions and will not peel off due to friction, scratching, or other external forces. 2. High and low temperature resistance testing: High-end packaging paper may need to be used in different climate conditions around the world, so it must have good high and low temperature resistance. Extreme temperature changes may cause the ink to crack, discolor, or fall off, affecting the overall quality and appearance of the packaging. 3. Alcohol resistance testing: High-end packaging paper often comes into contact with various chemicals, such as cleaning agents, disinfectants, etc., and alcohol is one of the most common solvents. Inks with poor alcohol resistance are easily dissolved or eroded, affecting the aesthetics of the packaging and information transmission. Especially for cosmetics, electronic products, and food packaging, it is necessary to ensure that the ink does not fade or fall off when in contact with alcohol to ensure the integrity of the packaging and the clarity of the information.

[0005] CN 111100498 B discloses a UV-LED curable ink and its application. The ink can be used to prepare packaging printing products, but its high and low temperature resistance is poor when used on coated paper. It has excellent folding resistance at room temperature, but the folding resistance effect at low temperature is not good, unable to meet the high requirements of the current market.

[0006] Therefore, there is an urgent need for an LED curable ink that can autonomously shrink to form a texture and its preparation method. Summary of the Invention

[0007] The object of the present invention is to provide an LED curable ink that can autonomously shrink to form a texture and its preparation method. Through the design of the formula, after printing, the ink autonomously shrinks to produce a unique texture of an LED curable ink.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] An LED curable ink that can autonomously shrink to form a texture, comprising the following components in weight percentages: photoinitiator 5-9%, dipropylene glycol diacrylate 27-32%, trimethylolpropane triacrylate 18-24%, organosilicon acrylate 3-7%, regulator 8-13%, pigment 3-7% and modified nanomaterial 5-8%, the balance being polymer; the polymer comprises epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer.

[0010] In a preferred embodiment, the polymer comprises epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer in a weight ratio of (1.4-1.7):1:(0.3-0.5).

[0011] In a preferred embodiment, the polyurethane acrylate has the model EBECRYL® 230 of Sartomer Company.

[0012] In a preferred embodiment, the tetrafunctional acrylate oligomer has the model polyester resin EBECRYL® 892 of Sartomer Company.

[0013] By using a specific ratio of epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer, the present invention can improve the adhesion of the ink to coated paper and the folding resistance. By adjusting the ratio of epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer, the film layer can withstand greater stress during bending or folding without cracking or peeling.

[0014] In a preferred embodiment, the modified nanomaterial is prepared by mixing nano calcium carbonate, nano silicon dioxide and nano titanium dioxide and then modifying with a diamino-functional silane.

[0015] In a preferred embodiment, the diamino-functional silane is the silane coupling agent KH602.

[0016] In a preferred embodiment, the weight ratio of the nano calcium carbonate, nano silica and nano titanium dioxide is (1.2 - 1.5):(0.5 - 0.7):1.

[0017] The modified filler prepared by adding the diamino-functional silane in the present invention can improve the high and low temperature resistance and alcohol resistance of the ink. By using the diamino-functional silane to modify the nano materials in the present invention, the interfacial bonding force between the nano materials and the resin matrix can be enhanced, and at the same time, the uniform dispersion in the resin matrix of the present invention can be improved.

[0018] In a preferred embodiment, the preparation method of the modified nano material comprises the following steps:

[0019] (1) Mix the nano calcium carbonate, nano silica and nano titanium dioxide to obtain a nano material;

[0020] (2) Mix the silane coupling agent KH602, ethanol and water in a weight ratio of 1:3:3 and stir for 15 - 20 min to obtain a modified liquid;

[0021] (3) Mix the nano material and the modified liquid in a weight ratio of 1:5, heat up to 80 - 85 °C and stir for 3 - 4 h, filter and dry to obtain the modified nano material.

[0022] In a preferred embodiment, the photoinitiator comprises one or two of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-benzyl-2-dimethylamino-1-(4-morpholinobenzyl)-1-butanone.

[0023] In a preferred embodiment, the photoinitiator comprises 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-benzyl-2-dimethylamino-1-(4-morpholinobenzyl)-1-butanone.

[0024] In a preferred embodiment, the regulator is an active amine.

[0025] In a preferred embodiment, an LED curing ink that autonomously shrinks to form a texture comprises the following components in weight percentages: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 4%, 2-benzyl-2-dimethylamino-1-(4-morpholinobenzyl)-1-butanone 3%, dipropylene glycol diacrylate 30%, trimethylolpropane triacrylate 20%, organosilicon acrylate 5%, active amine 10%, and the balance is polymer.

[0026] The present invention provides a preparation method of an LED-curable ink that autonomously shrinks to form a texture, comprising the following steps: successively adding dipropylene glycol diacrylate, trimethylolpropane triacrylate, and a polymer to an initiator, stirring evenly, and then successively adding a silicone acrylate, a regulator, a pigment, and a modified nanomaterial, and stirring evenly to obtain an LED-curable ink that autonomously shrinks to form a texture.

[0027] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0028] 1. Adding a silicone acrylate to the curable ink of the present invention can produce a shrinking effect and can spontaneously form a specific texture effect.

[0029] 2. By adding a polymer in a specific proportion, the present invention can improve the adhesion of the ink to coated paper and the bending resistance.

[0030] 3. By adding a modified filler prepared from a diamino-functional silane, the present invention can improve the high and low temperature resistance and alcohol resistance of the ink. Description of the Drawings

[0031] Figure 1 It is a schematic diagram after curing of the LED-curable ink that autonomously shrinks to form a texture prepared in Example 1.

[0032] Figure 2 It is a wrapping paper prepared using the LED-curable ink that autonomously shrinks to form a texture prepared in Example 1. Detailed Embodiments

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0034] All raw materials used in the following embodiments of the present invention are commercially available products:

[0035] The model of the polyurethane acrylate is EBECRYL® 230 of Sartomer Company.

[0036] The model of the tetra-functional acrylate oligomer is the polyester resin EBECRYL® 892 of Sartomer Company.

[0037] Nano calcium carbonate, Shanghai Liangjiang Titanium White Chemical Products Co., Ltd., model LP400 ink-grade nano active calcium carbonate.

[0038] Nano silicon dioxide, Nanjing Tianxing New Materials Co., Ltd., model TSP-H10.

[0039] Nano-titanium dioxide, Nanjing Tianxing New Materials Co., Ltd., model TTP-A12.

[0040] Organic silicone acrylate, Guangdong Haohui New Materials Co., Ltd., model CR90822-1.

[0041] Epoxy acrylate, Zeneca EBECRYL 6040.

[0042] Silane coupling agent KH602, Nanjing Pining Coupling Agent Co., Ltd.

[0043] The active amine is ethylenediamine.

[0044] Example 1

[0045] This example provides an LED curing ink that autonomously shrinks to form a texture, including the following components in weight percentages: 4% of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 3% of 2-benzyl-2-dimethylamino-1-(4-morpholinobenzyl)-1-butanone, 30% of dipropylene glycol diacrylate, 20% of trimethylolpropane triacrylate, 5% of organic silicone acrylate, 10% of active amine, 5% of pigment, 7% of modified nano-material, and the balance is polymer.

[0046] The polymer includes epoxy acrylate, polyurethane acrylate, and tetrafunctional acrylate oligomer in a weight ratio of 1.6:1:0.4.

[0047] The preparation method of the modified nano-material includes the following steps:

[0048] (1) Mix nano-calcium carbonate, nano-silica, and nano-titanium dioxide in a weight ratio of 1.3:0.6:1 to obtain nano-material;

[0049] (2) Mix the silane coupling agent KH602, ethanol, and water in a weight ratio of 1:3:3 and stir for 20 min to obtain a modified solution;

[0050] (3) Mix the nano-material and the modified solution in a weight ratio of 1:5, heat up to 82 °C and stir for 3.5 h, filter and dry to obtain the modified nano-material.

[0051] The preparation method of the LED curing ink that autonomously shrinks to form a texture includes the following steps: sequentially add dipropylene glycol diacrylate, trimethylolpropane triacrylate, and polymer to the initiator, stir evenly, and then sequentially add organic silicone acrylate, regulator, pigment, and modified nano-material, and stir evenly to obtain the LED curing ink that autonomously shrinks to form a texture.

[0052] Example 2

[0053] This embodiment provides an LED-curable ink that autonomously shrinks to form a texture, comprising components in the following weight percentages: 3% of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 5% of 2-benzyl-2-dimethylamino-1-(4-morpholinobenzyl)-1-butanone, 27% of dipropylene glycol diacrylate, 24% of trimethylolpropane triacrylate, 7% of silicone acrylate, 10% of active amine, 4% of pigment, 6% of modified nanomaterial, and the balance being polymer.

[0054] The polymer comprises epoxy acrylate, polyurethane acrylate, and tetrafunctional acrylate oligomer in a weight ratio of 1.4:1:0.5.

[0055] The preparation method of the modified nanomaterial comprises the following steps:

[0056] (1) Mix nanometer calcium carbonate, nanometer silicon dioxide, and nanometer titanium dioxide in a weight ratio of 1.3:0.6:1 to obtain a nanomaterial;

[0057] (2) Mix a silane coupling agent KH602, ethanol, and water in a weight ratio of 1:3:3, and stir for 20 min to obtain a modified liquid;

[0058] (3) Mix the nanomaterial and the modified liquid in a weight ratio of 1:5, heat to 80°C, stir for 4 h, filter, and dry to obtain the modified nanomaterial.

[0059] The preparation method of the LED-curable ink that autonomously shrinks to form a texture comprises the following steps: sequentially add dipropylene glycol diacrylate, trimethylolpropane triacrylate, and polymer to an initiator, stir evenly, and then sequentially add silicone acrylate, regulator, pigment, and modified nanomaterial, and stir evenly to obtain the LED-curable ink that autonomously shrinks to form a texture.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 1 is that the polymer is epoxy acrylate.

[0062] Comparative Example 2

[0063] The difference between this comparative example and Example 1 is that the polymer comprises epoxy acrylate and polyurethane acrylate in a weight ratio of 1.6:1.

[0064] Comparative Example 3

[0065] The difference between this comparative example and Example 1 is that the polymer comprises epoxy acrylate, polyurethane acrylate, and tetrafunctional acrylate oligomer in a weight ratio of 1:1:1.

[0066] Comparative Example 4

[0067] The difference between this comparative example and Example 1 is that the modified nanomaterial is prepared by modifying nano calcium carbonate with a bis-amino functional group silane.

[0068] The preparation method of the modified nanomaterial includes the following steps:

[0069] (1) Mix silane coupling agent KH602, ethanol, and water with a weight ratio of 1:3:3 and stir for 20 min to obtain a modified solution;

[0070] (2) Mix nano calcium carbonate and the modified solution with a weight ratio of 1:5, heat to 82 °C, stir for 3.5 h, filter, and dry to obtain the modified nanomaterial.

[0071] Comparative Example 5

[0072] This comparative example is prepared according to the preparation method of Example 1 in CN 111100498 B, a UV-LED curable ink and its application.

[0073] Performance Testing

[0074] Put the LED curable inks prepared in Examples 1-2 and Comparative Examples 1-5 and 300 g of coated paper into a screen printing machine for screen printing, and cure them with a UV-LED lamp tube. Mesh: 400 meshes, wire diameter: 0.05 mm; Curing conditions: Light source: 400, Energy: 120 mj / cm² to obtain samples.

[0075] (1) Adhesion detection: Use 3M #600 tape and refer to the cross-cut test in GB / T 9286-2021.

[0076] (2) Bending resistance detection: Check for any changes after bending at 90° at 10 °C, and check for any cracking or peeling of the paint film.

[0077] (3) High and low temperature resistance detection: Place in an environment of (60 °C, 3 h; -40 °C, 3 h) for 20 cycles, allow to return to room temperature naturally after the test is completed, check the appearance and perform adhesion detection. No cracking or peeling, and it is required that it does not peel off after being pasted with tape is qualified; Any of the above situations is unqualified.

[0078] (4) Alcohol resistance detection: Wrap a rubber eraser with 4 layers of lint-free cloth dipped in anhydrous ethanol, slide back and forth horizontally with a force of 500 g for 100 times without showing white, stroke 2 cm, and frequency 30 times / min is qualified.

[0079] The results are shown in Table 1.

[0080] Table 1 Performance Test Results

[0081] Adhesion Bending resistance test at 25°C Bending resistance test at 10°C High and low temperature resistance test Alcohol resistance test Example 1 Grade 0 No cracking, no peeling No cracking, no peeling Qualified Qualified Example 2 Grade 0 No cracking, no peeling No cracking, no peeling Qualified Qualified Comparative Example 1 Grade 1 Cracking, peeling Cracking, peeling Unqualified Unqualified Comparative Example 2 Grade 1 Cracking, no peeling Cracking, peeling Unqualified Unqualified Comparative Example 3 Grade 1 No cracking, no peeling Cracking, peeling Unqualified Qualified Comparative Example 4 Grade 0 No cracking, no peeling Cracking, peeling Unqualified Unqualified Comparative Example 5 Grade 0 No cracking, no peeling Cracking, peeling Unqualified Qualified

[0082] As can be seen from Table 1, the ink prepared in Examples 1-2 of the present invention has good adhesion to coated paper, excellent performance under extreme environmental conditions, and can meet the market requirements for high-grade packaging paper. By Figure 1 and Figure 2 it can be seen that the ink prepared by the present invention can autonomously shrink to form textures (also known as leather grains or glaze surfaces), and the packaging paper prepared with it has excellent quality.

[0083] In Comparative Example 1, the polymer is epoxy acrylate, and the adhesion of the ink to the surface of the coated paper decreases, and the bending resistance decreases.

[0084] In Comparative Example 2, the polymer comprises epoxy acrylate and polyurethane acrylate with a weight ratio of 1.6:1, and the adhesion of the ink to the surface of the coated paper decreases, and the bending resistance decreases.

[0085] In Comparative Example 3, the polymer comprises epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer with a weight ratio of 1:1:1, and the adhesion of the ink to the surface of the coated paper decreases, and the bending resistance decreases. It shows that only by using a polymer with a specific ratio can the present invention maintain high adhesion of the ink to the surface of the coated paper and excellent bending resistance.

[0086] In Comparative Example 4, the modified nanomaterial is only prepared with nano calcium carbonate, and the high and low temperature resistance and alcohol resistance of the ink decrease.

[0087] From Comparative Example 5, it can be seen that the performance of the ink in the prior art under extreme environmental conditions is not ideal. Comparative Example 5 has a good bending resistance effect at room temperature, but the effect is not good at 10°C, and it cannot meet the requirements for use in areas with lower temperatures. The high and low temperature resistance of the ink in Comparative Example 5 at 60°C and -40°C is also not ideal and cannot meet the market demand.

[0088] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. An LED curing ink that shrinks autonomously to form a texture, characterized in that: The invention comprises the following components in weight percentage: 5-9% of photoinitiator, 27-32% of tripropylene glycol diacrylate, 18-24% of trimethylolpropane triacrylate, 3-7% of organosilicon acrylate, 8-13% of regulator, 3-7% of pigment and 5-8% of modified nanomaterial, and the balance is polymer; the polymer comprises epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer.

2. The LED curing ink that shrinks autonomously to form a texture according to claim 1, characterized in that: The polymer includes epoxy acrylate, polyurethane acrylate and tetrafunctional acrylate oligomer in a weight ratio of (1.4-1.7):1:(0.3-0.5).

3. The LED curing ink that shrinks autonomously to form a texture according to claim 1, characterized in that: The modified nano material is prepared by mixing nano calcium carbonate, nano silicon dioxide and nano titanium dioxide and then modifying them with diamino functional group silane.

4. The LED curing ink that shrinks autonomously to form a texture according to claim 3, characterized in that: The diamino functional silane is the silane coupling agent KH602.

5. The LED curing ink that shrinks autonomously to form a texture according to claim 4, characterized in that: The weight ratio of the nano calcium carbonate, nano silicon dioxide and nano titanium dioxide is (1.2-1.5): (0.5-0.7):

1.

6. The LED curing ink that shrinks autonomously to form a texture according to claim 5, characterized in that: The preparation method of the modified nanomaterial comprises the following steps: (1) Mixing nano calcium carbonate, nano silicon dioxide and nano titanium dioxide to obtain nano materials; (2) Mix and stir silane coupling agent KH602, ethanol and water to obtain a modified liquid; (3) Mix the nanomaterial and the modified liquid, heat to 80-85°C and stir for 3-4 hours, filter and dry to obtain the modified nanomaterial.

7. The LED curing ink that shrinks autonomously to form a texture according to claim 1, characterized in that: The photoinitiator includes one or two of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-benzyl-2-dimethylamino-1-(4-morpholinylbenzyl)-1-butanone.

8. The LED curing ink that shrinks autonomously to form a texture according to claim 7, characterized in that: The photoinitiator includes 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-benzyl-2-dimethylamino-1-(4-morpholinylbenzyl)-1-butanone.

9. The LED curing ink that shrinks autonomously to form a texture according to claim 1, characterized in that: The regulator is an active amine.

10. A method for preparing the LED curing ink with autonomous shrinkage to form texture according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: sequentially adding tripropylene glycol diacrylate, trimethylolpropane triacrylate and a polymer into an initiator, stirring evenly, then sequentially adding silicone acrylate, a regulator, a pigment and a modified nano material, stirring evenly, and obtaining an LED curing ink that shrinks autonomously to form a texture.

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