Varnish composition, varnish as well as preparation method and application of varnish

Abstract

The invention discloses a varnish composition, varnish as well as a preparation method and application of the varnish. The varnish composition comprises a base material, modified polyhedral oligomeric silsesquioxane, a reactive slipping agent, a composite photoinitiator and an amine synergist, on the basis that the content of the base material is 100 parts by weight, the content of the modified polyhedral oligomeric silsesquioxane is 2-10 parts by weight; the content of the reactive slipping agent is 0.5 to 1.5 parts by weight; the content of the composite photoinitiator is 7.2 to 11.1 parts by weight; the content of the amine synergist is 7 to 9.2 parts by weight. The varnish prepared from the varnish composition disclosed by the invention has higher scratch resistance and flexibility; and the LED-UV curing can be realized.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a varnish composition, a varnish, a preparation method and application thereof. Background Art

[0002] Traditionally, the scratch resistance of coating materials can be improved by surface additives or nanocomposites. However, surface additives interact weakly with each other and with the substrate. Additives may affect the wettability of the formulation, and the resulting varnish coating can easily peel off. Another approach is to use nanocomposites (such as silica) to improve the overall hardness and mechanical properties of the coating, thereby improving scratch resistance. However, the manufacturing process is complicated and nano-silica may have aggregation problems, which affects the transparency of the coating. In particular, the UV varnish coatings currently on the market are not sufficient to meet the needs of paper products. The scratch resistance and folding performance of varnishes are unsatisfactory. First, the current varnishes have poor scratch resistance, so paper products with coatings are not durable; on the other hand, the flexibility of current varnishes is not good enough, and cracks will appear when paper products are folded.

[0003] Additionally, the varnish must be cured with high-energy Hg-UV lamps; the UV curing process using mercury arc lamps is harmful to the environment. It produces ozone and requires an exhaust system to prevent air pollution. In addition, the UV curing process using mercury lamps also requires high energy to operate and generates a lot of heat during operation.

[0004] Therefore, it is necessary to develop a varnish composition that can be cured using LED-UV and has scratch resistance and flexibility. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the first aspect of the present invention provides a varnish composition, and the varnish prepared from the varnish composition can be cured by LED-UV and has high scratch resistance and high flexibility.

[0006] The second aspect of the present invention also provides a varnish.

[0007] The third aspect of the present invention also provides a method for preparing a varnish.

[0008] The fourth aspect of the present invention also provides an application.

[0009] A varnish composition provided according to the first aspect of the present invention comprises a base material, a modified polyhedral oligomeric silsesquioxane (POSS), a reactive slip agent, a composite photoinitiator and an amine synergist;

[0010] Based on 100 parts by weight of the base material, the content of the modified polyhedral oligomeric silsesquioxane is 2 to 10 parts by weight; the content of the reactive lubricant is 0.5 to 1.5 parts by weight; the content of the composite photoinitiator is 7.2 to 11.1 parts by weight; and the content of the amine synergist is 7 to 9.2 parts by weight;

[0011] The base material includes polyurethane acrylate polymer, acrylate polymer, ethoxylated trimethylolpropane triacrylate and dipropylene glycol diacrylate;

[0012] The structural formula of the modified polyhedral oligomeric silsesquioxane is as follows:

[0013]

[0014] Among them, R is selected from At least one of; m and n are integers of 1 to 10.

[0015] The varnish composition according to the embodiment of the present invention has at least the following beneficial effects:

[0016] The present invention uses acryl functional groups and epoxy functional groups to modify polyhedral oligomeric silsesquioxane, so that the varnish composition of the present invention has higher scratch resistance and flexibility. This is because the POSS with methacryloyl groups will be more compatible with the varnish composition. The epoxy functional group further increases the hardness, while the methacryloyl functional group increases the compatibility.

[0017] Furthermore, the modified POSS provided by the present invention can effectively increase the reaction speed and realize low-energy curing (LED-UV).

[0018] Furthermore, the reactive lubricant of the present invention can improve the surface slipperiness and enhance the surface wear resistance.

[0019] According to some embodiments of the present invention, the mass ratio of the polyurethane acrylate polymer, the acrylate polymer, the ethoxylated trimethylolpropane triacrylate and the dipropylene glycol diacrylate is (2.5-3.5):(1.5-2.5):(1.5-2.5):1.

[0020] According to some embodiments of the present invention, the The molar ratio of is 1:(0.3-3). Therefore, the varnish prepared from the varnish composition of the present invention has higher scratch resistance and flexibility.

[0021] According to some embodiments of the present invention, the composite photoinitiator includes a combination of a thioxanthone photoinitiator and a cationic photoinitiator. Thus, the composite photoinitiator formed by the combination of the thioxanthone photoinitiator and the cationic photoinitiator can reduce the curing energy on the one hand, and promote the polymerization of various monomers on the other hand, and the resulting polymer coating forms a strong cross-linked interpenetrating network, further achieving higher scratch resistance.

[0022] According to some embodiments of the present invention, the cationic photoinitiator includes at least one of triarylsulfonium hexafluoroantimonate, cumylcyclopentadienylferroxenylphosphate, and cumylferrocene hexafluoroantimonate.

[0023] According to some embodiments of the present invention, the thioxanthone-based photoinitiator includes at least one of 2,4-diethylthioxanthone (DETX), 2-isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX).

[0024] According to some embodiments of the present invention, the composite photoinitiator includes a combination of triarylsulfonium hexafluoroantimonate, 2-isopropylthioxanthone and 2,4-diethylthioxanthone.

[0025] According to some embodiments of the present invention, the reactive lubricant is selected from at least one of ACR-3640, ACR-3580, TEGO Rad2300, TEGORad2330, and TEGORad2500. Thus, the double bonds of the reactive lubricant participate in the cross-linking network, and the covalent bonds are used to ensure the strength of the additive molecules in the overall polymer network, making the overall structure more wear-resistant.

[0026] According to some embodiments of the present invention, the amine synergist is selected from at least one of AgiSyn002 (Covestro), AgiSyn008 (Covestro), RJ10 (RYOJI) or ethyl 4-(dimethylamino)benzoate. Thus, the amine synergist can reduce the inhibition of oxygen on crosslinking, act as an oxygen scavenger and initiate the polymerization of acrylate.

[0027] According to some embodiments of the present invention, the varnish composition of the present invention further comprises an acrylate monomer.

[0028] According to some embodiments of the present invention, based on 100 parts by weight of the base material, the content of the acrylate monomer is 0 to 20 parts by weight.

[0029] According to some embodiments of the present invention, the acrylate monomer includes tripropylene glycol diacrylate and trimethylolpropane triacrylate, thereby providing scratch resistance and hydrophobicity, and increasing durability.

[0030] A varnish provided according to an embodiment of the second aspect of the present invention comprises the varnish composition described in the first aspect of the present invention.

[0031] The third aspect of the present invention provides a method for preparing the varnish according to the second aspect of the present invention, comprising the following steps:

[0032] The varnish composition described in the first aspect of the present invention is mixed and stirred to obtain the varnish composition.

[0033] The fourth aspect of the present invention provides use of the varnish composition described in the first aspect of the present invention or the varnish described in the second aspect of the present invention in paper materials.

[0034] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0036] Figure 1 1 is a microscope picture of the varnish coating formed in the examples of the present invention and the comparative example. DETAILED DESCRIPTION

[0037] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0038] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0039] Some of the raw materials of the present invention are as follows:

[0040] Methacrylamide cage polysilsesquioxane: MA0735; CAS number: 160185-24-0; commercially available.

[0041] The structural formula of the modified polyhedral oligomeric silsesquioxane is as follows: HC0407.11 (Hybrid Plastic) is commercially available.

[0042]

[0043] Base material: a combination of polyurethane acrylate polymer, acrylate polymer, ethoxylated trimethylolpropane triacrylate and dipropylene glycol diacrylate (brand number of the base material: H66B, purchased from Hampson Dongguan Hampson Industrial Materials Co., Ltd.).

[0044] Reactive lubricants: ACR 3580 and ACR 3640; purchased from Wyncoat Company;

[0045] Composite photoinitiator: a combination of triarylsulfonium hexafluoroantimonate, 2-isopropylthioxanthone and 2,4-diethylthioxanthone; purchased from Sigma and Aladdin Reagents.

[0046] Amine synergist: Tertiary amine AgiSyn 002; AgiSyn 008 provided by Covestro.

[0047] Examples 1 to 3

[0048] Examples 1 to 3 provide a series of varnish compositions, and the component contents (parts by weight) thereof are shown in Table 1.

[0049] Table 1

[0050]

[0051]

[0052] Embodiment 4-5

[0053] Examples 4-5 provide a series of varnish compositions, and the component contents (parts by weight) thereof are shown in Table 2.

[0054] Table 2

[0055]

[0056] Comparative Example 1

[0057] Comparative Example 1 provides a varnish composition, the component contents of which are substantially the same as those of Example 1, except that the varnish composition does not contain modified polyhedral oligomeric silsesquioxane.

[0058] Comparative Example 2

[0059] Comparative Example 2 provides a varnish composition, the component contents (parts by weight) are shown in Table 3:

[0060] Table 3

[0061]

[0062] Comparative Example 3

[0063] Comparative Example 3 provides a varnish composition, the component contents of which are substantially the same as those of Example 1, except that methacrylamide cage-type polysilsesquioxane is used instead of the modified polyhedral oligomeric silsesquioxane of Example 1.

[0064] Comparative Example 4

[0065] Comparative Example 4 provides a varnish composition, the component contents of which are substantially the same as those of Example 1, except that the photoinitiator is a mixture of 2-isopropylthioxanthone (ITX) and 2,4-diethylthioxanthone (DETX).

[0066] Performance Testing

[0067] The varnish compositions of the embodiments of the present invention and the comparative examples are prepared into varnishes, and the specific process is as follows:

[0068] The components of the varnish compositions in the examples of the present invention and the comparative examples were mixed and stirred (rotated at 2000 rpm for 2 minutes) to obtain the varnish compositions.

[0069] The varnish prepared in the examples and comparative examples of the present invention was coated on the surface of black paper and cured by LED-UV (the instrument was provided by Novachem Corporation Ltd) to obtain a coating with a thickness of 8 μm.

[0070] Abrasion resistance test: performed according to ASTM D5264-2019, using a weight of 2 Ib (0.91 kg). The results are shown in Table 4.

[0071] Table 4 Examples 1 to 5 and Comparative Examples 1 to 4

[0072] LED-UV curing energy Friction resistance Example 1 1000mj 4000 Example 2 1500mj 1200 Example 3 1000mj 1200 Example 4 1000mj 1000 Example 5 1000mj 1500 Comparative Example 1 1000mj 800 Comparative Example 2 1000mj 300 Comparative Example 3 1000mj 500 Comparative Example 4 1000mj 500

[0073] From the data in Table 4, it can be seen that the varnish compositions provided in Examples 1 to 5 of the present invention can obtain coatings with better wear resistance at a lower curing energy.

[0074] Furthermore, the flexibility performance was tested; the testing method was: bend the coating outward 180 degrees; and observe whether it was damaged under a microscope at a magnification of 140 times.

[0075] The varnish coatings of Example 1 and Comparative Example 2 of the present invention were tested, and the results are as follows: Figure 1 As shown, Figure 1 a is the varnish coating of Example 1 after bending, the upper picture is the state observed by naked eyes, and the lower picture is the state of the crease magnified 140 times by a microscope; Figure 1 b is the varnish coating of comparative example 2 after being bent. The upper picture shows the state observed with the naked eye, and the lower picture shows the state of the crease magnified 140 times under a microscope.

[0076] from Figure 1 It can be seen that the width of the white background cracked in Example 1 is narrow and thin. The white background cracked in Comparative Example 2 is wide and long. This result shows that the bending resistance of the formulation of Example 1 is better than that of Comparative Example 2.

[0077] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A varnish composition, characterized in that It includes base material, modified polyhedral oligomeric silsesquioxane, reactive lubricant, composite photoinitiator and amine synergist; Based on 100 parts by weight of the base material, the content of the modified polyhedral oligomeric silsesquioxane is 2 to 10 parts by weight; the content of the reactive lubricant is 0.5 to 1.5 parts by weight; the content of the composite photoinitiator is 7.2 to 11.1 parts by weight; and the content of the amine synergist is 7 to 9.2 parts by weight; The base material includes polyurethane acrylate polymer, acrylate polymer, ethoxylated trimethylolpropane triacrylate and dipropylene glycol diacrylate; The structural formula of the modified polyhedral oligomeric silsesquioxane is as follows: Among them, R is selected from At least one of; m and n are integers of 1 to 10.

2. The varnish composition according to claim 1, characterized in that The molar ratio is 1:(0.3~3).

3. The varnish composition according to claim 1 or 2, characterized in that The composite photoinitiator comprises a combination of a thioxanthone photoinitiator and a cationic photoinitiator.

4. The varnish composition according to claim 3, characterized in that The cationic photoinitiator includes at least one of triarylsulfonium hexafluoroantimonate, cumylcyclopentadienylferroxyl hexafluorophosphate, and cumylferrocene hexafluoroantimonate.

5. The varnish composition according to claim 3, characterized in that The thioxanthone photoinitiator includes at least one of 2,4-diethylthioxanthone, 2-isopropylthioxanthone or 2-chlorothioxanthone.

6. The varnish composition according to claim 1 or 2, characterized in that The reactive lubricant is selected from at least one of ACR-3640, ACR-3580, TEGO Rad 2300, TEGO Rad 2330 and TEGO Rad 2500.

7. The varnish composition according to claim 1 or 2, characterized in that The amine synergist is selected from at least one of AgiSyn 002, AgiSyn 008, RJ 10 or ethyl 4-(dimethylamino)benzoate.

8. A varnish, characterized in that: The varnish composition comprises the varnish composition according to any one of claims 1 to 7.

9. A method for preparing the varnish according to claim 8, characterized in that: The steps include: The varnish composition according to any one of claims 1 to 7 is mixed and stirred to obtain the varnish.

10. Use of the varnish composition according to any one of claims 1 to 7 or the varnish according to claim 8 in paper materials.

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