Varnish composition, varnish and preparation method and use thereof

Abstract

The application discloses a varnish composition, a varnish and a preparation method and application thereof; the varnish composition comprises a base material, modified polyhedral oligomeric silsesquioxane, a reactive slip agent, a composite photoinitiator and an amine synergist; the content of the modified polyhedral oligomeric silsesquioxane is 2-10 parts by weight, the content of the reactive slip agent is 0.5-1.5 parts by weight, the content of the composite photoinitiator is 7.2-11.1 parts by weight, and the content of the amine synergist is 7-9.2 parts by weight, which are all calculated on the basis of 100 parts by weight of the base material; the varnish prepared from the varnish composition has higher scratch resistance and flexibility; and the varnish can be cured by LED-UV.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a varnish composition, a varnish, a method for preparing the varnish, and its application. Background Technology

[0002] Traditionally, the scratch resistance of coating materials can be improved using surface additives or nanocomposites. However, surface additives have weak interactions with each other and with the substrate. Additives can affect the wettability of the formulation, and the resulting varnish coating is prone to peeling. Another approach is to use nanocomposites (such as silica) to improve the overall hardness and mechanical properties of the coating, thereby enhancing scratch resistance. However, the manufacturing process is complex, and nano-silica may experience aggregation problems, which can affect the transparency of the coating. In particular, current UV varnish coatings on the market are insufficient to meet the needs of paper products. The scratch resistance and folding performance of varnishes are unsatisfactory. Firstly, current varnishes have poor scratch resistance, so coated paper products are not durable; secondly, current varnishes are not flexible enough, and cracks may appear when folding paper products.

[0003] Furthermore, varnishes must be cured using high-energy Hg-UV lamps; ultraviolet curing processes using mercury arc lamps are environmentally harmful. They produce ozone, necessitating exhaust systems to prevent air pollution. In addition, UV curing processes using mercury lamps require high energy to operate and generate significant 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 at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present invention provides a varnish composition, wherein the varnish prepared from the varnish composition can be cured by LED-UV and has high scratch resistance and high flexibility.

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

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

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

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

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

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

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

[0013]

[0014] Where R is selected from At least one of the following; m and n are integers from 1 to 10.

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

[0016] This invention utilizes acryloyl and epoxy functional groups to modify polyhedral oligomeric silsesquioxanes, resulting in varnish compositions with improved scratch resistance and flexibility. This is because POSS containing methacryl groups is more compatible with the varnish composition. The epoxy-containing functional groups further enhance hardness, while the methacryl-containing functional groups improve compatibility.

[0017] Furthermore, the modified POSS provided by this invention can effectively improve the reaction rate and achieve low-energy curing (LED-UV).

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

[0019] According to some embodiments of the present invention, the mass ratio of the polyurethane acrylate polymer, acrylate polymer, trimethylolpropane triacrylate ethoxylate and 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 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 comprises a combination of thioxanthone photoinitiators and cationic photoinitiators. Thus, the composite photoinitiator formed by using a combination of thioxanthone photoinitiators and cationic photoinitiators can, on the one hand, reduce curing energy, and on the other hand, promote the polymerization of various monomers, resulting in a polymer coating that forms a robust 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, isopropylphenylcyclopentadiene iron hexafluorophosphate, and isopropylphenyl ferrocene hexafluoroantimonate.

[0023] According to some embodiments of the present invention, the thioxanthone 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 comprises a combination of triarylsulfonium hexafluoroantimonate, 2-isopropylthioxanthanone, and 2,4-diethylthioxanthanone.

[0025] According to some embodiments of the present invention, the reactive slip agent is selected from at least one of the brands ACR-3640, ACR-3580, TEGO Rad2300, TEGORad2330, and TEGORad2500. Thus, the double bonds of the reactive slip agent participate in the cross-linking network, using covalent bonds to ensure the strength of the additive molecules within 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 the brands AgiSyn002 (Covestro), AgiSyn008 (Covestro), RJ10 (RYOJI), or ethyl 4-(dimethylamino)benzoate. Thus, the amine synergist can reduce the inhibition of crosslinking by oxygen, act as an oxygen scavenger, and initiate the polymerization of acrylates.

[0027] According to some embodiments of the present invention, the varnish composition of the present invention further includes acrylate monomers.

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

[0029] According to some embodiments of the present invention, the acrylate monomers include tripropylene glycol diacrylate and trimethylolpropane triacrylate. This provides scratch resistance and hydrophobicity, increasing durability.

[0030] A varnish according to a second aspect of the present invention includes the varnish composition described in the first aspect of the present invention.

[0031] A third aspect of the present invention provides a method for preparing a varnish as described in the second aspect of the present invention, comprising the following steps:

[0032] The varnish composition described in the first aspect of this invention is obtained by mixing and stirring.

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

[0034] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

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

[0036] Figure 1 These are microscope images of the varnish coatings formed in the embodiments and comparative examples of the present invention. Detailed Implementation

[0037] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be 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 this invention are all conventional reagents, methods and equipment in this technical field.

[0039] Some of the raw materials used in this invention are as follows:

[0040] Methacrylamide cage-type polysilsesquioxane: MA0735; CAS No.: 160185-24-0; commercially available.

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

[0042]

[0043] Base material: A combination of polyurethane acrylate polymer, acrylate polymer, trimethylolpropane triacrylate ethoxylate and dipropylene glycol diacrylate (base material grade: H66B, purchased from Hampson Dongguan Industrial Materials Co., Ltd.).

[0044] Reactive slip agents: ACR 3580 and ACR 3640; purchased from Wyncoat.

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

[0046] Amine synergists: Tertiary amine AgiSyn 002; AgiSyn 008 is supplied by Covestro.

[0047] Examples 1-3

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

[0049] Table 1

[0050]

[0051]

[0052] Examples 4-5

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

[0054] Table 2

[0055]

[0056] Comparative Example 1

[0057] Comparative Example 1 provides a varnish composition whose component content is basically the same as that of Example 1, except that it does not contain modified polyhedral oligomeric silsesquioxane.

[0058] Comparative Example 2

[0059] Comparative Example 2 provides a varnish composition, the component content (parts by weight) of which is shown in Table 3:

[0060] Table 3

[0061]

[0062] Comparative Example 3

[0063] Comparative Example 3 provides a varnish composition whose component content is basically the same as that of Example 1. The difference is 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 with the same component content as in Example 1, except that the photoinitiator is a mixture of 2-isopropylthioxanthanone (ITX) and 2,4-diethylthioxanthanone (DETX).

[0066] Performance testing

[0067] The varnish compositions of the embodiments and comparative examples of the present invention were prepared into varnishes using the following specific processes:

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

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

[0070] Abrasion resistance test: conducted 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 1-5 and Comparative Examples 1-4

[0072] 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] As can be seen from the data in Table 4, the varnish compositions provided in Examples 1 to 5 of the present invention can obtain coatings with better wear resistance under lower curing energy.

[0074] Further testing of flexibility was conducted. The testing method involved bending the coating outward by 180 degrees and observing for damage under a microscope at 140x magnification.

[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, where Figure 1 a) The varnish coating of Example 1 is bent. The upper image shows the state observed with the naked eye, and the lower image shows the state of the crease under a microscope at 140x magnification. Figure 1 b shows the varnish coating of Comparative Example 2 after bending. The upper image is the state observed with the naked eye, and the lower image is the state of the crease under a microscope at 140x magnification.

[0076] from Figure 1 As can be seen, the white crackling pattern in Example 1 is narrow and thin. In Comparative Example 2, the white crackling pattern is wide and long. This result indicates that the flexural resistance of the formulation in Example 1 is superior to that in Comparative Example 2.

[0077] The present invention has been described in detail above with reference to the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A varnish composition, characterized in that, It includes base material, modified polyhedral oligomeric silsesquioxane, reactive slip agent, composite photoinitiator and amine synergist; Based on a base material content of 100 parts by weight, the modified polyhedral oligomeric silsesquioxane content is 2-10 parts by weight; the reactive slip agent content is 0.5-1.5 parts by weight; the composite photoinitiator content is 7.2-11.1 parts by weight; and the amine synergist content is 7-9.2 parts by weight. The base material includes polyurethane acrylate polymer, acrylate polymer, ethoxytrimethylolpropane triacrylate and dipropylene glycol diacrylate; The structural formula of the modified polyhedral oligomeric silsesquioxane is as follows: ； Where R is selected from At least one of the following; m and n are integers from 1 to 10; The molar ratio is 1:(0.3~3); The composite photoinitiator includes a combination of thioxanthone photoinitiators and cationic photoinitiators; The reactive slip agent is selected from at least one of the following brands: ACR-3640, ACR-3580, TEGO Rad 2300, TEGO Rad 2330, and TEGO Rad 2500.

2. The varnish composition according to claim 1, characterized in that, The cationic photoinitiator includes at least one of triarylsulfonium hexafluoroantimonate, isopropylphenylcyclopentadiene iron hexafluorophosphate, and isopropylphenyl ferrocene hexafluoroantimonate.

3. The varnish composition according to claim 1, characterized in that, The thioxanthone photoinitiator includes at least one of 2,4-diethylthioxanthone, 2-isopropylthioxanthone, or 2-chlorothioxanthone.

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

5. A varnish, characterized in that, Includes the varnish composition according to any one of claims 1 to 4.

6. A method for preparing the varnish as described in claim 5, characterized in that, Includes the following steps: The varnish composition according to any one of claims 1 to 4 is obtained by mixing and stirring.

7. The use of the varnish composition according to any one of claims 1 to 4 or the varnish according to claim 5 in paper materials.

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