Purple hardening liquid and preparation method thereof

Abstract

The invention discloses ultraviolet hardening liquid and a preparation method thereof, and relates to the technical field of ultraviolet curing. The preparation method comprises the following steps: providing a polyhedral oligomeric silsesquioxane oligomer, a low-functional-group polyurethane modified acrylate oligomer, nano hybrid modified acrylic resin, an auxiliary agent, a silane coupling agent, a free radical initiator, a cationic initiator and a solvent, wherein the polyhedral oligomeric silsesquioxane oligomer has an acid bond structure; the ultraviolet hardening liquid is prepared from the polyhedral oligomeric silsesquioxane oligomer, the low-functional-group polyurethane modified acrylate oligomer, the nano-hybrid modified acrylic resin, an auxiliary agent, a silane coupling agent, a free radical initiator, a cationic initiator and a solvent. The invention aims to solve the problems of poor adhesive force on a plastic base material, poor boiling resistance, easy cracking and poor hardness and scratch resistance after curing of the existing ultraviolet and hardening liquid.

Description

Technical Field

[0001] The present application relates to the field of ultraviolet curing technology, and in particular to an ultraviolet curing liquid and a preparation method thereof. Background Art

[0002] UV curing fluid is a UV-curable liquid material used to increase the surface hardness and wear resistance of materials. UV curing fluid is primarily used to improve the surface hardness, wear resistance, and weather resistance of materials such as plastics and glass. It is widely used in electronics, furniture, and decorative materials.

[0003] However, existing UV hardening liquids have some problems in practical application, such as poor adhesion to plastic substrates, poor water boiling resistance, and easy cracking. In addition, after curing, the UV hardening liquids also have poor hardness and scratch resistance. Summary of the Invention

[0004] The present application provides a UV hardening liquid and a preparation method thereof, aiming to solve the problems of existing UV hardening liquid on plastic substrates, such as poor adhesion, poor water boiling resistance, easy cracking, and poor hardness and scratch resistance after curing.

[0005] In a first aspect, the present application provides a UV hardening liquid, which is prepared from the following raw materials: a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an additive, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent, wherein the cage-type polysilsesquioxane oligomer has an acid bond structure.

[0006] In a second aspect, the present application provides a method for preparing a UV hardening solution, the preparation method comprising:

[0007] Provided are a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an auxiliary agent, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent, wherein the cage-type polysilsesquioxane oligomer has an acid bond structure;

[0008] The ultraviolet hardening liquid is prepared by using the cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin, auxiliary agent, silane coupling agent, free radical initiator, cationic initiator and solvent.

[0009] The present application provides a UV hardening solution and a preparation method thereof. The UV hardening solution is prepared by reacting a cage-type polysilsesquioxane oligomer having an acid bond structure, a low-functionality polyurethane-modified acrylate oligomer, and a nano-hybrid modified acrylic resin. The UV hardening solution is used to cure a material, thereby forming a strong cross-linked network, thereby improving the material's hardness and temperature resistance. It also reduces surface energy, enhancing the material's surface scratch resistance, wear resistance, chemical resistance, and water resistance, and imparting a certain toughness to the cross-linked and cured film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the description of the embodiments. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0011] Figure 1 Schematic diagram of the chemical reaction of a fluorine-modified caged silsesquioxane oligomer provided in an embodiment of the present application;

[0012] Figure 2 This is a flow chart of an embodiment of a method for preparing a UV hardening solution provided in an embodiment of the present application;

[0013] Figure 3 This is a flow chart of another embodiment of a method for preparing a UV hardening solution provided in an embodiment of the present application. DETAILED DESCRIPTION

[0014] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0015] It will be understood that when used in this specification and the appended claims, the terms “comprises” and “comprising” indicate the presence of described features, integers, steps, operations, elements and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups thereof.

[0016] It should also be understood that the terms used in this specification are for the purpose of describing specific embodiments only and are not intended to limit the present application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly indicates otherwise.

[0017] It should be further understood that the term "and / or" used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

[0018] The following describes some embodiments of the present application in detail with reference to the accompanying drawings. In the absence of conflict, the following embodiments and features therein may be combined with each other.

[0019] As electronic products like mobile phones place increasingly stringent material demands, traditional plastics like polycarbonate (PC) struggle to meet these high-performance requirements due to their low hardness and poor wear resistance. Polymethyl methacrylate (PMMA) + PC composites, treated with UV curing agents, have emerged to meet the market's dual demands for aesthetics and durability.

[0020] Although the existing UV hardening liquid surface treatment technology is widely used, as consumer electronics have increasingly higher requirements for materials, it also has some shortcomings in actual application. For example, the UV hardening liquid has poor water boiling resistance and is prone to cracking. During the processing process, the leveling property is not good enough, which easily produces rainbow patterns. The hardness and scratch resistance of the cured film layer are not enough, and it is easy to produce scratches.

[0021] To solve the above problems, an embodiment of the present application provides a UV hardening liquid, which is prepared from the following raw materials: a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an additive, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent, wherein the cage-type polysilsesquioxane oligomer has an acid bond structure.

[0022] Wherein, cage type polysilsesquioxane oligomer can be the oligomer of cage type polysilsesquioxane (polysilsesquioxane, POSS).The POSS structure is the inorganic kernel that the silicon oxygen skeleton that is alternately connected by Si-O forms, and its shape is as a " cage ", and its three-dimensional size is between 1-3nm, and wherein the distance between the Si atom is 0.5nm, and between the R group, distance is 1.5nm, belongs to nano compound.In the present application embodiment, cage type polysilsesquioxane oligomer has acid bond structure, can react with low-functionality polyurethane modified acrylate oligomer and nano hybrid modified acrylic resin by acid bond structure thus, thereby prepare ultraviolet hardening liquid

[0023] The low-functionality polyurethane-modified acrylate oligomer can be a polyurethane-modified acrylic resin, etc. Using a polyurethane-modified acrylate resin as the main resin can enhance the strength and elasticity of the film layer. The functionality of the low-functionality polyurethane-modified acrylate oligomer is generally less than or equal to 3 functional groups, which facilitates cross-linking with the cage-type polysilsesquioxane oligomer to form a network structure. This gives the cross-linked and cured film a certain toughness, prevents cracking in hot and humid environments, and enhances the adhesion and weather resistance of UV curing liquids to various substrates. Nano-hybrid modified acrylic resins can further increase the cross-linking density, thereby improving the surface hardness and wear resistance of the cross-linked and cured film layer.

[0024] The embodiment of the present application provides a kind of ultraviolet hardening liquid, and this ultraviolet hardening liquid utilizes the cage type polysilsesquioxane oligomer with acid bond structure, low functional group polyurethane modified acrylate oligomer and nano hybrid modified acrylic resin to react, and prepares ultraviolet hardening liquid.After utilizing this ultraviolet hardening liquid to solidify the material, it is possible to form a firm cross-linked network after the material is solidified, thereby being able to improve the hardness and temperature resistance of the material, and simultaneously it is also possible to reduce the surface energy, enhance the scratch resistance, wear resistance, chemical resistance, waterproof performance and friction resistance of the material surface, so that the film layer after cross-linking and curing has certain toughness. At the same time, this ultraviolet hardening liquid has low viscosity, and can be adjusted according to different processing techniques, is suitable for processing techniques such as spraying, curtain coating, roller coating, and has excellent leveling effect on different substrate surfaces, does not have defects such as orange peel, shrinkage cavity, sagging, irregular rainbow pattern, can achieve mirror leveling effect, and has no effect on optical properties. It can also greatly reduce the oxygen inhibition effect while ensuring the curing rate, thereby improving the curing rate and making the film layer have better scratch resistance, wear resistance, corrosion resistance and other properties.

[0025] In some embodiments, the UV curing liquid further comprises a low-functional polyester-modified acrylate oligomer, thereby further enhancing the adhesion of the UV curing liquid to various substrate surfaces.

[0026] For example, the low-functional polyester-modified acrylate oligomer can be a polyurethane-modified acrylic resin, etc. The functionality of the low-functional polyester-modified acrylate oligomer is generally less than or equal to 3 functional groups, which can further enhance the adhesion of the UV hardening liquid to the surfaces of various substrates, especially for plastic substrates.

[0027] In some embodiments, the content of the cage-type polysilsesquioxane oligomer is 20%-40%, for example, 20%, 25%, 30%, 40%, etc., by weight percentage; the content of the low-functionality polyurethane-modified acrylate oligomer is 5%-10%, for example, 5%, 7%, 9%, 10%, etc.; the content of the low-functionality polyester-modified acrylate oligomer is 5%-10%, for example, 5%, 7%, 8%, 10%, etc.; the content of the nano-hybrid modified acrylic resin is 5%-10%, for example, 5% , 7%, 9%, 10%, etc.; the content of auxiliary agent is 1%-3%, for example: 1%, 2%, 2.5%, 4%, etc.; the content of silane coupling agent is 1%-2%, for example: 1%, 1.5%, 2%, etc.; the content of free radical initiator is 1%-2%, for example: 1%, 1.5%, 2%, etc.; the content of cationic initiator is 1%-3%, for example: 1%, 1.5%, 2%, 3%, etc.; the content of solvent is 40%-60%, for example: 40%, 45%, 50%, 60%, etc.

[0028] Since UV hardening liquid is mainly composed of cage-type polysilsesquioxane oligomers and solvents, its proportion is relatively high; low-functionality polyurethane modified acrylate oligomers, low-functionality polyester modified acrylate oligomers, and nano-hybrid modified acrylic resins all mainly react with cage-type polysilsesquioxane oligomers, thereby forming a strong cross-linked network after the material is cured, so its proportion is generally less than that of cage-type polysilsesquioxane oligomers and solvents; additives, silane coupling agents, free radical initiators and cationic initiators mainly play an auxiliary role, so their proportion is relatively low.

[0029] Exemplarily, the proportion of cage-type polysilsesquioxane oligomers in the UV hardening liquid can be 25%, the proportion of low-functionality polyurethane modified acrylate oligomers in the UV hardening liquid can be 8%, the proportion of low-functionality polyester modified acrylate oligomers in the UV hardening liquid can be 7%, the proportion of nano-hybrid modified acrylic resin in the UV hardening liquid can be 10%, the proportion of additives in the UV hardening liquid can be 1%, the proportion of silane coupling agents in the UV hardening liquid can be 1%, the proportion of free radical initiators in the UV hardening liquid can be 1%, the proportion of cationic initiators in the UV hardening liquid can be 2%, and the proportion of solvents in the UV hardening liquid can be 45%.

[0030] In some embodiments, the nano-hybrid modified acrylic resin may be a high-functionality nano-hybrid modified acrylic resin, which can further increase the cross-linking density and enhance the surface hardness and wear resistance of the film layer.

[0031] For example, the functionality of the high-functionality nano-hybrid modified acrylic resin is generally greater than or equal to 3 functional groups, thereby further increasing the cross-linking density and improving the surface hardness and wear resistance of the film layer.

[0032] In some embodiments, the cage polysilsesquioxane oligomer may be any one or more of a fluorine-modified cage polysilsesquioxane oligomer, a cage polysilsesquioxane oligomer having an epoxy group on the side chain, a cage polysilsesquioxane oligomer having an acryloxypropyl group on the side chain, and a cage polysilsesquioxane oligomer having a methacryloyloxypropyl group on the side chain.

[0033] Wherein, the above-mentioned cage-type polysilsesquioxane oligomers all have an acid bond structure.

[0034] like Figure 1 As shown, exemplary, a cage-type polysilsesquioxane oligomer can be reacted with a silane coupling agent comprising an acid bond structure and a silane coupling agent comprising a fluorine-based structure to prepare a fluorine-modified cage-type silsesquioxane oligomer (MA-F-POSS). The ultraviolet curing solution provided by the application introduces a fluorine-modified cage-type silsesquioxane oligomer having an acid bond, so that a strong cross-linked network can be formed after the material is cured, thereby improving the hardness and temperature resistance of the material, while also being able to reduce the surface energy and enhance the scratch resistance, wear resistance, chemical resistance and water resistance of the material surface.

[0035] It should be noted that the cage-type polysilsesquioxane oligomer can be an oligomer that can provide an acid bond structure and a POSS structure. Preferably, the best effect is achieved when a fluorine-modified cage-type silsesquioxane oligomer is selected, so that the UV hardening liquid can further improve the hardness and temperature resistance of the material, while also reducing the surface energy and enhancing the scratch resistance, wear resistance, chemical resistance and waterproof properties of the material surface.

[0036] In some embodiments, the low-functionality polyurethane-modified acrylate oligomer can be selected from any one or more of Sartomer's CN983NS, Sartomer's CN996NS, Kunshan Castel's 9537, Changxing Materials' 6151, Changxing Materials' DR-U084, Changxing Materials' DR-U299, Changxing Materials' DR-U379, Changxing Materials' DR-U384, and Changxing Materials' DR-U388.

[0037] For example, the low-functionality polyurethane-modified acrylate oligomers provided above can be cross-linked with cage-type polysilsesquioxane oligomers to form a network structure, so that the cross-linked and cured film layer has a certain toughness and can not crack in a hot and humid environment. It can also enhance the adhesion and weather resistance of the UV curing liquid to various substrates.

[0038] For example, Sartomer's CN983NS is a low-molecular-weight oligomer with a fast curing reaction and high crosslink density. Sartomer's CN9996NS, for example, offers excellent mechanical properties and a fast curing speed, providing high strength, hardness, and good wear resistance. It also exhibits excellent water resistance, acid and alkali resistance to polar solvents, and maintains stability and performance in damp or humid environments. Sartomer's CN9996NS, for example, exhibits yellowing resistance, excellent weather resistance, strong adhesion, and excellent flexibility.

[0039] In some embodiments, the low-functionality polyester-modified acrylate oligomer can be selected from any one or more of Eternal Materials' 6371, Eternal Materials' 6372, Amerisource's HR6100, Amerisource's HR6200, Amerisource's PS4500, Amerisource's PS4040, Amerisource's PS610, Sartomer's CN2254NS, Sartomer's CN2303, Sartomer's CN2303, Sartomer's CN293, Sartomer's CN750, Sartomer's CN790, Sartomer's CN8008NS, and Sartomer's CN8201 NS.

[0040] For example, the low-functionality polyester-modified acrylate oligomers provided above can further enhance the adhesion of the UV curing solution to the surface of the plastic substrate.

[0041] For example, Sartomer's CN2254NS offers excellent fast curing, high gloss, and abrasion resistance, as well as chemical resistance, maintaining its performance and structural stability without being damaged or corroded by chemicals. Sartomer's CN8021NS, for example, offers excellent ink-water balance, excellent pigment dispersion, good flexibility, low shrinkage, and excellent water resistance.

[0042] In some embodiments, the nano-hybrid modified acrylic resin can be any one or more of Haohui New Materials' CR91000, Haohui New Materials' CR91093, Haohui New Materials' CR90223, Haohui New Materials' HU280, Lankelu's L-6902X, Lankelu's L-6901, and Lankelu's L-6902.

[0043] For example, the low-functionality polyester-modified acrylate oligomers provided above can further increase the cross-linking density and enhance the surface hardness and wear resistance of the film layer.

[0044] For example, Haohui New Materials' CR91000 coating has excellent wear resistance, chemical resistance, scratch resistance, surface hardness, and excellent fingerprint resistance after curing. Haohui New Materials' CR91093 coating has excellent wear resistance, chemical resistance, scratch resistance, surface hardness, and excellent fingerprint resistance after curing.

[0045] In some embodiments, the additive may be any one or more of BYK333, BYK3550, BYK302, BYK3500, BYK3530, BYK3570, Deqian 407, Deqian 410, Deqian 411, Deqian 432, Deqian 435, and Deqian 455.

[0046] For example, the above-mentioned additives may be leveling additives, which can improve the appearance of the UV hardening liquid and make it smooth and flat.

[0047] In some embodiments, the silane coupling agent can be selected from any one or more of γ-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloyloxypropyltri(methoxyethoxy)silane, methacryloxypropyltri(dimethylsiloxy)silane, γ-(acryloyloxy)propyltrimethoxysilane, γ-(acryloyloxy)propyltriethoxysilane, allyltri(trimethylsiloxy)silane, 1,3-bis(3-methacryloyloxypropyl)tetrakis(trimethylsiloxy)disiloxane, and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0048] Exemplarily, the above silane coupling agents can all improve the adhesion of the substrate surface.

[0049] In some embodiments, the free radical initiator can be any one or more of 1173, 184, TPO, TPO-L, 127, 369, I TX, BDK, 819, 754, 380, and BMF.

[0050] Illustratively, the above-mentioned free radical initiators can all initiate the polymerization of cage-type polysilsesquioxane oligomers, low-functionality polyurethane-modified acrylate oligomers, and nano-hybrid-modified acrylic resins to form a cross-linked network, while reducing the shrinkage of the system.

[0051] In some embodiments, the cationic initiator can be selected from ANTHRACUREUVS-1331, ANTHRACUREUVS-1101, Easep i 6992, Easep i 1176, Easep i 250, U-160 of Shenzhen Youyang, U-180 of Shenzhen Youyang, U-261 of Shenzhen Youyang, U-1600L of Shenzhen Youyang, U-2500 of Shenzhen Youyang, UVI 6976 of Nantong Synasia New Materials, KIP100F of Nantong Synasia New Materials, KIP125 of Nantong Synasia New Materials, KIP150 of Nantong Synasia New Materials, CP I-100P of Sanyo Chemical, CP I-101A of Sanyo Chemical, CP I 200K of Sanyo Chemical, CP I210S of Sanyo Chemical, CP I 310B of Sanyo Chemical, CP Any one or more of I-410S and I K-1 produced by Sanyo Chemical.

[0052] Exemplarily, the above cationic initiators can all initiate cationic polymerization reactions, thereby initiating polymerization of cage-type polysilsesquioxane oligomers, low-functionality polyurethane-modified acrylate oligomers, and nano-hybrid-modified acrylic resins to form a cross-linked network, while reducing the shrinkage of the system.

[0053] For example, ANTHRACUREUVS-1331 is 9,10-dibutoxyanthracene, and its corresponding CAS Registry Number is 76275-14-4. ANTHRACUREUVS-1101 is 9,10-diethoxyanthracene, and its corresponding CAS Registry Number is 68818-86-0. Easep i 6992 is a mixed triarylsulfonium salt, and its corresponding CAS Registry Numbers are 68156-13-8, 74227-35-3 and 108-32-7. Easep i 1176 is a liquid phenyl hexafluoroantimonate sulfonium salt mixed with a monosalt and a disalt, and its corresponding CAS Registry Numbers are 8945-2-37-9 and 71449-78-0.

[0054] In some embodiments, the solvent can be selected from any one or more of ethanol, isopropanol, isobutanol, n-butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide, methyl ethyl ketone, dimethyl sulfoxide, butyl acetate, N-methylpyrrolidone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol.

[0055] Illustratively, the above solvents can all be used to reduce the viscosity of the system.

[0056] It should be noted that the multiple different types of cage-type polysilsesquioxane oligomers, low-functionality polyurethane-modified acrylate oligomers, low-functionality polyester-modified acrylate oligomers, nano-hybrid modified acrylic resins, additives, silane coupling agents, free radical initiators, cationic initiators, and solvents exemplified above generally have different molecular weights, functional groups, or hardness, but all belong to the same category of substances.

[0057] See also Figure 2 , Figure 2 1 is a flow chart of an embodiment of a method for preparing a UV hardening solution provided in an embodiment of the present application, wherein the preparation method comprises: step S101 and step S102.

[0058] Step S101: providing a caged polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an auxiliary agent, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent, wherein the caged polysilsesquioxane oligomer has an acid bond structure.

[0059] It should be noted that the specific examples of the cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin, additives, silane coupling agent, free radical initiator, cationic initiator and solvent can be referred to the above examples and will not be repeated here.

[0060] Step S102: preparing a UV curing solution by using cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin, additives, silane coupling agent, free radical initiator, cationic initiator, and solvent.

[0061] The present application embodiment provides a kind of preparation method of ultraviolet hardening liquid, the preparation method of this ultraviolet hardening liquid utilizes the cage type polysilsesquioxane oligomer with acid bond structure, low functional group polyurethane modified acrylate oligomer and nano hybrid modified acrylic resin to react, prepare ultraviolet hardening liquid.After utilizing this ultraviolet hardening liquid to solidify material, it is possible to form a firm cross-linked network after material solidification, thereby can improve material hardness and temperature resistance, simultaneously can also reduce surface energy, strengthen the scratch resistance, wear resistance, chemical resistance, waterproof performance and friction resistance of material surface, make the rete after cross-linking and curing have certain toughness. Meanwhile, this ultraviolet hardening liquid has low viscosity, and can be adjusted according to different processing techniques, is applicable to processing techniques such as spraying, shower coating, roller coating, all has excellent leveling effect on different substrate surfaces, does not have defects such as orange peel, shrinkage cavity, sagging, irregular rainbow pattern, can reach mirror leveling effect, has no influence on optical performance. It can also greatly reduce the oxygen inhibition effect while ensuring the curing rate, thereby improving the curing rate and making the film layer have better scratch resistance, wear resistance, corrosion resistance and other properties.

[0062] In some embodiments, in step S102, a UV curing solution is prepared by using a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an additive, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent. The process may include: sub-steps S1021 and S1022. Figure 3 shown.

[0063] S1021: adding a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin and a solvent into a container, and stirring and mixing them uniformly based on a first stirring parameter.

[0064] S1022: Adding an auxiliary agent, a silane coupling agent, a free radical initiator and a cationic initiator into a container, stirring and mixing them uniformly based on a second stirring parameter, letting them stand and filtering to obtain a filtered UV hardening liquid.

[0065] Specifically, cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin and solvent are added into a container, and stirred and mixed uniformly based on a first stirring parameter, so that the above materials are completely dispersed and dissolved.

[0066] Exemplarily, the first stirring parameter includes a first stirring temperature, a first stirring speed, and a first stirring duration. The first stirring speed can be 600 r / min, and the first stirring temperature can be 21°-25°. Preferably, the first stirring temperature can be 23°, and the first stirring temperature is the liquid temperature in the container during stirring. The first stirring duration is 60 minutes. When stirring and mixing, the cage-type polysilsesquioxane oligomer, the low-functionality polyurethane-modified acrylate oligomer, the nano-hybrid modified acrylic resin, and the solvent can be added to the container and slowly stirred at a speed of 600 r / min for 60 minutes. The liquid temperature in the above-mentioned maintenance container is between 21°-25°.

[0067] Specifically, the auxiliary agent, the silane coupling agent, the free radical initiator and the cationic initiator are added into a container, stirred and mixed uniformly based on the second stirring parameter, allowed to stand and filtered to obtain a filtered UV hardening solution.

[0068] Exemplarily, the second stirring parameter includes a second stirring temperature, a second stirring speed, and a second stirring time. The second stirring temperature can be 21°-25°, and the second stirring time can be 60 minutes. Preferably, the second stirring temperature can be 23°, the second stirring temperature is the liquid temperature in the container during stirring, the second stirring speed is 1000r / min, and the second stirring time is 60 minutes. When stirring and mixing evenly, the speed can be adjusted to 1000r / min, and then the auxiliary agent, silane coupling agent, free radical initiator and cationic initiator are slowly added, and stirring is continued for 60 minutes, and the liquid temperature in the container is maintained between 21°-25° during the process. After stirring is completed, let it stand for 30 minutes, and then filter under pressure with a 0.22μm organic filter to obtain a slightly white and transparent optical grade UV hardening liquid.

[0069] The preparation method and performance of the UV hardening solution of the present application are described below through specific examples.

[0070] Example 1:

[0071] (1) Add 55g of butyl acetate, 25g of homemade fluorine-modified caged silsesquioxane oligomer, 5g of Sartomer CN983NS, 5g of Changxing Materials 6371, and 5g of Haohui New Materials CR91000 into a container and slowly stir at a speed of 600r / min for 60 minutes to completely dissolve the system and obtain a uniform solution. During the process, the liquid temperature in the container is maintained at 23°C.

[0072] (2) Adjust the speed to 1000 r / min, then slowly add 1 g of γ-(methacryloyloxy)propyltrimethoxysilane, 1 g of BYK333, 2 g of Easepi 1176, and 1 g of 184, and continue stirring for 60 minutes. During the process, maintain the liquid temperature in the container at 23 °C.

[0073] (3) After stirring, let it stand for 30 minutes, then filter it under pressure with a 0.22μm organic filter to obtain a slightly white and transparent optical grade UV hardening liquid.

[0074] Therefore, in Example 1, the amount of cage-type polysilsesquioxane oligomer accounts for 25%, the amount of low-functionality polyurethane modified acrylate oligomer accounts for 5%, the amount of low-functionality polyester modified acrylate oligomer accounts for 5%, the amount of nano-hybrid modified acrylic resin accounts for 5%, the amount of auxiliary agent accounts for 1%, the amount of silane coupling agent accounts for 1%, the amount of free radical initiator accounts for 1%, the amount of cationic initiator accounts for 2%, and the amount of solvent accounts for 55%.

[0075] Example 2:

[0076] (1) Add 40g of n-butanol, 40g of caged silsesquioxane oligomer with epoxy groups on the side chain, 5g of CN996NS from Sartomer, 5g of HR6100 from Meiyuan, and 5g of CR91093 from Haohui New Materials into a container and slowly stir at a speed of 600r / min for 60 minutes to completely dissolve the system and obtain a uniform solution. During the process, the liquid temperature in the container is maintained at 23°C.

[0077] (2) Adjust the speed to 1000 r / min, then slowly add 1 g of vinyl trimethoxysilane, 1 g of BYK3550, 1 g of Easepi 6992, and 1 g of TPO, and continue stirring for 60 minutes. During the process, maintain the liquid temperature in the container at 23 °C.

[0078] (3) After stirring, let it stand for 30 minutes, then filter it under pressure with a 0.22μm organic filter to obtain a slightly white and transparent optical grade UV hardening liquid.

[0079] Therefore, in Example 2, the amount of cage-type polysilsesquioxane oligomer accounts for 40%, the amount of low-functionality polyurethane modified acrylate oligomer accounts for 5%, the amount of low-functionality polyester modified acrylate oligomer accounts for 5%, the amount of nano-hybrid modified acrylic resin accounts for 5%, the amount of auxiliary agent accounts for 1%, the amount of silane coupling agent accounts for 2%, the amount of free radical initiator accounts for 1%, the amount of cationic initiator accounts for 1%, and the amount of solvent accounts for 40%.

[0080] Example 3:

[0081] (1) Add 60g of N,N-dimethylformamide, 20g of caged silsesquioxane structure oligomer with acryloxypropyl group on the side chain, 5g of 9537 from Kunshan Kaster, 5g of HR6100 from Meiyuan, and 5g of L-6902X from Lankelu into a container, and stir slowly at a speed of 600r / min for 60 minutes to completely dissolve the system and obtain a uniform solution. During the process, maintain the liquid temperature in the container at 23°C.

[0082] (2) Adjust the speed to 1000 r / min, then slowly add 1g of vinyltrimethoxysilane, 1g of BYK3530, 1g of Shenzhen Youyang's U-180, and 2g of BDK, and continue stirring for 60 minutes. During the process, maintain the liquid temperature in the container at 23°C.

[0083] (3) After stirring, let it stand for 30 minutes, then filter it under pressure with a 0.22μm organic filter to obtain a slightly white and transparent optical grade UV hardening liquid.

[0084] Therefore, in Example 3, the amount of cage-type polysilsesquioxane oligomer accounts for 20%, the amount of low-functionality polyurethane modified acrylate oligomer accounts for 5%, the amount of low-functionality polyester modified acrylate oligomer accounts for 5%, the amount of nano-hybrid modified acrylic resin accounts for 5%, the amount of auxiliary agent accounts for 1%, the amount of silane coupling agent accounts for 1%, the amount of free radical initiator accounts for 2%, the amount of cationic initiator accounts for 1%, and the amount of solvent accounts for 60%.

[0085] Example 4:

[0086] (1) 41 g of methyl isobutyl ketone, 21 g of caged silsesquioxane oligomer with methacryloyloxypropyl group on the side chain, 10 g of DR-U384 of Changxing Materials, 10 g of CN750 of Sartomer, and 10 g of L-6901 of Lancolu were added to a container and slowly stirred at a speed of 600 r / min for 60 minutes to completely dissolve the system and obtain a uniform solution. During the process, the liquid temperature in the container was maintained at 23°C.

[0087] (2) Adjust the speed to 1000 r / min, then slowly add 1g of 3-methacryloyloxypropyl tris(methoxyethoxy)silane, 3g of Deqian 455, 3g of Shenzhen Youyang's U-261, and 1g of 819, and continue stirring for 60 minutes. During the process, maintain the liquid temperature in the container at 23°C.

[0088] (3) After stirring, let it stand for 30 minutes, then filter it under pressure with a 0.22μm organic filter to obtain a slightly white and transparent optical grade UV hardening liquid.

[0089] Therefore, in Example 4, the amount of cage-type polysilsesquioxane oligomer accounts for 21%, the amount of low-functionality polyurethane modified acrylate oligomer accounts for 10%, the amount of low-functionality polyester modified acrylate oligomer accounts for 10%, the amount of nano-hybrid modified acrylic resin accounts for 10%, the amount of auxiliary agent accounts for 3%, the amount of silane coupling agent accounts for 1%, the amount of free radical initiator accounts for 1%, the amount of cationic initiator accounts for 3%, and the amount of solvent accounts for 41%.

[0090] The UV hardening solution provided in the above embodiment was used for performance testing, and the performance test experimental data are shown in Table 1. The specification values ​​in Table 1 are the specification values ​​of UV hardening solution in the related art, and the specification values ​​are used for comparison with the UV hardening solution provided in the above embodiment to confirm whether the UV hardening solution provided in the above embodiment meets the specification values.

[0091] Table 1

[0092]

[0093]

[0094] The test methods and test conditions corresponding to the above test items are as follows:

[0095] Appearance test method: visual inspection.

[0096] Viscosity test method: GB T 2794-2022.

[0097] Solid content test method: GB 1725-1979.

[0098] Test conditions for hardness after curing: 1. Test surface: hardened surface; 2. Load: 1000g; 3. Test angle: 45°; 4. Sliding distance: 5mm.

[0099] Test method for flow coating surface condition: flow coating and hardening.

[0100] Water contact angle test method: GB T 30693-2014.

[0101] Transmittance testing method: haze meter.

[0102] Yellowness testing method: haze meter.

[0103] Haze testing method: haze meter.

[0104] Testing method of boiling water + 100-grid test: 1. Boil in 80℃ water for 30 minutes; 2. Perform 100-grid test.

[0105] High temperature and high humidity test method: 1. 240h@60℃, 90%RH; 2. 100-grid test.

[0106] Adhesion test method: 100-grid test.

[0107] Artificial sweat resistance test method: 1. Wrapping method: 20ml artificial sweat, pH value 4.5-4.7, tightly wrapped with dust-free cloth, sealed with sealing tape, and placed in a high temperature and high humidity environment of 55±1℃ / 93±2%RH for 48 hours; 2. After returning to normal temperature for 2 hours, compare the appearance with the normal sample; 3. Conduct a 100-grid test.

[0108] Salt spray resistance test method: 1. Saturation chamber temperature: 35±1°C, 95% water (deionized or purified), 5% sodium chloride, pH=6.5-7.2, air pressure: 1±0.3 kg²; 2. Duration: 24 hours. 3. Remove and rinse with clean water, bake at 50-60°C for 30 minutes, and store in natural conditions for at least 2 hours. Observe and compare the appearance with a normal sample; 4. Perform a 100-grid test.

[0109] Test conditions for steel wool friction: 1. Test surface: hard surface; 2. Steel wool: 0000#; 3. Test head area: 2cm*2cm; 4. Vertical force: 500g; Friction method: back and forth as one time.

[0110] Rubber friction test conditions: 1. Test surface: hardened surface; 2. Rubber: minoan-MB006004; 3. Load: 1000g; 4. Speed: 60 cycles / min; 5. Stroke: 40mm (adjustable according to product size)

[0111] Alcohol friction test conditions: 1. Test surface: hard surface; 2. Alcohol concentration: ≥99.5%; 3. Test head area: 1cm2; 4. Load: 500g; 5. Speed: 40 cycles / min; 6. Stroke: 40mm (can be adjusted appropriately according to product size).

[0112] The UV curing solution provided in this application forms a strong cross-linked network upon curing, thereby improving the material's hardness and temperature resistance. It also reduces surface energy, enhancing the material's surface resistance to scratching, abrasion, chemicals, water, and friction, resulting in a certain toughness in the cross-linked film. This can be demonstrated through post-curing hardness, water resistance testing, coating surface condition, friction testing, and resistance to artificial sweat and salt spray.

[0113] As can be seen from Table 1, the appearance of the UV hardening liquid provided in the embodiment of the present application meets the standard value of a slightly white transparent liquid; the viscosity meets the standard value of 5-11 mPa.s; the solid content meets the standard value of 40-50%; the hardness after curing meets the standard value of greater than or equal to 2H; the surface state of the coating meets the standard value of a smooth surface and no rainbow lines; the water contact angle meets the standard value of 95-105°; the transmittance meets the standard value of greater than or equal to 98%; the yellowness meets the standard value of less than or equal to 0.3; the haze meets the standard value of less than or equal to 0.1; the water boiling + hundred grid test meets the standard value of greater than or equal to 4B; the high temperature and high humidity test meets the standard value of greater than or equal to 4B; the adhesion test meets the standard value of greater than or equal to 4B; the artificial sweat resistance test meets the standard value of greater than or equal to 4B; the salt spray resistance test meets the standard value of greater than or equal to 4B; the steel wool friction test meets the standard value of greater than or equal to 3000 times; the rubber friction test meets the standard value of greater than or equal to 5000 times; and the alcohol friction test meets the standard value of greater than or equal to 5000 times. It can be seen that the UV hardening liquid provided in the present application can form a strong cross-linked network after the material is cured, thereby improving the hardness and temperature resistance of the material. At the same time, it can also reduce the surface energy, enhance the scratch resistance, wear resistance, chemical resistance, waterproof performance and friction resistance of the material surface, so that the cross-linked and cured film layer has a certain toughness.

[0114] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present application, and such modifications or substitutions should be included in the scope of protection of the present application. Therefore, the scope of protection of the present application should be based on the scope of protection of the claims.

Claims

1. A UV hardening liquid, It is characterized in that The ultraviolet curing liquid is prepared from the following raw materials: cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin, auxiliary agent, silane coupling agent, free radical initiator, cationic initiator, and solvent, wherein the cage-type polysilsesquioxane oligomer has an acid bond structure.

2. The UV hardening solution according to claim 1, It is characterized in that The ultraviolet curing liquid also includes low-functional polyester-modified acrylate oligomer.

3. The UV hardening solution according to claim 2, It is characterized in that In terms of weight percentage, the content of the cage-type polysilsesquioxane oligomer is 20%-40%, the content of the low-functional group polyurethane modified acrylate oligomer is 5%-10%, the content of the low-functional group polyester modified acrylate oligomer is 5%-10%, the content of the nano-hybrid modified acrylic resin is 5%-10%, the content of the auxiliary agent is 1%-3%, the content of the silane coupling agent is 1%-2%, the content of the free radical initiator is 1%-2%, the content of the cationic initiator is 1%-3%, and the content of the solvent is 40%-60%.

4. The UV hardening solution according to claim 1, It is characterized in that The nano hybrid modified acrylic resin is a high-functional group nano hybrid modified acrylic resin.

5. The UV hardening solution according to claim 1, It is characterized in that The cage polysilsesquioxane oligomer is at least one of a fluorine-modified cage polysilsesquioxane oligomer, a cage polysilsesquioxane oligomer having an epoxy group on the side chain, a cage polysilsesquioxane structure oligomer having an acryloxypropyl group on the side chain, and a cage polysilsesquioxane oligomer having a methacryloxypropyl group on the side chain.

6. The UV hardening solution according to claim 1, It is characterized in that The low-functional polyurethane modified acrylate oligomer is at least one of CN983NS of Sartomer, CN996NS of Sartomer, 9537 of Kunshan Custer, 6151 of Changxing Materials, DR-U084 of Changxing Materials, DR-U299 of Changxing Materials, DR-U379 of Changxing Materials, DR-U384 of Changxing Materials, and DR-U388 of Changxing Materials.

7. The UV hardening solution according to claim 2, It is characterized in that The low-functional polyester modified acrylate oligomer is at least one of Changxing Material's 6371, Changxing Material's 6372, Meyuan's HR6100, Meyuan's HR6200, Meyuan's PS4500, Meyuan's PS4040, Meyuan's PS610, Sartomer's CN2254NS, Sartomer's CN2303, Sartomer's CN2303, Sartomer's CN293, Sartomer's CN750, Sartomer's CN790, Sartomer's CN8008NS, and Sartomer's CN8201 NS.

8. The UV hardening solution according to claim 1, It is characterized in that The nano-hybrid modified acrylic resin is at least one of CR91000, CR91093, CR90223, HU280, L-6902X, L-6901 and L-6902 of Haohui New Materials.

9. The UV hardening solution according to claim 1, It is characterized in that The auxiliary agent is at least one of BYK333, BYK3550, BYK302, BYK3500, BYK3530, BYK3570, Deqian 407, Deqian 410, Deqian 411, Deqian 432, Deqian 435, and Deqian 455.

10. The UV hardening solution according to claim 1, It is characterized in that The silane coupling agent is at least one of γ-(methacryloxy)propyl trimethoxysilane, vinyl trimethoxysilane, vinyl tri(2-methoxyethoxy)silane, vinyl triethoxysilane, γ-(methacryloxy)propyl triethoxysilane, methacryloxymethyl triethoxysilane, 3-methacryloxypropyl tri(methoxyethoxy)silane, methacryloxypropyl tri(dimethylsiloxy)silane, γ-(acryloxy)propyl trimethoxysilane, γ-(acryloxy)propyl triethoxysilane, allyl tri(trimethylsiloxy)silane, 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, and N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane.

11. The UV hardening solution according to claim 1, It is characterized in that The free radical initiator is at least one of 1173, 184, TPO, TPO-L, 127, 369, ITX, BDK, 819, 754, 380, and BMF.

12. The UV hardening solution according to claim 1, It is characterized in that The cationic initiator is ANTHRACUREUVS-1331, ANTHRACUREUVS-1101, Easepi 6992, Easepi1176, Easepi 250, U-160 of Shenzhen Youyang, U-180 of Shenzhen Youyang, U-261 of Shenzhen Youyang, U-1600L of Shenzhen Youyang, U-2500 of Shenzhen Youyang, UVI 6976 of Nantong Synasia New Materials, KIP100F of Nantong Synasia New Materials, KIP125 of Nantong Synasia New Materials, KIP150 of Nantong Synasia New Materials, CPI-100P of Sanyo Chemical, CPI-101A of Sanyo Chemical, CPI 200K of Sanyo Chemical, CPI 210S of Sanyo Chemical, CPI At least one of 310B, CPI-410S of Sanyo Chemical, and IK-1 of Sanyo Chemical.

13. The UV hardening solution according to claim 1, It is characterized in that The solvent is at least one of ethanol, isopropanol, isobutanol, n-butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide, methyl ethyl ketone, dimethyl sulfoxide, butyl acetate, N-methylpyrrolidone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol.

14. A method for preparing a UV hardening solution, It is characterized in that The method comprises: Provide a cage-type polysilsesquioxane oligomer, a low-functionality polyurethane-modified acrylate oligomer, a nano-hybrid modified acrylic resin, an auxiliary agent, a silane coupling agent, a free radical initiator, a cationic initiator, and a solvent, wherein the cage-type polysilsesquioxane oligomer has an acid bond structure; The ultraviolet hardening liquid is prepared by using the cage-type polysilsesquioxane oligomer, low-functionality polyurethane-modified acrylate oligomer, nano-hybrid modified acrylic resin, auxiliary agent, silane coupling agent, free radical initiator, cationic initiator and solvent.

15. The preparation method according to claim 14, It is characterized in that The method of preparing the ultraviolet hardening liquid by using the cage-type polysilsesquioxane oligomer, the low-functionality polyurethane-modified acrylate oligomer, the nano-hybrid modified acrylic resin, the auxiliary agent, the silane coupling agent, the free radical initiator, the cationic initiator, and the solvent comprises: Adding the cage-type polysilsesquioxane oligomer, the low-functionality polyurethane-modified acrylate oligomer, the nano-hybrid modified acrylic resin and the solvent into a container, and stirring and mixing them uniformly based on a first stirring parameter; The auxiliary agent, silane coupling agent, free radical initiator and cationic initiator are added into the container, and stirred and mixed evenly based on the second stirring parameter, and then allowed to stand and filtered to obtain a filtered UV hardening liquid.

16. The preparation method according to claim 15, It is characterized in that The first stirring parameters include a first stirring temperature, a first stirring speed and a first stirring time, the first stirring temperature is 21°-25°, the first stirring speed is 600r / min, and the first stirring time is 60 minutes; the second stirring parameters include a second stirring temperature, a second stirring speed and a second stirring time, the second stirring temperature is 21°-25°, the second stirring speed is 1000r / min, and the second stirring time is 60 minutes.

Images