Uv light resistant agent, method for producing the same, resin mixture, and use thereof

Abstract

The application discloses a high-curing ultraviolet resistant agent, a preparation method thereof, a resin mixture and application of the high-curing ultraviolet resistant agent. The high-curing ultraviolet resistant agent comprises a hydroquinone group, two benzotriazole groups located at ortho or meta positions of the hydroquinone group, one triazine group connected with the benzotriazole groups, and a first substituent group located on the triazine group. The high-curing ultraviolet resistant agent disclosed by the application can form intrinsic hydrogen bonds and chelate rings because the nitrogen in the benzotriazole group is close to the hydroxyl group on the hydroquinone group. After absorbing ultraviolet light, the molecule is subjected to thermal vibration, the internal hydrogen bonds are broken, the chelate ring is opened, and the ultraviolet light energy is converted into heat energy and released. The hydroxyl group on the opened chelate ring can form hydrogen bonds with the surface of a substrate coated with the high-curing ultraviolet resistant agent, thereby improving the adhesion of the high-curing ultraviolet resistant agent. The triazine group absorbs ultraviolet light and enhances the ultraviolet resistance effect. The first substituent group improves the flexibility of the whole molecule.

Description

Technical Field

[0001] This invention relates to the field of optical materials, and more particularly to highly curable UV stabilizers and their preparation methods, resin mixtures and their applications. Background Technology

[0002] Existing resin mixtures are prone to yellowing during the curing process, with a significant degree of yellowing. During light curing, the curing process is slow, the curing effect is poor, and adhesion is difficult, greatly affecting the manufacturing process and yield of optical products. For resin mixtures containing commercially available UV stabilizers, their effectiveness is limited because these stabilizers hardly participate in crosslinking during the curing process, thus limiting their dosage. Summary of the Invention

[0003] In view of this, the present invention proposes a high-curing UV-resistant agent, a resin mixture and its application, aiming to achieve high UV resistance while achieving efficient curing.

[0004] The first aspect of the present invention provides a high-curing UV stabilizer comprising: a hydroquinone group; two benzotriazole groups located at the ortho or meta position of the hydroquinone group; a triazine group connected to the benzotriazole group; and a first substituent group located on the triazine group.

[0005] As can be seen from the above technical solution, the high-curing UV stabilizer proposed in this invention achieves effective UV protection through the combination of benzotriazole and hydroquinone groups, while the triazine group provides auxiliary UV protection. The nitrogen in the benzotriazole group is close to the hydroxyl group on the hydroquinone group, allowing for intrinsic hydrogen bonding and the formation of a chelate ring. Upon absorbing UV light, the molecule undergoes thermal vibration, breaking the internal hydrogen bonds and opening the chelate ring, releasing UV energy as heat. Furthermore, the benzotriazole group absorbs wavelengths between 300 and 400 nm, but does not absorb blue light (450-490 nm) or even longer wavelengths of natural light; therefore, the high-curing UV stabilizer itself does not color and is less prone to yellowing. The hydroxyl groups on the opened chelate ring can form hydrogen bonds with the substrate coated with the high-curing UV stabilizer, improving its adhesion. The triazine group has a high electron density, allowing it to absorb and be excited by UV light, thus enhancing the overall UV protection performance of the molecule. The first substituent group attached to the triazine group increases the molecular chain length and stress absorption capacity of the high-curing UV stabilizer, thereby improving the overall flexibility of the molecule.

[0006] A second aspect of the present invention provides a resin mixture comprising: a diluent; a high-curing UV-resistant agent as described in the foregoing examples; a photoinitiator; wherein the amount of the diluent is (30% to 90%) of the total formulation mass, the amount of the high-curing UV-resistant agent is (5% to 69%) of the total formulation mass, and the amount of the photoinitiator is (0.1% to 5%) of the total formulation mass.

[0007] A third aspect of the invention provides for the application of a resin mixture in adhesives, filters, display materials, or UV-resistant coatings.

[0008] A fourth aspect of this invention provides a method for preparing a highly curable UV stabilizer, comprising the following steps:

[0009] Compound c is generated by reacting compound a with compound b;

[0010] The structural formula of compound a is: ;

[0011] The structural formula of compound b is: ;

[0012] The structural formula of compound c is: ;

[0013] Compound c is used to react with compound d to generate compound e;

[0014] The structural formula of compound d is: ;

[0015] The structural formula of compound e is: ;

[0016] Compound e is used to react with compound f to generate compound g;

[0017] The structural formula of compound f is: ;

[0018] The structural formula of compound g is:

[0019] ;

[0020] Compound i is generated by reacting compound g with compound h.

[0021] The structural formula of compound h is: ;

[0022] The structural formula of compound i is:

[0023] ;

[0024] Compound i and compound j are used to generate compound k;

[0025] The structural formula of compound j is: ;

[0026] The structural formula of compound k is:

[0027]

[0028] The high-curing UV stabilizer is generated using the compound k.

[0029] The structural formula of the high-curing UV-resistant agent is:

[0030] .

[0031] The fifth aspect of this invention discloses a method for preparing a highly curable UV stabilizer, comprising the following steps:

[0032] Compound c is generated by reacting compound a with compound b;

[0033] The structural formula of compound a is: ;

[0034] The structural formula of compound b is: ;

[0035] The structural formula of compound c is: ;

[0036] Compound c is used to react with compound d to generate compound e;

[0037] The structural formula of compound d is: ;

[0038] The structural formula of compound e is: ;

[0039] Compound e is used to react with compound f to generate compound g;

[0040] The structural formula of compound f is: ;

[0041] The structural formula of compound g is:

[0042] ;

[0043] Compound i is generated by reacting compound g with compound h.

[0044] The structural formula of compound h is: ;

[0045] The structural formula of compound i is:

[0046] ;

[0047] Compound i and compound j are used to generate compound k;

[0048] The structural formula of compound j is: ;

[0049] The structural formula of compound k is:

[0050] ;

[0051] The high-curing UV stabilizer is generated using the compound k.

[0052] The structural formula of the high-curing UV-resistant agent is:

[0053] .

[0054] The sixth aspect of this invention discloses a method for preparing a highly curable UV stabilizer, comprising the following steps:

[0055] Compound c is generated by reacting compound a with compound b;

[0056] The structural formula of compound a is: ;

[0057] The structural formula of compound b is: ;

[0058] The structural formula of compound c is: ;

[0059] Compound c is used to react with compound d to generate compound e;

[0060] The structural formula of compound d is: ;

[0061] The structural formula of compound e is: ;

[0062] Compound e is used to react with compound f to generate compound g;

[0063] The structural formula of compound f is: ;

[0064] The structural formula of compound g is:

[0065] ;

[0066] Compound i is generated by reacting compound g with compound h.

[0067] The structural formula of compound h is: ;

[0068] The structural formula of compound i is:

[0069] ;

[0070] Compound i and compound j are used to generate compound k;

[0071] The structural formula of compound j is: ;

[0072] The structural formula of compound k is:

[0073] ;

[0074] The high-curing UV stabilizer is generated using the compound k.

[0075] The structural formula of the high-curing UV-resistant agent is:

[0076] .

[0077] The seventh aspect of this invention discloses a method for preparing a highly curable UV stabilizer, comprising the following steps:

[0078] Compound c is generated by reacting compound a with compound b;

[0079] The structural formula of compound a is: ;

[0080] The structural formula of compound b is: ;

[0081] The structural formula of compound c is: ;

[0082] Compound c is used to react with compound d to generate compound e;

[0083] The structural formula of compound d is: ;

[0084] The structural formula of compound e is: ;

[0085] Compound e is used to react with compound f to generate compound g;

[0086] The structural formula of compound f is: ;

[0087] The structural formula of compound g is: ;

[0088] Compound i is generated by reacting compound g with compound h.

[0089] The structural formula of compound h is: ;

[0090] The structural formula of compound i is:

[0091] ;

[0092] Compound i and compound j are used to generate compound k;

[0093] The structural formula of compound j is: ;

[0094] The structural formula of compound k is:

[0095] ;

[0096] The high-curing UV stabilizer is generated using the compound k.

[0097] The structural formula of the high-curing UV-resistant agent is:

[0098] .

[0099] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit the disclosure of the embodiments of the present invention. Attached Figure Description

[0100] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0101] Figure 1 The present invention provides a general structural formula I for a high-curing UV-resistant agent, wherein the triazine group is located at the meta position on the benzene ring of the phenylpropanetriazine group;

[0102] Figure 2 The present invention provides a high-curing UV-resistant agent with general structural formula II, wherein the triazine group is located ortho-positioned on the benzene ring of the phenylpropanetriazine group;

[0103] Figure 3 The structure of a specific compound of the high-curing UV-resistant agent proposed in some embodiments of the present invention is A-1.

[0104] Figure 4 The structure of a specific compound of the high-curing UV-resistant agent proposed in some embodiments of the present invention is A-2.

[0105] Figure 5 The structure of a specific compound of the high-curing UV-resistant agent proposed in some embodiments of the present invention is A-3.

[0106] Figure 6 The structural formula of a specific compound of the high-curing UV-resistant agent proposed in some embodiments of the present invention is A-4.

[0107] Figure 7 This refers to the multi-step reaction included in the preparation method of the high-curing UV-resistant agent with the compound structural formula (A-1) proposed in some embodiments of the present invention.

[0108] Figure 8 This refers to the multi-step reaction included in the preparation method of the high-curing UV-resistant agent with compound structural formula (A-2) proposed in some embodiments of the present invention.

[0109] Figure 9 This refers to the multi-step reaction included in the preparation method of the high-curing UV-resistant agent with compound structural formula (A-3) proposed in some embodiments of the present invention.

[0110] Figure 10 This refers to the multi-step reaction included in the preparation method of the high-curing UV-resistant agent with the compound structural formula (A-4) proposed in some embodiments of the present invention. Detailed Implementation

[0111] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0112] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the scope of the 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.

[0113] It should also be further understood that the term "and / or" as used in this application specification and the appended claims refers to any combination of one or more of the associated listed items, and all possible combinations, and includes such combinations. Unless otherwise specified, the following embodiments and features described herein can be combined with each other.

[0114] In the field of optical materials, resin mixtures used for photocuring often include UV stabilizers. Commercially available UV stabilizers do not participate in cross-linking during the curing process, so their dosage is limited, their effectiveness is limited, and the curing process is slow and prone to yellowing.

[0115] In view of this, the present invention proposes a high-curing UV stabilizer, such as... Figures 1 to 6 As shown, it includes: a hydroquinone group; two benzotriazole groups located at the ortho or meta position of the hydroquinone group; a triazine group attached to the benzotriazole group; and a first substituent group located on the triazine group. It should be noted that in the embodiments of this application, the hydroquinone group has two active hydroxyl groups at the para position, with one hydroxyl group at the ortho position of the other hydroxyl group and the other at the meta position. That is, the benzotriazole group is ortho to one of the hydroxyl groups of the hydroquinone group and meta to the other hydroxyl group, making the two benzotriazole groups adjacent to one of the hydroxyl groups respectively, close to each other, facilitating a reaction.

[0116] In this invention, the benzotriazole group, in combination with the hydroquinone group, achieves effective UV protection, while the triazine group provides auxiliary UV protection. Specifically, the nitrogen in the benzotriazole group is close to the hydroxyl group on the hydroquinone group, readily forming intrinsic hydrogen bonds and a chelate ring. Upon absorbing UV light, the molecule undergoes thermal vibration, the internal hydrogen bonds break, the chelate ring opens, and the UV light energy is converted into heat energy and released. The triazine group of this application has a high electron density, allowing it to be excited by UV light energy more quickly and absorb ultraviolet light, thus achieving an auxiliary UV protection effect.

[0117] In this application, the benzotriazole group absorbs wavelengths between 300 and 400 nm. It does not absorb violet light greater than 400 nm, nor does it absorb blue light with wavelengths between 450 and 490 nm, nor does it absorb natural light with longer wavelengths. Therefore, the high-curing UV stabilizer itself does not color and is not prone to yellowing.

[0118] When the UV light is absorbed and heat energy is released, the hydroxyl groups on the opened chelate ring can form hydrogen bonds with the substrate coated with the high-curing UV-resistant agent, thereby improving the adhesion of the high-curing UV-resistant agent.

[0119] Furthermore, the first substituent group attached to the triazine group in this application increases the molecular chain length and stress absorption capacity of the high-curing UV stabilizer, thereby enhancing the overall flexibility of the molecule.

[0120] Understandably, compared to the shortcomings of existing technologies, such as limited usage of UV stabilizers, poor curing effect, and susceptibility to yellowing, the high-curing UV stabilizer of this invention can achieve internal chelation within the molecule, good UV absorption effect, and efficient curing process.

[0121] In the description of this application, "multiple" means two or more, unless otherwise expressly and specifically defined.

[0122] In some embodiments, two benzotriazole groups are symmetrically disposed at the ortho or meta positions of the hydroquinone group, and each benzotriazole group is connected to a triazine group at the same position. The first substituents on each triazine group are of the same type. That is, in these examples, the high-curing UV stabilizer exhibits a generally symmetrical structure centered on the hydroquinone group, either with two benzotriazole groups symmetrically disposed at the ortho positions of the hydroquinone group or two benzotriazole groups symmetrically disposed at the meta positions of the hydroquinone group. This increases the benzotriazole content in the molecule, resulting in the formation of more chelate rings and the absorption of more UV energy during photocuring, opening the chelate rings and thus improving the UV resistance. Simultaneously, the increased content of triazine groups connected to the benzotriazole groups allows for the inclusion of more first substituents, enabling the grafting of more functional groups, increasing the curing rate and the molecule's stress resistance. The overall symmetrical molecular structure and the relatively uniform properties on both sides of the molecule enhance stress resistance in different directions.

[0123] For example, such as Figure 1 , Figure 3 and Figure 4 As shown, a triazine group is attached to the meta position of the benzene ring of each benzotriazole group, which makes the symmetry of the entire high-curing UV stabilizer stronger.

[0124] For example, such as Figure 2 , Figure 5 and Figure 6 As shown, a triazine group is attached to the ortho position of the benzene ring of each benzotriazole group, thereby giving the entire high-curing UV stabilizer extremely high symmetry.

[0125] Optionally, when two benzotriazole groups are symmetrically disposed at the two ortho positions of the hydroquinone group, a second substituent group is also symmetrically disposed at the meta position of the hydroquinone group relative to the hydroquinone group. This makes all the substituent groups at the two ortho positions of the hydroquinone group symmetrical overall. The nitrogen on the benzotriazole group at the ortho position can form an intrinsic hydrogen bond with the hydroxyl group on the hydroquinone group, chelating them, and the chelate ring opens during photocuring. The second substituent group at the meta position can further increase the number of branches in the molecule, thereby further improving the overall mechanical properties of the molecule.

[0126] Optionally, when two benzotriazole groups are symmetrically disposed at the two meta positions of the hydroquinone group, a second substituent group is also symmetrically disposed at the ortho position of the hydroquinone group relative to the hydroquinone group. This makes the substituent groups at the two meta positions of the hydroquinone group overall symmetrical. The nitrogen on the benzotriazole group at the meta position can form an intrinsic hydrogen bond with the hydroxyl group on the hydroquinone group, chelating them, and the chelate ring opens during photocuring. The second substituent group at the ortho position can further increase the number of branches in the molecule, thereby further improving the overall mechanical properties of the molecule.

[0127] The second substituent group mentioned above includes substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-30 alkyl ether group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 One of aralkyl and fluoroalkyl groups. When the second substituent group includes a long-chain alkane structure, the overall steric hindrance is small, and the chemical bonds can rotate freely. When subjected to external impact, stress transfer can occur, thus giving the molecule good flexibility. When the second substituent group includes an alkyl ether group, the rotational property of the molecular chain is improved, thus making the overall molecule more flexible. When the second substituent group includes an aryl group, the molecule has high rigidity. When the second substituent group includes an aralkyl group, it has both a certain degree of flexibility and rigidity. When the second substituent group includes a fluoroalkyl group, the lubricity of the molecule is improved. Fluorine atoms have high electronegativity and small atomic radii; when they replace hydrogen atoms in alkanes, they alter the electron cloud distribution of the carbon chain. This change reduces the flexibility of the carbon chain, making the molecular structure more rigid and stable. During lubrication, the rigid molecular structure can better withstand pressure and shear forces, maintaining the integrity of the lubricating film and thus exhibiting good lubricity. Simultaneously, the introduction of fluorine atoms lowers the surface energy of the molecules. Lower surface energy allows fluorinated alkanes to spread more easily at the friction interface, forming a uniform lubricating film, reducing direct contact between friction surfaces, lowering the coefficient of friction, and thus exhibiting lubricity. In this invention, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, features defined with "first" and "second" may explicitly or implicitly include one or more of the stated features.

[0128] In some embodiments, the first substituent group includes substituted or unsubstituted acrylate groups. These acrylate groups can link surrounding small molecules together to form a large network structure, thereby increasing the mixing speed of the high-curing UV stabilizer with other small molecules.

[0129] Optionally, such as Figure 1 and Figure 2As shown, the first substituent group includes an alkane attached to a triazine group and a substituted or unsubstituted acrylate group attached to the end of the alkane. In these examples, increasing the alkane can further increase the overall molecular length of the high-curing UV stabilizer and allow the acrylate group to extend to a wider area to connect with surrounding small molecules, thereby further improving the effectiveness of the high-curing UV stabilizer.

[0130] In some embodiments, such as Figure 1 and Figure 2 As shown, the high-curing UV stabilizer has the following general structural formula (Ⅰ) and general structural formula (Ⅱ):

[0131] (I);

[0132] (II)

[0133] Wherein, R1, R2, R3, R4, R5, and R6 are hydrogen, substituted, or unsubstituted C atoms, respectively. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 7-30 One of the aryl alkylene groups; R7, R8, R9, R 10 They are hydrogen or methyl, respectively; R 11 R 12 C164, C2 ... 1-20 Alkyl, substituted or unsubstituted C 1-30 alkyl ether group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 One of aralkyl and fluoroalkyl; (-CH2-) n In this context, n takes the value of a positive integer greater than or equal to 2. It should be noted that R1, R2, R3, R4, R5, and R6 can be the same structure or different structures; using the same structure makes the structure more symmetrical, while using different structures makes the branches more diverse and functional. R7, R8, R9, R... 10 It can be the same structure or different structures; using the same structure makes the structure more symmetrical, while using different structures makes the branches more diverse and the functionality stronger. 11 R 12 It can be the same structure or different structures; choosing the same structure can make the structure more symmetrical, while choosing different structures can make the branches more diverse and the functionality stronger.

[0134] For example, n can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

[0135] As can be seen from the above, in this invention, the overall structure of the high-curing UV stabilizer exhibits a roughly symmetrical structure with the hydroquinone group as the center, forming composite groups on both sides. This increases the number of benzotriazole groups, triazine groups, and first substituent groups in a single molecule, enabling the entire molecule to achieve reliable UV resistance, rapid curing performance, and excellent mechanical properties in multiple directions. When the content of benzotriazole in the molecule increases, more chelate rings are formed within the molecule, absorbing more UV light energy during the photocuring process. This causes the chelate rings to open, converting UV energy into heat energy, thereby enhancing the UV resistance effect. Simultaneously, the increased content of triazine groups connected to the benzotriazole group allows for the inclusion of more first substituent groups, enabling the grafting of more functional groups and increasing the curing rate and the molecule's stress resistance.

[0136] In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 They are hydrogen and (-CH2-), respectively. n In this case, if n takes the value of 2, then the following compounds can be obtained, such as... Figure 3 and Figure 5 As shown, the structural formulas of the compounds are A-1 and A-3.

[0137] A-1

[0138] In A-1, the two triazine groups are located at the meta position of the benzene ring of the phenylpropanetriazine group.

[0139] A-3

[0140] In A-3, the two triazine groups are located ortho to the benzene ring of the phenylpropanetriazine group.

[0141] In some embodiments, R1, R2, R3, R4, R5, R6, R 11 R 12 They are hydrogen, R7, R8, R9, and R... 10 All are methyl groups, (-CH2-) n In this case, if n takes the value of 2, then the following compounds can be obtained, such as... Figure 4 and Figure 6 As shown, the structural formulas of the compounds are A-2 and A-4.

[0142] A-2

[0143] In A-2, the two triazine groups are located at the meta position of the benzene ring of the benzotriazole group.

[0144] A-4

[0145] In A-4, the two triazine groups are located ortho to the benzene ring of the benzotriazole group.

[0146] In the examples above, compounds A-1, A-2, A-3, and A-4 all achieved relatively symmetrical structures and possessed high folding properties, excellent UV resistance, and high curing rates.

[0147] Of course, in other embodiments, the high-curing UV stabilizer can also be other structures, mainly containing hydroquinone groups, benzotriazole groups and triazine groups, within the range of the above general formula.

[0148] Optionally, the absorption wavelength of the high-curing UV stabilizer of the present invention is 300nm~400nm. Since light with wavelengths less than 400nm has high energy, it can damage chemical bonds and affect the stability of the compound. However, the high-curing UV stabilizer of the present application has an absorption wavelength of 300nm~400nm. After absorbing ultraviolet light, the intrinsic hydrogen bond formed between the nitrogen in the benzotriazole group and the hydroxyl group on the hydroquinone group is preferentially opened, allowing the hydroxyl group of hydroquinone to further bind to the substrate surface. This avoids damaging other chemical bonds within the molecule after absorbing ultraviolet light, thus improving the stability of the high-curing UV stabilizer. In the prior art, organic materials absorb blue light in the 450nm~490nm wavelength range and violet light in the 400nm~450nm wavelength range. The remaining light mixes and appears yellow, i.e., yellowing. The optical monomers in the embodiments of this application absorb wavelengths of 300nm~400nm. They do not absorb violet light greater than 400nm, nor do they absorb blue light in the 450~490nm wavelength range, nor do they absorb natural light with longer wavelengths. Therefore, the resin materials prepared will not be colored and are not prone to yellowing. In addition, the resin mixture prepared by the high-curing UV-resistant agent of this application will not be colored and is not prone to yellowing.

[0149] This invention proposes a resin mixture having the high-curing UV-resistant agent described in the above embodiments, comprising: a diluent; the high-curing UV-resistant agent of the aforementioned examples; a photoinitiator; the diluent accounting for 30%~90% of the total formulation mass, the high-curing UV-resistant agent accounting for 5%~69% of the total formulation mass, and the photoinitiator accounting for 0.1%~5% of the total formulation mass. The photoinitiator can rapidly absorb light under illumination, generating active free radicals, which can link individual molecules into a network structure, thereby initiating the polymerization reaction of the diluent and the high-curing UV-resistant agent. The high-curing UV-resistant agent can also absorb excessive UV radiation, preventing UV damage to the cured film layer. It can also absorb a small amount of residual active free radicals to a certain extent, and can rapidly aggregate the diluent around itself to form a network structure, allowing the various substances in the resin mixture to fully react and cure. Because the benzotriazole group in the high-curing UV stabilizer of this application absorbs wavelengths between 300 and 400 nm, it does not absorb violet light greater than 400 nm, nor does it absorb blue light with wavelengths between 450 and 490 nm, nor does it absorb natural light with longer wavelengths. Therefore, it does not compete with the photoinitiator. The photoinitiator can quickly form enough free radicals to initiate the polymerization reaction during the light irradiation process. The high-curing UV stabilizer can also absorb excess photoinitiator. The high-curing UV stabilizer itself does not get colored and is not prone to yellowing.

[0150] In an optional example, the resin mixture may include the following components by weight percentage: 30% of the total formulation mass of diluent, 65% of the total formulation mass of high-curing UV stabilizer, and 5% of the total formulation mass of photoinitiator.

[0151] In an optional example, the resin mixture may include the following components by weight percentage: 50% of the total formulation mass of diluent, 47% of the total formulation mass of high-curing UV stabilizer, and 3% of the total formulation mass of photoinitiator.

[0152] In an optional example, the resin mixture may include the following components by weight percentage: 60% of the total formulation mass of diluent, 38% of the total formulation mass of high-curing UV stabilizer, and 2% of the total formulation mass of photoinitiator.

[0153] In an optional example, the resin mixture may include the following components by weight percentage: 70% of the total formulation mass of diluent, 29% of the total formulation mass of high-curing UV stabilizer, and 1% of the total formulation mass of photoinitiator.

[0154] In an optional example, the resin mixture may include the following components by weight percentage: 80% of the total formulation mass of diluent, 19.5% of the total formulation mass of high-curing UV stabilizer, and 0.5% of the total formulation mass of photoinitiator.

[0155] In an optional example, the resin mixture may include the following components by weight percentage: 90% of the total formulation mass of diluent, 9.9% of the total formulation mass of high-curing UV stabilizer, and 0.1% of the total formulation mass of photoinitiator.

[0156] In an optional example, the resin mixture may include the following components by weight percentage: 90% of the total formulation mass of diluent, 5% of the total formulation mass of high-curing UV stabilizer, and 5% of the total formulation mass of photoinitiator.

[0157] In an optional example, the resin mixture may include the following components by weight percentage: 30% of the total formulation mass of diluent, 69% of the total formulation mass of high-curing UV stabilizer, and 1% of the total formulation mass of photoinitiator.

[0158] In some examples, the diluent includes trimethylolpropane triacrylate, 1,20-eicosenediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,3-cyclohexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,7-octanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1 One or a mixture of two or more of the following: 1,8-octadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,19-nonadecanediol di(meth)acrylate, neopentanediol di(meth)acrylate, pentaerythritol tetraacrylate, and 3-phenoxybenzyl acrylate. All of the above-mentioned diluents are small molecule substances with good compatibility with other components and can also adjust the concentration and viscosity of the entire resin mixture. The above-mentioned diluents are easy to polymerize around the high-curing UV-resistant agent of the present invention, especially easy to polymerize with acrylate groups to form a huge network structure, thereby enabling the entire resin mixture to cure quickly.

[0159] In some examples, the photoinitiator absorbs wavelengths from 368 nm to 420 nm. The photoinitiator can be excited and activated under ultraviolet light of these wavelengths, enabling it to initiate the polymerization reaction under these light conditions. The presence of a high-curing UV-resistant agent in the resin mixture does not affect the overall light transmittance of the resin material.

[0160] Optionally, the photoinitiator includes acylphosphine oxide, thioxanthone and its derivatives, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxyl chloride, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, diethoxyacetophenone, 4-tert-butyltrichloroacetophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-dimethylaminoethylbenzoate, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, bis(2,4) ,6-Trimethylbenzoyl)-phenylphosphine oxide, benzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diethoxyphenylphosphine oxide, benzoyl diethoxyphosphine oxide, benzophenone and its derivatives, benzoyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, p-dimethylaminoethyl benzoate, diphenyl disulfide, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2 At least one of the following photoinitiators: 3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 2-methyl-1-[4-(methylthio)phenyl-13-yl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, α-aminoalkylphenyl ketone derivatives, phenyl-glyoxylic acid-methyl ester or oxy-phenyl-acetic acid 2-[2-oxy-2-phenyl-ethoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester. When these photoinitiators are irradiated by a light source, they can be rapidly activated and generate active free radicals, thereby initiating polymerization reactions between the substances in the resin mixture, further achieving curing. The substances in these embodiments mainly absorb light in the wavelength range of 368nm to 420nm, while the high-curing UV absorber can absorb excessive UV light to prevent UV light from damaging the cured resin mixture. The use of photoinitiator does not affect the overall light transmittance of the cured resin mixture.

[0161] The resin mixture of the present invention, after curing, yields a resin material. The specific steps are as follows:

[0162] Step 1: Place the above resin mixture into a reaction vessel, mix and filter to form a mixture. Optionally, mix vigorously for 2 hours under light-protected conditions, then filter using a 0.45μm syringe filter to obtain the mixture.

[0163] Step 2: Coat the mixture onto the substrate. Optionally, coat the mixture onto the wafer and perform spin coating. The spin coating speed is 1000 rpm to 10000 rpm, and the spin coating time is 10 s to 300 s. For example, the spin coating speed can be 1000 rpm, 2000 rpm, 3000 rpm, 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, 9000 rpm, or 10000 rpm, etc., and the spin coating time can be 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 200 s, or 300 s, etc.

[0164] Step 3: The mixture coated on the substrate is cured to obtain a resin material. Ultraviolet curing (365nm) can be performed under oxygen-free conditions. This invention proposes applications for the resin mixture, including adhesives, filters, display materials, and anti-UV coatings. When used as an adhesive, the resin mixture exhibits strong adhesion and bonding force after coating and light curing, resulting in good adhesion to the substrate. When used as a filter, the resin mixture of this application can absorb a certain amount of ultraviolet light after curing, preventing ultraviolet light transmission. When used as a display material, it has high light transmittance and can be attached to a display screen without affecting light transmission. When used as an anti-UV coating, it can achieve significant absorption of ultraviolet light, effectively preventing ultraviolet light transmission and reducing the likelihood of yellowing.

[0165] This invention also proposes a method for preparing a highly curable UV stabilizer, used to prepare a highly curable UV stabilizer containing the compound with the structural formula (A-1) in the aforementioned example. The method includes the following steps:

[0166] Compound c is generated by reacting compound a with compound b;

[0167] The structural formula of compound a is: ;

[0168] The structural formula of compound b is: ;

[0169] The structural formula of compound c is: ;

[0170] Compound c is used to react with compound d to generate compound e;

[0171] The structural formula of compound d is: ;

[0172] The structural formula of compound e is: ;

[0173] Compound e is used to react with compound f to generate compound g;

[0174] The structural formula of compound f is: ;

[0175] The structural formula of compound g is:

[0176] ;

[0177] Compound i is generated by reacting compound g with compound h.

[0178] The structural formula of compound h is: ;

[0179] The structural formula of compound i is:

[0180] ;

[0181] Compound i and compound j are used to generate compound k;

[0182] The structural formula of compound j is: ;

[0183] The structural formula of compound k is:

[0184]

[0185] The high-curing UV stabilizer is generated using the compound k.

[0186] The structural formula of the high-curing UV-resistant agent is:

[0187] .

[0188] This invention also proposes a method for preparing a highly curable UV stabilizer, used to prepare a highly curable UV stabilizer containing the compound with the structural formula (A-2) in the aforementioned examples. The method includes the following steps:

[0189] Compound c is generated by reacting compound a with compound b;

[0190] The structural formula of compound a is: ;

[0191] The structural formula of compound b is: ;

[0192] The structural formula of compound c is: ;

[0193] Compound c is used to react with compound d to generate compound e;

[0194] The structural formula of compound d is: ;

[0195] The structural formula of compound e is: ;

[0196] Compound e is used to react with compound f to generate compound g;

[0197] The structural formula of compound f is: ;

[0198] The structural formula of compound g is:

[0199] ;

[0200] Compound i is generated by reacting compound g with compound h.

[0201] The structural formula of compound h is: ;

[0202] The structural formula of compound i is:

[0203] ;

[0204] Compound i and compound j are used to generate compound k;

[0205] The structural formula of compound j is: ;

[0206] The structural formula of compound k is:

[0207] ;

[0208] The high-curing UV stabilizer is generated using the compound k.

[0209] The structural formula of the high-curing UV-resistant agent is:

[0210] .

[0211] This invention also proposes a method for preparing a highly curable UV stabilizer, used to prepare a highly curable UV stabilizer containing the compound with the structural formula (A-3) in the aforementioned examples. The method includes the following steps:

[0212] Compound c is generated by reacting compound a with compound b;

[0213] The structural formula of compound a is: ;

[0214] The structural formula of compound b is: ;

[0215] The structural formula of compound c is: ;

[0216] Compound c is used to react with compound d to generate compound e;

[0217] The structural formula of compound d is: ;

[0218] The structural formula of compound e is: ;

[0219] Compound e is used to react with compound f to generate compound g;

[0220] The structural formula of compound f is: ;

[0221] The structural formula of compound g is:

[0222] ;

[0223] Compound i is generated by reacting compound g with compound h.

[0224] The structural formula of compound h is: ;

[0225] The structural formula of compound i is:

[0226] ;

[0227] Compound i and compound j are used to generate compound k;

[0228] The structural formula of compound j is: ;

[0229] The structural formula of compound k is:

[0230] ;

[0231] The high-curing UV stabilizer is generated using the compound k.

[0232] The structural formula of the high-curing UV-resistant agent is:

[0233] .

[0234] This invention also proposes a method for preparing a highly curable UV stabilizer, used to prepare a highly curable UV stabilizer containing the compound with the structural formula (A-4) in the aforementioned examples. The method includes the following steps:

[0235] Compound c is generated by reacting compound a with compound b;

[0236] The structural formula of compound a is: ;

[0237] The structural formula of compound b is: ;

[0238] The structural formula of compound c is: ;

[0239] Compound c is used to react with compound d to generate compound e;

[0240] The structural formula of compound d is: ;

[0241] The structural formula of compound e is: ;

[0242] Compound e is used to react with compound f to generate compound g;

[0243] The structural formula of compound f is: ;

[0244] The structural formula of compound g is: ;

[0245] Compound i is generated by reacting compound g with compound h.

[0246] The structural formula of compound h is: ;

[0247] The structural formula of compound i is:

[0248] ;

[0249] Compound i and compound j are used to generate compound k;

[0250] The structural formula of compound j is: ;

[0251] The structural formula of compound k is:

[0252] ;

[0253] The high-curing UV stabilizer is generated using the compound k.

[0254] The structural formula of the high-curing UV-resistant agent is:

[0255] .

[0256] For specific examples, the conditions and reaction formulas required for the reaction of high-curing UV stabilizers with compound structural formulas A-1, A-2, A-3, and A-4 can be found in [reference needed]. Figure 7 , Figure 8 , Figure 9 and Figure 10 For example, the specific reaction operation steps are as follows:

[0257] Compound a (33.6 g, 200 mmol) was added to 800 ml of acetic acid solvent and allowed to stand at room temperature for 10 min. Then, compound b (40.2 g, 200 mmol) was added and stirred for 60 min until a slurry formed. Stirring was continued overnight. Stirring was stopped, brine was added, and the mixture was extracted with diethyl ether and purified by column chromatography to give an orange-yellow solid. The solid was recrystallized from ethanol to give compound c (64.26 g, 140 mmol, 70% yield).

[0258] Compound c (64.26 g, 140 mmol), ethanol (1000 ml), and sodium hydroxide solution (4 mol / L, 1000 ml) were added to a reaction vessel and heated to 80 °C. Then, compound d (66.5 g, 4.4 eq) was added and stirred for 15 min to obtain a colorless solid suspension. Then, d (33.3 g, 2.2 eq) was added to obtain a light yellow liquid. The reaction was stopped, and the mixture was extracted with brine and ether. The mixture was purified by column chromatography to obtain compound e, 52.36 g, in 85% yield.

[0259] In a nitrogen atmosphere, 1200 ml of tetrahydrofuran and 44 g (100 mmol) of compound e were added to a 2000 ml reactor. The temperature was lowered to 0 °C, and 28.2 g (200 mmol) of compound f were added. The mixture was stirred for 1 h, and then 33.6 g (400 mmol) of sodium acetate was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, saturated brine was added to the system, the organic layer was extracted with dichloromethane, and the solvent was removed under reduced pressure to obtain 49.6 g of compound g, with a yield of 80%.

[0260] In a nitrogen atmosphere, 1200 ml of tetrahydrofuran and 49.6 g (80 mmol) of compound g were added to a 2000 ml reactor. The temperature was lowered to 0 °C, and 43.4 g (350 mmol) of compound f were added. The mixture was stirred for 1 h, and then 33.6 g (400 mmol) of sodium acetate was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, saturated brine was added to the system, the organic layer was extracted with dichloromethane, and the solvent was removed under reduced pressure to obtain 43.32 g of compound i, with a yield of 68%.

[0261] Compound i (43.32 g, 54.4 mmol) and compound j (6.3 g, 70 mmol) were reacted in dichloromethane solvent with triethylamine for 25 h to give compound k (44.61 g, 81% yield).

[0262] Compound i (44.61 g, 44.06 mmol), 385 ml of hydrobromic acid, and 320 ml of acetic acid were added to the reaction vessel, and the mixture was boiled and refluxed for 36 h to obtain a highly curable UV stabilizer with the compound structure A-1, A-2, A-3, or A-4, 32.53 g, yield 75%.

[0263] like Figure 7 , Figure 8 , Figure 9 and Figure 10 As shown, the aforementioned high-curing UV stabilizers with compound structures A-1, A-2, A-3, and A-4 can be prepared using similar reaction steps. Compared to preparing the high-curing UV stabilizer with compound structure A-1, preparing the high-curing UV stabilizers with compound structures A-2, A-3, and A-4 only requires changing the corresponding reactants and using the corresponding compound monomers. For example, in preparing A-2, compared to preparing A-1, only compound j needs to be replaced with methacryloyl chloride. In preparing A-3, compared to preparing A-1, only compound b needs to be replaced with 2,3-dinitrochlorobenzene. In preparing A-4, compared to preparing A-1, only compound b needs to be changed to 2,3-dinitrochlorobenzene, and compound j needs to be changed to methacryloyl chloride.

[0264] The compounds and resin mixtures of the present invention will be further described below with reference to specific embodiments and test data.

[0265] Example 1

[0266] Formation of compound A-1:

[0267] like Figure 7 As shown, compound a (33.6 g, 200 mmol) was added to 800 ml of acetic acid solvent and left at room temperature for 10 min. Then compound b (40.2 g, 200 mmol) was added, and the mixture was stirred for 60 min until a slurry appeared. Stirring was continued overnight. Stirring was stopped, brine was added, and the mixture was extracted with diethyl ether and purified by column chromatography to obtain an orange-yellow solid. The solid was recrystallized from ethanol to give compound c (64.26 g, 140 mmol, 70% yield).

[0268] Compound c (64.26 g, 140 mmol), ethanol (1000 ml), and sodium hydroxide solution (4 mol / L, 1000 ml) were added to a reaction vessel and heated to 80 °C. Then, compound d (66.5 g, 4.4 eq) was added and stirred for 15 min to obtain a colorless solid suspension. Then, d (33.3 g, 2.2 eq) was added to obtain a light yellow liquid. The reaction was stopped, and the mixture was extracted with brine and ether. The mixture was purified by column chromatography to obtain compound e, 52.36 g, in 85% yield.

[0269] In a nitrogen atmosphere, 1200 ml of tetrahydrofuran and 44 g (100 mmol) of compound e were added to a 2000 ml reactor. The temperature was lowered to 0 °C, and 28.2 g (200 mmol) of compound f were added. The mixture was stirred for 1 h, and then 33.6 g (400 mmol) of sodium acetate was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, saturated brine was added to the system, the organic layer was extracted with dichloromethane, and the solvent was removed under reduced pressure to obtain 49.6 g of compound g, with a yield of 80%.

[0270] In a nitrogen atmosphere, 1200 ml of tetrahydrofuran and 49.6 g (80 mmol) of compound g were added to a 2000 ml reactor. The temperature was lowered to 0 °C, and 43.4 g (350 mmol) of compound f were added. The mixture was stirred for 1 h, and then 33.6 g (400 mmol) of sodium acetate was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, saturated brine was added to the system, the organic layer was extracted with dichloromethane, and the solvent was removed under reduced pressure to obtain 43.32 g of compound i, with a yield of 68%.

[0271] Compound i (43.32 g, 54.4 mmol) and compound j (6.3 g, 70 mmol) were reacted in dichloromethane solvent with triethylamine for 25 h to give compound k (44.61 g, 81% yield).

[0272] Compound i (44.61 g, 44.06 mmol), 385 ml of hydrobromic acid, and 320 ml of acetic acid were added to the reaction vessel, and the mixture was boiled and refluxed for 36 h to obtain a high-curing UV stabilizer with the compound structure A-1, 32.53 g, yield 75%.

[0273] Preparation of resin mixture HIA-1: 10 g of trimethylolpropane triacrylate, 1 g of A-1, and 0.4 g of phosphine oxide (TPO) as a photoinitiator were added to a 50 mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain the final mixture. The mixture was then homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0274] Example 2

[0275] Preparation of A-2, such as Figure 8 As shown, the overall process is the same as A-1, but compound j is replaced with methacryloyl chloride.

[0276] 10 g of trimethylolpropane triacrylate, 1 g of A-2, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and Outgassing of the cured film were tested.

[0277] Example 3

[0278] Preparation of A-3, such as Figure 9 As shown, the overall process is the same as A-1, but compound b is replaced with 2,3-dinitrochlorobenzene.

[0279] 10 g of trimethylolpropane triacrylate, 1 g of A-3, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0280] Example 4

[0281] Preparation of A-4, such as Figure 10 As shown, the overall process is the same as A-1, except that compound b is replaced with 2,3-dinitrochlorobenzene, and compound j is replaced with methacryloyl chloride.

[0282] 10 g of trimethylolpropane triacrylate, 1 g of A-4, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0283] Example 5

[0284] 10 g of trimethylolpropane triacrylate, 3 g of A-1, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0285] Example 6

[0286] Add 10g of trimethylolpropane triacrylate, 0.2g of A-1, and 0.4g of phosphine oxide (TPO) as photoinitiators to a 50mL volumetric flask. Mix vigorously for 2 hours under light-protected conditions, then filter through a 0.45μm syringe filter to obtain a resin mixture. Spin-coat the mixture onto a 4-inch glass wafer (3500 rpm, 60s), and cure under anaerobic conditions using ultraviolet light (365nm). Test the surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, cure rate, and Outgassing of the cured film.

[0287] Comparative Example 1

[0288] 10 g of trimethylolpropane triacrylate and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and Outgassing of the cured film were tested.

[0289] Comparative Example 2

[0290] 10 g of trimethylolpropane triacrylate, 0.2 g of UV-234, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0291] Comparative Example 3

[0292] 10 g of trimethylolpropane triacrylate, 1 g of UV-234, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0293] Comparative Example 4

[0294] 10 g of trimethylolpropane triacrylate, 3 g of UV-234, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0295] Comparative Example 5

[0296] 10 g of trimethylolpropane triacrylate, 1 g of UV-326, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and Outgassing of the cured film were tested.

[0297] Comparative Example 6

[0298] 10 g of trimethylolpropane triacrylate, 1 g of UV-1130, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and Outgassing of the cured film were tested.

[0299] Comparative Example 7

[0300] 10 g of trimethylolpropane triacrylate, 1 g of UV-327, and 0.4 g of phosphine oxide (TPO) were added to a 50 mL volumetric flask as photoinitiators. The mixture was vigorously mixed for 2 h under light-protected conditions, and then filtered through a 0.45 μm syringe filter to obtain a high-refractive-index resin mixture. The mixture was homogenized on a 4-inch glass wafer (3500 rpm, 60 s) and cured under anaerobic conditions using ultraviolet light (365 nm). The surface condition, yellowness, haze, adhesion, yellowness after UV aging, adhesion after UV aging, curing rate, and outgassing of the cured film were tested.

[0301] The phosphine oxide (TPO) used in this example and comparative example was purchased from IGM; the trimethylolpropane triacrylate used was purchased from Sartoma. The commercially available UV stabilizers in the comparative examples above, UV-234 and UV-326, were purchased from BASF, with the main compound being 1-(2H-benzotriazol-2-yl)-4,6-di(1-methyl-1-phenylethyl)phenol; UV-326 was purchased from BASF, with the main compound being 1-(5-chloro-2-benzyltriazolyl)-6-tert-butyl-p-cresol; UV-1130 was purchased from BASF, with the main compound being 1-benzotriazol-5-tert-butyl-4-hydroxyphenylpropionate; and UV-327 was purchased from BASF, with the main compound being 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole.

[0302] It should be noted that in the above embodiments, acylphosphine oxide was selected as the photoinitiator and trimethylolpropane triacrylate was selected as the diluent to prepare the resin mixture for specific performance testing. However, other photoinitiators and other diluents listed in this invention also have similar effects and should be included in the protection scope of this application.

[0303] The cured films of the above-mentioned embodiments and comparative examples were subjected to performance tests, and the test results are shown in Table 1.

[0304] The performance testing methods and standards are as follows:

[0305] (1) Yellowness: High-precision haze meter (HM-150 Murakami Color MCRL);

[0306] (2) Adhesion: Cross-cut adhesion test;

[0307] (3) Ultraviolet aging: Ultraviolet aging test chamber (light source power 650mw, irradiation for 4h, stop for 4h as one cycle, total 24 cycles);

[0308] (4) Haze; High-precision haze meter (HM-150 Murakami Color MCRL)

[0309] (5) Outgass: Tested using TC-MS (TurboMatrix 350 PerkinElmer);

[0310] (6) Curing rate: The change in double bond content before and after curing was tested using FT-IR (Nicolet iN10Thermo).

[0311]

[0312] As shown in Examples 1-6, the UV-resistant structures A-1, A-2, A-3, and A-4 in this invention all exhibit excellent UV resistance, effectively suppressing the effects of UV radiation and improving adhesion. As the test results of Example 6 show, by adding a small amount of high-curing UV-resistant agent to the resin mixture, the cured film achieves a certain level of adhesion, with a smaller change in yellowness compared to the comparative example, and a relatively guaranteed curing rate.

[0313] In Comparative Example 1, because no UV stabilizer was added, the yellowness was high, and the yellowness changed significantly after UV aging.

[0314] In Comparative Example 2, 2% of commercially available UV stabilizer UV-234 was added. The yellowness was significantly improved compared to Comparative Example 1, but it was still higher than that of the present invention. It did not improve the curing rate. The Outgas test value was higher because the UV stabilizer did not participate in the curing process.

[0315] In Comparative Example 3, the UV-234 content was 10%, and the film surface was no longer dry, so the haze increased and the outgassing further increased.

[0316] In Comparative Example 4, the UV-234 content was 30%, and the haze increased sharply, indicating that the curing degree of UV-234 in the whole system was poor and the Outgas value continued to increase.

[0317] In Comparative Examples 5-7, the results were similar to those in Comparative Example 3. This further indicates that commercially available UV stabilizers UV-236, UV-1130, and UV-327 have problems with poor curing performance and severe yellowing.

[0318] Therefore, the high-curing UV-resistant agent of the present invention has a good anti-yellowing effect, can appropriately increase adhesion, and can significantly improve the overall curing effect.

[0319] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention 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 invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An anti-ultraviolet agent, characterized in that, The UV-resistant agent has the following general structural formula (Ⅰ) and general structural formula (Ⅱ): （Ⅰ）； （Ⅱ） Among them, R1, R2, R3, R4, R5, and R6 are hydrogen; R7, R8, R9, R 10 They are either hydrogen or methyl; R 11 R 12 Hydrogen or unsubstituted C, respectively. 1-20 alkyl; The value of n is a positive integer greater than or equal to 1.

2. The UV stabilizer as described in claim 1, characterized in that, The UV stabilizer includes the following compounds, with structural formulas (A-1), (A-2), (A-3), or (A-4): (A-1); or, (A-2); or, (A-3); or, （A-4）。 3. The UV stabilizer as described in claim 1 or 2, characterized in that, The absorption wavelength of the UV stabilizer is 300nm~400nm.

4. A resin mixture, characterized in that, include: Diluent; UV protectant as described in any one of claims 1-3; Photoinitiator; The amount of the diluent is 30% to 90% of the total formula mass, the amount of the UV protectant is 5% to 69% of the total formula mass, and the amount of the photoinitiator is 0.1% to 5% of the total formula mass.

5. The resin mixture as described in claim 4, characterized in that, The diluent is selected from trimethylolpropane triacrylate, 1,20-eicosenediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,3-cyclohexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,7-octanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 2 One or a mixture of two or more of the following: 4-diethyl-1,5-pentanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,19-nonadecanediol di(meth)acrylate, neopentanediol di(meth)acrylate, pentaerythritol tetraacrylate, and 3-phenoxybenzyl acrylate.

6. The resin mixture according to claim 4, characterized in that, The absorption wavelength of the photoinitiator is 368 nm to 420 nm; and / or, the photoinitiator is selected from acylphosphine oxide, thioxanthone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxyl chloride, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, diethoxyacetophenone, 4-tert-butyltrichloroacetophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-dimethylaminoethylbenzoate, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, bis(2,4) ,6-Trimethylbenzoyl)-phenylphosphine oxide, benzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diethoxyphenylphosphine oxide, benzoyl diethoxyphosphine oxide, benzophenone, benzoin, anthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, p-dimethylaminoethyl benzoate, diphenyl disulfide, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2 At least one of the following: 3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 2-methyl-1-[4-(methylthio)phenyl-13-yl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, phenyl-glyoxylic acid-methyl ester or oxy-phenyl-acetic acid 2-[2-oxy-2-phenyl-ethoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester.

7. The application of a resin mixture as described in any one of claims 4-6, characterized in that, Resin mixtures are used in adhesives, filters, display materials, or UV-resistant coatings.

8. A method for preparing an anti-ultraviolet agent, characterized in that, Includes the following steps: Compound c is generated by reacting compound a with compound b; The structural formula of compound a is: ; The structural formula of compound b is: ; The structural formula of compound c is: ; Compound c is used to react with compound d to generate compound e; The structural formula of compound d is: ; The structural formula of compound e is: ; Compound e is used to react with compound f to generate compound g; The structural formula of compound f is: ; The structural formula of compound g is: ； Compound i is generated by reacting compound g with compound h. The structural formula of compound h is: ; The structural formula of compound i is: ； Compound i and compound j are used to generate compound k; The structural formula of compound j is: ; The structural formula of compound k is: The UV protectant is generated using the compound k. The structural formula of the UV-resistant agent is: 。 9. A method for preparing an anti-ultraviolet agent, characterized in that, Includes the following steps: Compound c is generated by reacting compound a with compound b; The structural formula of compound a is: ; The structural formula of compound b is: ; The structural formula of compound c is: ; Compound c is used to react with compound d to generate compound e; The structural formula of compound d is: ; The structural formula of compound e is: ; Compound e is used to react with compound f to generate compound g; The structural formula of compound f is: ; The structural formula of compound g is: ； Compound i is generated by reacting compound g with compound h. The structural formula of compound h is: ; The structural formula of compound i is: ； Compound i and compound j are used to generate compound k; The structural formula of compound j is: ; The structural formula of compound k is: ； The UV protectant is generated using the compound k. The structural formula of the UV-resistant agent is: 。 10. A method for preparing an anti-ultraviolet agent, characterized in that, Includes the following steps: Compound c is generated by reacting compound a with compound b; The structural formula of compound a is: ; The structural formula of compound b is: ; The structural formula of compound c is: ; Compound c is used to react with compound d to generate compound e; The structural formula of compound d is: ; The structural formula of compound e is: ; Compound e is used to react with compound f to generate compound g; The structural formula of compound f is: ; The structural formula of compound g is: ； Compound i is generated by reacting compound g with compound h. The structural formula of compound h is: ; The structural formula of compound i is: ； Compound i and compound j are used to generate compound k; The structural formula of compound j is: ; The structural formula of compound k is: ； The UV protectant is generated using the compound k. The structural formula of the UV-resistant agent is: 。 11. A method for preparing an anti-ultraviolet agent, characterized in that, Includes the following steps: Compound c is generated by reacting compound a with compound b; The structural formula of compound a is: ; The structural formula of compound b is: ; The structural formula of compound c is: ; Compound c is used to react with compound d to generate compound e; The structural formula of compound d is: ; The structural formula of compound e is: ; Compound e is used to react with compound f to generate compound g; The structural formula of compound f is: ; The structural formula of compound g is: ; Compound i is generated by reacting compound g with compound h. The structural formula of compound h is: ; The structural formula of compound i is: ； Compound i and compound j are used to generate compound k; The structural formula of compound j is: ; The structural formula of compound k is: ； The UV protectant is generated using the compound k. The structural formula of the UV-resistant agent is: 。

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