A blue light blocking compound, preparation method and composition thereof

Abstract

The present invention provides a blue light protection compound, a preparation method and a composition thereof. The compound of the present invention has high stability and is suitable for high temperature processing conditions and outdoor exposure environments. On the other hand, the present invention also invents a novel method for covalently linking a blue light absorbing compound and an ultraviolet light absorbing compound to increase stability. The compound of the present invention can absorb ultraviolet light (UVA, UVB) and short-wavelength blue light to protect the eyes. It can also absorb long-wavelength blue light in a decreasing manner, so that the penetrating light has an excellent visual experience. The present invention can be applied to products such as optical films, plate optical lenses, goggles, skin care, lighting, coatings, adhesives, or panels.

Description

[0001] The present invention is a divisional application with application number 2018104135928, application date May 3, 2018, and titled "A blue light protection compound, preparation method and application thereof." Technical Field

[0002] The present invention relates to novel blue light absorbing compounds, their synthesis and compositions. The compounds of the present invention have high stability and are suitable for high temperature processing conditions and outdoor exposure environments. The compounds of the present invention can absorb ultraviolet light (UVA, UVB) and short wavelength blue light to protect the eyes. They can also absorb long wavelength blue light in a decreasing manner, so that the penetrating light has a particularly good visual experience. The present invention can be applied to products such as optical films, optical lenses, goggles, skin care, lighting, coatings, adhesives, or panels. On the other hand, the present invention also invents a novel method for covalently linking a blue light absorbing compound and an ultraviolet light absorbing compound to increase stability. Background of the Invention

[0003] It is well known that ultraviolet light can trigger free radicals that are harmful to the human body. UVA (about 320-400nm) ultraviolet light can penetrate glass and is the main ultraviolet light band in indoor environments. UVB (about 290-320nm) ultraviolet light is the main ultraviolet light band that causes photobiological effects on the skin due to solar radiation. In many applications, it is expected to absorb both UVA (about 320-400nm) and full-band blue light (about 380nm-450nm). Short-wave blue light can trigger free radicals in the body, which can cause macular degeneration in the long term (Investigative Ophthalmology & Visual Science (20140731), 55 (7), pp. 4119-4127. Therefore, compounds that can absorb ultraviolet light and short-wave blue light are widely used in the plastic, film or lens industries. In high-end applications, the absorption of longer wavelength blue light by blue light blocking agents needs to gradually decrease as the wavelength increases, that is, the longer wavelength blue light must have increasing penetration. In this way, a better visual experience can be created.

[0004] At present, most blue light blocking compounds are inorganic compounds, but due to the poor compatibility of inorganic compounds with film resins, the light transmittance of the film is generally reduced (Journal of Shandong University of Science and Technology, Vol. 30 (4) 2011 Aug. p. 71-85).

[0005] In contrast, blue light blocking organic compounds are more compatible with film resins. However, they are still not stable enough and are prone to degradation when processed at high temperatures or used outdoors. For example, in the injection molding of polycarbonate (PC) lenses, when the temperature reaches above 300°C, general blue light blocking organic compounds will degrade and cannot be used in high temperature injection processes.

[0006] Therefore, the requirements for being a high-end blue light blocking agent are very strict, and there are very few blue light blocking products on the market that meet the above characteristics. Summary of the invention

[0007] Three urgent needs of the anti-blue light industry are high-transmittance organic compounds with high stability or thermal processability, high visual sensitivity, and the ability to absorb ultraviolet light (UVA, UVB) and short-wavelength blue light at the same time.

[0008] The inventors have designed a novel polycyclic compound that meets these three requirements at the same time. The strategy of the present invention is to covalently link the blue light absorbing group and the ultraviolet light absorbing group. This new design concept has achieved a surprising breakthrough.

[0009] Surprisingly, the compound of formula (1) of the present invention has a high thermal stability and can even be used at temperatures above 300°C, and can be applied to the injection processing of engineering plastic lenses such as polycarbonate (PC). In addition, the compound of formula (1) of the present invention can absorb both ultraviolet light and short-wave blue light. Furthermore, the compound of the present invention has a high visual perception (showing a decreasing absorption of longer wavelength blue light).

[0010] A commercial UV-blocking compound UV-P and a blue light blocking agent (blue-1) were used as a control group, and the novel compound (4) of Example 2 of the present invention were used to compare thermal stability.

[0011]

[0012] Thermogravimetric analysis (TGA) results showed that the control group, UV-P, had a 5% weight loss at 190°C. The control group, blue-1, had a 5% weight loss at 178.3°C. Therefore, the control group cannot be used in most plastic injection processes. Surprisingly, the attached Figure 5 The TGA graph shows that the blue light absorbing compound (4) of Example 4 of the present invention has a thermal weight loss of less than 1% when the temperature rises to 300°C. The thermal stability of the blue light absorbing compound, blue-1, is greatly increased. It can be used in polycarbonate (PC) processing and injection molding.

[0013] It is very surprising that the covalent bonding of UV-P and blue-1 produces a better than expected ultra-high thermal stability. This novel concept and method of the present invention of covalently bonding blue light absorbing compounds and ultraviolet light absorbing compounds to increase stability has not even been tried.

[0014] The structure of the compound of the present invention is shown in formula (1):

[0015]

[0016] The novel compounds of the present invention have a multi-ring structure. One of the common structural features of the compounds of the present invention is that they include at least three rings, A, B, and C. The second common feature is that they have a common blue light absorbing group.

[0017] in,

[0018] R1 to R3 are a bond and / or any divalent linking group;

[0019] A, B, and C are unsubstituted or R4-substituted benzene rings, benzocarbocyclic rings, nitrogen-containing heterocyclic rings, or benzonitrogen-containing heterocyclic rings;

[0020] R4 is one or more substituents, each independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, straight or branched C1-C 18 Alkyl, C1~C 18 alkenyl, phenyl, OR5, SR5, SO2R5, SO3R5, COOR5, COR5, OCOR5, C(O)NR6R7, SO2NR6R7, and NR6R7, wherein R5, R6, and R7 are independently hydrogen or a linear or branched C1-C8 alkyl group, preferably, R5, R6, and R7 are independently hydrogen or a linear or branched C1-C4 alkyl group, preferably, halogen is selected from chlorine and bromine;

[0021] X is 1 or more, each independently selected from COOR8, CN, CONR6R7 and COR8, preferably, X is 1 or 2, each independently selected from COOR8, CN, CONR6R7 and COR8, more preferably, X is 2, each independently selected from COOR8, CN;

[0022] R8 is selected from H, straight or branched C1-C 18 Alkyl, C1~C 18 Alkenyl, polyethylene glycol with a molecular weight of 50 to 1000, preferably, R8 is selected from H, linear or branched C1 to C8 alkyl;

[0023] Z is a carbon atom, and Z and R3 are linked via a single, double, or triple bond, preferably, Z and R3 are linked via a double bond;

[0024] Z and X are linked via 1 or 2 single bonds, preferably, when n=2, Z and X are linked via 2 single bonds;

[0025] The C ring and R3 are linked via 1 or 2 single bonds, and preferably, when m=1, C and R3 are linked via 1 single bond;

[0026] [A]r and R1 are linked via 1 or 2 single bonds, preferably, when r = 1, [A]r and R1 are linked via 1 single bond;

[0027] m=1-4, preferably, m=1-2, particularly preferably, m=1;

[0028] n=1-3, preferably, n=1-2, particularly preferably, n=2;

[0029] r=1-3, preferably, r=1-2, particularly preferably, r=1;

[0030] Optimally, m = 1, n = 2, r = 1, and the structure is as follows:

[0031]

[0032] In the compound (1) of the present invention,

[0033] It is a blue light absorbing group;

[0034] [A] r -----R1-B is an ultraviolet light absorbing group.

[0035] The compound (1) of the present invention comprises at least one blue light absorbing group,

[0036] Selected from:

[0037]

[0038] Among them, R 11 -R 14 are the same or different and are independently selected from H, straight or branched C1~C 20 Preferably, R 11 -R 14 H, straight chain or branched chain C1~C 18 Preferably, R 11 -R 12 is H, a straight or branched C1-C8 alkyl, an unsubstituted or C1-C4 substituted phenyl, R 13 -R 14It is H, a straight or branched C1-C8 alkyl or alkenyl group, or an unsubstituted or halogen or C1-C4 substituted phenyl group.

[0039] Furthermore, the compound (1) of the present invention comprises at least one ultraviolet light absorbing group selected from:

[0040] Benzotriazole:

[0041] Oxanilide:

[0042] Triazine:

[0043] Benzophenone:

[0044] Carbazole:

[0045] Dibenzothiophene:

[0046] Dibenzofuran:

[0047] Diphenyl sulfide:

[0048] Diphenyl ether (Oxydibenzene):

[0049] Benzoxazinone:

[0050] Dibenzoylmethane:

[0051] Phenylformamidine:

[0052] Azomethine:

[0053] Quinazoline: and

[0054] Benzoic acid derivatives:

[0055] In the compound (1) of the present invention, R1 to R3 are a bond and / or any divalent linking group.

[0056] Preferably, R1 to R3 are a bond or / and a chain consisting of 1-10 groups selected from the following groups: -O-, -S-, -C(=O)-, -COO-, -C(=S)-, -C(=NR9)-, -CH2-, -CH(R9)-, -C(R9)2-, -C(R9)=, -C≡, -C(R9)=C(R9)-, -C≡C-, -N(R9)-, -C(R9)=N-, phenyl; more preferably, R1 to R3 are a bond or / and a chain consisting of 1-6 groups selected from the following groups: -O-, - S-, -C(=O)-, -COO-, -C(=NR9)-, -CH2-, -CH(R9)-, -C(R9)2-, -C(R9)=, -C≡, -C(R9)=C(R9)-, -C≡C-, -N(R9)-, -C(R9)=N-, phenyl, more preferably, R1 and R3 are a bond or / and are represented by -(R9)N-CH=N-, -NH-C(=O)-C(=O)-NH-, -COO-, -CON-, -CH2CH2CON-, -CH=N-, -(CHR9) q N(R9)- is a chain, R2 is a bond, or -(CHR9) q N(R9)-, particularly preferably, R2 is a bond, -CH2N(CH3)-, or -CH2N(CH2CH3)-;

[0057] q=0-8, preferably, q=0-4, more preferably, q=1-2, particularly preferably, q=1.

[0058] R9 is H, a linear or branched C1-C8 alkyl group, an unsubstituted phenyl group, or a phenyl group substituted by OH, a halogen, a C1-C4 alkoxy group, or a linear or branched C1-C4 alkyl group. Preferably, R9 is H, a linear or branched C1-C4 alkyl group, or an unsubstituted phenyl group. More preferably, R9 is H, a linear or branched C1-C2 alkyl group.

[0059] In the compound represented by formula (1) of the present invention,

[0060] A is selected from:

[0061]

[0062] B is selected from:

[0063]

[0064] C is selected from:

[0065]

[0066] R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C1-C8 alkyl, C1-C8 alkenyl, OR5, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, and adjacent R4s can form a fused ring of 3-6 atoms, wherein R5, R6, and R7 are independently hydrogen, or straight or branched C1-C8 alkyl;

[0067] p=1-3, preferably, p=1-2.

[0068] In the compound represented by formula (1) of the present invention, [A] r -----R1-B, preferably, r=1-2

[0069] When r = 2, ----R1- is a bond, and B is triazine, [A] r ----R1-B is

[0070]

[0071] When r = 1, ----R1- is a bond or a chain, and B is a ring, [A] r ----R1-B is selected from:

[0072]

[0073]

[0074] When r = 1, ----R1- is a bond and a chain, and B is a ring, [A] r -----R1-B is selected from:

[0075]

[0076] Wherein, R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight-chain or branched C1-C8 alkyl, C1-C8 alkenyl, OR5, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, R7 are independently hydrogen, or straight-chain or branched C1-C6 alkyl;

[0077] p=1-3, preferably, p=1-2.

[0078] R 10 is H, a linear or branched C1-C8 alkyl, a phenyl or a substituted phenyl. Preferably, R 10 It is H, a linear or branched C1-C6 alkyl group, or a phenyl group.

[0079] The compound represented by formula (1) of the present invention preferably has a polycyclic structure, characterized in that B=C=benzene ring and Z and R3 are connected via a double bond, and its structure is as shown in the compound represented by formula (2).

[0080]

[0081] in,

[0082] R1, R3 is a bond, or a chain consisting of 1-6 of the following groups:

[0083] -O-, -N(R9)-, -C(=O)-, -COO-, -CH2-, -CH(R9)-, -C(R9)2-,

[0084] -C(R9)=, -C≡, -C(R9)=N-, phenyl, preferably, R1, R3 are a bond or / and

[0085] -(R9)N-CH=N-, -NH-C(=O)-C(=O)-NH-, -COO-, -CON-,

[0086] -CH2CH2CON-, or -CH=N-;

[0087] R2 is a key, or -(CHR9) q N(R9)-, preferably, R2 is a bond, or -CH2N(R9)-, more preferably, R2 is a bond, -CH2N(CH3)-, or -CH2N(CH2CH3)-;

[0088] R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C1-C8 alkyl, C1-C8 alkenyl, OR5, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, and R7 are independently hydrogen or straight or branched C1-C6 alkyl, preferably, R5, R6, and R7 are independently hydrogen or straight or branched C1-C4 alkyl, and multiple R4s can form a condensed ring with a benzene ring;

[0089] R9 is H, a linear or branched C1-C8 alkyl group, an unsubstituted phenyl group, or a phenyl group substituted by OH, a halogen, a C1-C4 alkoxy group, or a linear or branched C1-C4 alkyl group. Preferably, R9 is H, a linear or branched C1-C4 alkyl group, or an unsubstituted phenyl group. More preferably, R9 is H, a linear or branched C1-C2 alkyl group.

[0090] X is one or more, each independently selected from COOR8, CN, CONR6R7 and COR8, preferably, X is one or two, each independently selected from COOR8, CN;

[0091] Z is a carbon atom, and Z and X are linked via a single or double bond, preferably, Z and X are linked via a single bond;

[0092] m=1-2, preferably, m=1;

[0093] n=1-2, preferably, n=2;

[0094] q=0-8, preferably, q=0-4, more preferably, q=1-2, particularly preferably, q=1.

[0095] The compound represented by formula (1) of the present invention preferably has a polycyclic structure, characterized in that B=C=benzene ring and Z and R3 are connected via a double bond, and its structure is as follows:

[0096]

[0097] in,

[0098] X is the same or different, and each is independently selected from COOR8, CN, CONR6R7 and COR8. Preferably, X is the same or different, and each is independently selected from COOR8 and CN;

[0099] Z is a carbon atom;

[0100] A is selected from:

[0101]

[0102] R1, R3 is a bond, or a chain consisting of 1-6 of the following groups:

[0103] -O-, -N(R9)-, -C(=O)-, -COO-, -CH2-, -CH(R9)-, -C(R9)2-,

[0104] -C(R9)=, -C≡, -C(R9)=N-, phenyl, preferably, R1, R3 are a bond or / and

[0105] -(R9)N-CH=N-, -NH-C(=O)-C(=O)-NH-, -COO-, -CON-,

[0106] -CH2CH2CON-, -CH=N-;

[0107] R2 is a key, or -(CHR9) qN(R9)-, preferably, R2 is a bond, or -CH2N(R9)-, more preferably, R2 is a bond, -CH2N(CH3)-, or -CH2N(CH2CH3)-;

[0108] q=0-8, preferably, q=0-4, more preferably, q=1-2, particularly preferably, q=1.

[0109] R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C1-C8 alkyl, C1-C8 alkenyl, OR5, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, and R7 are independently hydrogen or straight or branched C1-C6 alkyl, preferably, R5, R6, and R7 are independently hydrogen or straight or branched C1-C4 alkyl, and multiple R4s can form a condensed ring with a benzene ring;

[0110] R9 is H, a linear or branched C1-C8 alkyl group, an unsubstituted phenyl group, or a phenyl group substituted by OH, a halogen, a C1-C4 alkoxy group, or a linear or branched C1-C4 alkyl group. Preferably, R9 is H, a linear or branched C1-C4 alkyl group, or an unsubstituted phenyl group. More preferably, R9 is H, a linear or branched C1-C2 alkyl group.

[0111] Among the compounds represented by formula (1) of the present invention, the best is as follows:

[0112]

[0113]

[0114] The present invention also provides a method for manufacturing a blue light blocking compound, characterized in that the blue light blocking compound and the ultraviolet light blocking compound are covalently bonded.

[0115] The method for preparing the compound represented by formula (1) of the present invention comprises the following reaction steps:

[0116]

[0117] The first method described above is shown in Examples 1-18, and the second method is shown in Examples 19-31.

[0118] in,

[0119] R 15 is H, a linear or branched C1-C8 alkyl group or a phenyl group; A-C, R1-R3, X, and Z are as defined for compound (1).

[0120] The specific preparation method of the blue light protection compound of the present invention is as follows:

[0121] Specific method 1 (Example 1-18):

[0122]

[0123]

[0124] Specific method 2 :

[0125]

[0126] p-Hydroxybenzaldehyde, potassium carbonate and compound (32) were reacted in DMF at 80°C overnight under nitrogen protection to obtain compound (67). Ethyl 2-cyanoacetate was added to react to obtain compound (68) Specific method 3 :

[0127] Specific preparation method of compound (17) of the present invention (Example 17):

[0128]

[0129] Specific method 4 :

[0130] Specific preparation method of traditional benzotriazole compounds (Example 13):

[0131]

[0132] Its synthesis method usually uses 2-nitroaniline and various substituted phenols as starting materials. The first step forms an azo compound, and the second step is a reduction reaction to form a benzotriazole compound (US 3773751). 15 Selected from halogen, hydroxyl, amino, nitro, cyano, straight chain or branched C1~C 18 Alkyl, C1~C 18 alkenyl, phenyl, OR5, SR5, SO2R5, SO3R5, COOR5, COR5, OCOR5, C(O)NR6R7, SO2NR6R7, and NR6R7, wherein R5, R6, and R7 are independently hydrogen or a linear or branched C1-C8 alkyl group.

[0133] Specific method 5 (Examples 19-31):

[0134]

[0135] The present invention also includes a blue light and / or ultraviolet light protection composition, characterized in that it includes a compound structure of formula (1). The composition can be used to manufacture products such as optical films, optical lenses, goggles, coatings, adhesives, or panels.

[0136] The present invention also includes lenses or goggles that block blue light or / and UV light, including lenses made of glass and polymer materials, such as polycarbonate (PC), polymethyl methacrylate (PMMA), nylon (PA), TPX (Polymethylpentene), polystyrene, and diethylene glycol dialkyl carbonate resin (PEDC). The blue light blocking agent can be added to the resin in a specific proportion for co-molding, and the blue light blocking agent has a mass content of 0.01% to 20%, preferably 0.05% to 10%, and more preferably 0.1% to 5%. The present invention can also use an impregnation process to immerse the lens in a composition containing an anti-blue light agent. The present invention can also use a thin film process to form an anti-blue light film on the surface of the lens. The present invention can also use a transfer coating process, for example, first coating on a release film and then transferring to an optical lens. Usually, about 1-5% of the embodiment compound is added to a 50μm film.

[0137] The anti-blue light or / and anti-ultraviolet light film system of the present invention has a basic structure including one or more anti-blue light film layers, and / or a substrate layer, and / or a release layer. Basically, the anti-blue light composition is coated on the substrate layer or the release layer and then dried. Or a transfer coating process is adopted, first coated on the release film, and then transferred to the substrate layer. The upper and lower layers of the anti-blue light film are each bonded with a layer of release film, which is OCA optical adhesive (Optically Clear Adhesive). The coating method is a conventional technique, including traditional brush coating, spray coating, curtain coating, roller coating, slit coating, air knife coating, scraper coating, and metering rod coating. The drying method includes natural drying, microwave drying, ultraviolet drying, infrared drying, and hot air drying. The substrate layer includes one or more mixtures of polyester, glass, polyethylene, polypropylene, polycarbonate, polyamide, polyacrylate, polymethacrylate, polyvinyl acetate, and polyvinyl chloride. The release film includes silicone-oxygen compound type and non-silicone-oxygen compound materials. Non-silicon compounds include, for example, polyethylene, polypropylene, polyurea, polyacrylic acid, polyester and a mixture of one or more fluorocarbons. OCA optical adhesives can be used in different fields according to their thickness, such as bonding of transparent devices, display assembly, lens assembly, panel, glass or polycarbonate and other plastic materials. The anti-blue light film can also include other film layers, such as UV absorption film layers, anti-fog film layers, and anti-static film layers. The anti-blue light film can be used in the optical or electronic industries, such as optical lenses, goggles, lenses, displays, panels, and lighting protection.

[0138] The film of anti-ultraviolet light or anti-blue light agent can also be made of resin raw materials such as polyvinyl chloride, low-density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), metallocene linear polyethylene (MLLDPE), etc., and various functional additives are added, and it is made by blow molding and calendering process. For example, the specific manufacturing method is to take 1kg of low-density polyethylene as the base material, 200g of metallocene linear polyethylene, 5g of anti-blue light agent, 8g of antioxidant, 5g of ultraviolet absorber, and 9g of glyceride, mix them well, and then blow mold them by the film blowing unit according to the conventional method. A transparent film with a thickness of 0.03 to 0.50mm.

[0139] The amount of blue light blocking agent added in the present invention depends on the type and thickness of the film and the required transmittance. The transmittance can be roughly calculated based on the standard absorption value (1 cm optical path) and the actual film thickness. The range includes but is not limited to 0.001%-20%.

[0140] Thermally initiated anti-blue light compositions usually include anti-blue light agents, thermal initiators, monomers, solvents, and additives. Thermal initiators are divided into high-temperature (above 100°C) initiators according to the use temperature range of the initiator, such as one or more mixtures of alkyl peroxides, alkyl hydroperoxide compounds, and peroxyester compounds. Medium-temperature (40-100°C) initiators, such as azo compounds, diacyl peroxides, persulfates, etc. Low-temperature (0-40°C) initiators, such as redox initiation systems. Thermal initiators can be mainly divided into two categories according to their molecular structure: azo compounds and peroxides. Commonly used azo compounds include azobisisobutyronitrile (ABIN), azobisisoheptanenitrile (ABVN), and azo compounds with carboxyl or sulfonic acid groups. Commonly used peroxides include benzoyl peroxide (BPO), di(2,4-dichlorobenzoyl) peroxide, diacetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, diisopropylbenzene peroxide (DCP), di-tert-butyl peroxide (DTBP), tert-butyl perbenzoate (BPB), isopropylbenzene hydroperoxide (CHP) and tert-butyl hydroperoxide (TBH), diisopropyl peroxydicarbonate (IPP), diisobutyl peroxydicarbonate (IBP), dicarbonic acid peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, persulfate and hydrogen peroxide. Monomers are small molecular compounds containing double bonds or other active functional groups. Double bond monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, hydroxy acrylic acid esters, hydroxy methacrylic acid esters, diacetone acrylamide, ethylene, styrene, diene, vinyl fluoride, vinyl chloride, acrylonitrile, vinyl acetate, silicone acrylate, epoxy acrylate, polyurethane acrylate. Acrylic acid or acrylate monomers include acrylic acid soft monomers, acrylic acid hard monomers, acrylic acid functional monomers, and crosslinking monomers. Preferred acrylic acid soft monomers include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate. Preferred acrylic acid hard monomers include methyl acrylate and methyl methacrylate. Preferred acrylic acid functional monomers include acrylic acid and methacrylic acid. Preferred crosslinking monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and adipic acid dihydrazide (ADH). Thermosetting resins used in anti-blue light films include polyurethane resins, epoxy resins, phenolic resins, polyurea resins, unsaturated polyester resins, and alkyd resins. The monomers thereof may be isocyanates, epichlorohydrin, phenols, aldehydes, polyols, fatty acids, polyacids, anhydrides, polythiols, polyamines, alcoholamines, and thiolamines.Solvents include acetonitrile, acetone, methyl ethyl ketone, butanone, cyclohexanone, benzene, toluene, xylene, ethyl acetate, butyl acetate, methyl isobutyl ketone, methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butanediol, vinyl chloride, dichloromethane, chloroform, carbon disulfide, tetrahydrofuran, dimethylformamide (DMF), polyethylene glycol methyl ether (EGMME). Polyurethane is produced by the reaction of polyester polyol or polyether polyol and isocyanate. In a specific embodiment, for example, polyol and isocyanate, chain extender, and catalyst (such as dimethylaminocyclohexane) are mixed, and then injected into a mold for curing and forming. Or isocyanate and polyol react first to form a prepolymer, and then a chain extender is added. Epoxy resin monomer is produced by the reaction of epichlorohydrin and bisphenol A compounds. The specific implementation includes reacting bisphenol A and epichlorohydrin, and then adding a hardener, such as dicyandiamide (Dicy) or adipic acid dihydrazide (ADH), and an accelerator 2-methylimidazole. The monomers of alkyd resin include polyols and fatty acids. The specific implementation includes, for example, placing glycerol, isophthalic anhydride and fatty acids in a reactor and heating to 200-250°C until the desired viscosity and acid value are reached. Unsaturated polyester resin is a linear polymer compound having ester bonds and unsaturated double bonds. The monomers include unsaturated dibasic acids and unsaturated diols, or saturated dibasic acids and unsaturated diols. The specific implementation includes, for example, carrying out a condensation polymerization reaction of propylene glycol, maleic anhydride, and phthalic anhydride in a reactor. The generated unsaturated polyester is added with styrene monomer to become a viscous resin, and cyclohexanone peroxide is added when used. The additives may include a stabilizer, a coupling agent, a leveling agent, a defoamer, a dispersant, a solvent, a chain transfer agent, a catalyst, a toughener, a tackifier, a plasticizer, a thickener, a diluent, a flame retardant, an inhibitor, a preservative, a hardener, and a mixture of one or more of an acid-base reconciling agent. Common chain transfer agents include aliphatic mercaptans and dodecyl mercaptan. Common stabilizers include UV absorbers, hindered amines, antioxidants, anti-hydrolysis agents, peroxide scavengers, and free radical scavengers. The thermally initiated anti-blue light composition may include an anti-blue light agent with a mass content of 0.01% to 20%, an initiator with a mass content of 0.01% to 10%, a monomer or prepolymer or polymer with a content of 50% to 99.98%, and an additive with a mass content of 0% to 80%. The mass content of the anti-blue light agent is preferably 0.05% to 10%, and more preferably 0.1% to 5%. In a specific implementation, for example, acrylic soft monomer, acrylic hard monomer, acrylic functional monomer, and acrylic cross-linking monomer are mixed to form a monomer mixture. The monomer mixture, initiator, and solvent are added to a reaction kettle, and the temperature is raised to react. After the reaction is completed, the temperature is lowered to room temperature, the material is discharged, and evenly coated on the base layer.

[0141] The photoinitiator anti-blue light composition usually includes an anti-blue light agent, a polymerized monomer or / and a prepolymer, a photoinitiator, and an auxiliary agent. The photoinitiators mainly include free radical photoinitiators and cationic photoinitiators, among which free radical photoinitiators are further divided into cleavage photoinitiators and hydrogen abstraction photoinitiators. The cleavage free radical photoinitiators are mainly aromatic alkyl ketone compounds, including benzoin derivatives, dialkoxyacetophenones, α-hydroxyalkyl phenones, α-aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aromatic peroxyester compounds, halogenated methyl aromatic ketones, organic sulfur-containing compounds, and benzoylformic acid esters. The hydrogen abstraction free radical photoinitiator includes one or more mixtures of active amines, benzophenones, thioxanthones and their derivatives, anthraquinones, active amines, coumarones, and camphorquinones. Cationic photoinitiators include one or more mixtures of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron aromatic salts, sulfonyloxy ketones and triarylsiloxane ethers. Prepolymers may be oligomers containing functional groups and further reactable, such as methacrylate oligomers, acrylate oligomers, epoxy acrylate oligomers, polyurethane acrylate oligomers, silicone acrylate oligomers, amino acrylate oligomers, carboxyl acrylate oligomers, phosphate acrylate oligomers, hydroxy polyacrylate oligomers, polyester acrylate oligomers, and polyether acrylate oligomers. Polymerized monomers may be one or more mixtures of various small molecules that undergo addition or condensation polymerization. The double bond monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, hydroxy acrylic acid esters, hydroxy methacrylic acid esters, diacetone acrylamide, ethylene, styrene, diene, vinyl fluoride, vinyl chloride, acrylonitrile, vinyl acetate, silicone acrylate, epoxy acrylate, polyurethane acrylate. Acrylic acid or acrylic acid ester monomers include acrylic acid soft monomers, acrylic acid hard monomers, acrylic acid functional monomers, and crosslinking monomers. Preferred acrylic acid soft monomers include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate. Preferred acrylic acid hard monomers include methyl acrylate and methyl methacrylate. Preferred acrylic acid functional monomers include acrylic acid and methacrylic acid. Preferred crosslinking monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and adipic acid dihydrazide. The mass content of the anti-ultraviolet / blue light agent of formula (1) is 0.01% to 20%, preferably 0.05% to 10%, and more preferably 0.1% to 5%. The additives may include a stabilizer, a coupling agent, a leveling agent, a defoamer, a dispersant, a solvent, a chain transfer agent, a catalyst, a toughening agent, a tackifier, a plasticizer, a thickener, a diluent, a flame retardant, an inhibitor, a preservative, a hardener, and an acid-base modifier. Common additives include coupling agents, such as silane coupling agents.Commonly used additives include stabilizers, such as a mixture of one or more of UV absorbers, hindered amines, antioxidants, and free radical scavengers. The photoinitiator anti-blue light composition includes an anti-blue light agent with a mass content of 0.01% to 20%, an initiator with a mass content of 0.01% to 10%, a monomer and / or prepolymer with a mass content of 5% to 99.98%, and an additive with a mass content of 0% to 95%. Preferably, the anti-blue light agent has a mass content of 0.05% to 10%, an initiator with a mass content of 0.05% to 5%, a monomer and / or prepolymer with a mass content of 5% to 99.9%, and an additive with a mass content of 0% to 50%. In a specific embodiment, the photoinitiator anti-blue light composition (such as a combination of acrylate monomers, acrylate prepolymers, blue light absorbers, and initiator Photocure 84) can be mixed and evenly applied to a clean substrate layer, and then cured with UV light to obtain an anti-blue light film.

[0142] A non-reactive anti-blue light composition, comprising an anti-blue light agent, a polymer, a solvent, and / or an auxiliary agent. It mainly utilizes the volatilization of the solvent or other dispersion medium in the coating to form a solid film. The polymer can be selected from but not limited to polyacrylate, polymethacrylate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylonitrile-styrene copolymer, thermoplastic polyurethane, polyimide, cellulose, polyphenylene sulfide, polyoxymethylene, polysulfone, polyetheretherketone, polyamide-imide, polyetherimide, polyethersulfone, polyetherimide, or one or more mixtures. The non-initiating anti-blue light composition may include an anti-blue light agent with a mass content of 0.01% to 20%, a polymer content of 5 to 99.99%, and an auxiliary agent with a mass content of (0 to 95%). In a specific implementation method, taking polystyrene as an example, the polystyrene plastic is dried, then crushed into small pieces, and put into a xylene / ethyl acetate mixed solvent and stirred until completely dissolved. Then a plasticizer (such as dibutyl phthalate) and an anti-blue light agent are added and heated and stirred to obtain a composition. After coating and drying to remove the solvent, an anti-blue light film is obtained. Plasticizers for polystyrene include phthalates, diterpenes, epoxy soybean oil, epoxy soybean oleate, and alkylbenzene sulfonates. BRIEF DESCRIPTION OF THE DRAWINGS

[0143] Figure 1 The UV-VIS absorption diagram of the compound 4) L-486 of the present invention (10 mg / chloroform), wherein A is the spectral absorption diagram and B is the peak data;

[0144] Figure 2 UV-VIS absorption diagram of compound 5, L-500 of the present invention (10 mg / chloroform), wherein A is the spectral absorption diagram and B is the peak data;

[0145] Figure 3 UV-VIS absorption diagram of compound 6, L-467 of the present invention (10 mg / chloroform); wherein A is the spectral absorption diagram and B is the peak data;

[0146] Figure 4 UV-VIS absorption diagram of compound 9, L-538, of the present invention (10 mg / chloroform); wherein A is the spectral absorption diagram and B is the peak data;

[0147] Figure 5 TGA chart of compound 4, L-486, of the present invention;

[0148] Figure 6 TGA chart of compound 5, L-500 of the present invention. DETAILED DESCRIPTION

[0149] Specific embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0150] Example 1, Preparation of 2-(2-hydroxy-3-(chloromethyl)-5-methyl)benzotriazole (Compound 32)

[0151]

[0152] In a 5000ml reaction bottle, add 350g of 2-(2-hydroxy-5-methyl)benzotriazole (UV-P), 55g of paraformaldehyde, 2000g of acetic acid, and 300g of 35% hydrochloric acid, raise the temperature to 60°C, keep the temperature for 10 hours, and take samples to monitor the reaction. Cool down, wash with water, and dry to obtain 409g of white powder (compound 32), with a yield of more than 90%, C 14 H 12 ClN3O. Melting point: 163-164°C.

[0153] Example 2, Preparation of 2-(2-hydroxy-3-(N,N-dimethylaniline)-5-methyl)benzotriazole (Compound 33)

[0154]

[0155] Add 180 ml of toluene, 17 g of potassium carbonate, 13.9 g of N-methylaniline, 0.2 g of phase catalyst, and 33.3 g of compound (32), raise the temperature to 90-100 °C and react for 5 hours, take samples to monitor the reaction. Cool down to 30 °C, wash with water and recover toluene. Add 180 g of methanol and stir, filter and dry to obtain 42 g of solid (compound 33). The yield is about 80%, C 21 H 20 N4O. Melting point: 98-100℃.

[0156] Example 3, Preparation of 2-(2-hydroxy-3-(4-formyl-N,N-dimethylaminophenyl)-5-methyl)benzotriazole (Compound 34)

[0157]

[0158] Add 35g of compound (33) and 8.7g of DMF, and drop 18.4g of phosphorus oxychloride at room temperature. Heat to 90℃ and react for 2 hours, take samples to monitor the reaction. Slowly add the reaction material to 300g of water below 30℃ for hydrolysis, neutralize with 30% liquid alkali and adjust the pH to 8, filter out the solid. Dissolve in 150g of toluene, wash twice with 50℃ water, cool to 15℃ to precipitate 31.8g of solid (compound 34), with a yield of about 80%, C 21 H 19 N4O2. Melting point: 111-113℃.

[0159] Example 4, Preparation of dimethyl (4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonate (Compound 4, L-486)

[0160]

[0161] Add 60 g of 2-(2-hydroxy-3-(4-formyl-N,N-dimethylaminobenzene)-5-methyl)benzotriazole (Compound 34), 21 g of dimethyl malonate, and 150 g of toluene, heat to raise the temperature, add 10 g of ammonium acetate and 20 g of acetic acid, first react at about 95 ° C for 2 hours, then reflux and dehydrate at about 112 ° C for 6 hours, monitor the reaction, and cool to 30 ° C after passing the reaction, filter out the solid, wash the solid twice with water, and dry it to obtain a yellow solid (Compound 4), C 27 H 26 N4O5. Melting point: 191℃-193℃.

[0162] Example 5, Preparation of dimethyl (4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)benzylidene)malonate (Compound 5, L-500)

[0163]

[0164] According to the method of Example 1-4, but using N-ethylaniline instead of N-methylaniline, 2-(2-hydroxy-3-(4-formyl-N-ethyl-anilino)-5-methyl)benzotriazole (Compound 35) was obtained. 22 H 22 N4O2. Melting point: 156-157℃.

[0165] According to the method of Example 1-4, dimethyl malonate was added to react to obtain compound (5), C 28 H 28 N4O5. Melting point: 173℃-178℃.

[0166] Example 6, Preparation of ethyl 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)phenyl)-2-cyanoacrylate (Compound 6, L-467)

[0167]

[0168] Add 60g of 2-(2-hydroxy-3-(4-formyl-N,N-dimethylaminobenzene)-5-methyl)benzotriazole (Compound 34), 18g of ethyl 2-cyanoacetate, and 150g of toluene, heat to raise the temperature, add 10g of ammonium acetate and 20g of acetic acid, first react at about 95°C for 2 hours, then reflux for dehydration reaction, react for 6 hours, take samples to monitor the reaction, cool to 30°C after passing the reaction, filter out the solid, wash the solid with water and dry it to obtain a solid (Compound 6), C 27 H 25 N5O3. Melting point: 177-179℃.

[0169] Example 7, Preparation of diisopropyl 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonate (Compound 7, L-542)

[0170]

[0171] According to the method of Example 1-4, diisopropyl malonate was added instead of methyl malonate. The reaction gave compound (7), C 31 H 34 N4O5. Melting point: 80℃-87℃.

[0172] Embodiment 8,

[0173] Preparation of diisopropyl 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-ethylbenzyl)(ethyl)amino)benzylidene)malonate (Compound 8, L-556)

[0174]

[0175] According to the method of Example 7, but replacing N-methylaniline with N-methylaniline, compound (8, L-556) was obtained. 32 H 36N4O5. Melting point: 87℃-90℃.

[0176] Example 9, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)dipropionic acid-1-en-2-yl ester (Compound 9, L-538)

[0177]

[0178] According to the method of Example 7, diisopropyl malonate was added instead of diisopropyl malonate to obtain compound (9), C 31 H 30 N4O5. Melting point: 132-141°C.

[0179] Embodiment 10,

[0180] Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonate (Compound 10, L-682)

[0181]

[0182] 24 g of compound (34) was dissolved in toluene and heated to reflux at 110°C in a condenser. 13 g of 2-ethylhexanol and 1.5 g of p-toluenesulfonic acid were added to the toluene solution. Samples were taken to monitor the reaction. After the reaction was completed, the product was purified by column chromatography to obtain compound (10), C 61 H 94 N4O5.

[0183] Example 11, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonic acid di(octadecyl)ester (Compound 11)

[0184]

[0185] According to the method of Example 10, but adding stearyl alcohol instead of 2-ethylhexanol. Sampling is taken to monitor the reaction. After the reaction is completed, the product is purified by column chromatography to obtain compound (11). 61 H 94 N4O5.

[0186] Example 12, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)malonic acid polyether ester (Compound 12)

[0187]

[0188] According to the method of Example 10, methoxypolyethylene glycol was added instead of 2-ethylhexanol. The reaction was monitored by HPLC. After the reaction was completed, the product was purified by GPC (colloid permeation chromatography) to obtain the compound of formula (12).

[0189] Example 13, Preparation of dimethyl 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)benzyl)(ethyl)amino)benzylidene)malonate (Compound 13) Using 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (Tinuvin 329) instead of UV-P as the starting material. According to the method of Examples 1-4, Compound (13) was obtained, C 34 H 38 N6O4.

[0190]

[0191] Raw material Tinuvin 329 (Eutec co., Eusorb UV 329). Or Specific method 4 The method is as follows: 13.8 grams of o-nitroaniline is added to 25 milliliters of 37% hydrochloric acid and stirred, diluted with 40 ml of water and cooled to -15°C. 7.5 g of sodium nitrite (dissolved in water) is added, and the temperature is maintained at 0-5°C to obtain the diazonium salt. 5.2 g of 4-tert-Octylphenol, 20 ml of petroleum ether, 5 ml of water and 2.5 g of calcium hydroxide are mixed, and a sample is taken to monitor the reaction. 20 g of ice is added and the temperature is raised to 0°C. The aforementioned diazonium salt is added and stirred for 2 hours. Concentrated hydrochloric acid is added to neutralize, and after drying, 2-((2-nitrophenyl)diazenyl)-4-(2,4,4-trimethylpentan-2-yl)phenol (Compound 36) is obtained, C 20 H 25 N3O3. Melting point: 114-115℃.

[0192]

[0193] Take 35.7g of compound (36) and dissolve it in 100ml of petroleum ether, add 17.2g of zinc and 100ml of water. Add 41.6g of NaOH solution (25%) at 50℃ within 4 hours and leave it for 1 hour. Add 100ml of concentrated hydrochloric acid and leave it for 2 hours. Take samples to monitor the reaction, wash the organic layer with water, remove the solvent and obtain Tinuvin 329 compound. 20 H 25N3O, melting point: 102-106℃.

[0194] Example 14, Preparation of dimethyl 2-(4-((3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxybenzyl)(ethyl)amino)benzylidene)malonate (Compound 14)

[0195]

[0196] According to the method of Example 13, but using 4-chloro-2-nitroaniline instead of o-nitroaniline as the starting material, 2-(2'-hydroxy-phenyl)-5-chloro-benzotriazole (Compound 37) was obtained. 12 H8ClN3O. Melting point: 139-140°C. According to the method of Example 1-4, but using 2-(2'-hydroxy-phenyl)-5-chloro-benzotriazole (Compound 37) instead of (UV-P) as the starting material, compound (14) was obtained. 27 H 25 ClN4O5.

[0197] Example 15, Preparation of dimethyl 2-(4-(ethyl(2-hydroxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl)amino)benzylidene)malonate (Compound 15).

[0198]

[0199] According to the method of Example 14, but using 4-methoxy-2-nitroaniline instead of 4-chloro-2-nitroaniline as the starting material, 2-(2-hydroxy-phenyl)-5-methoxy-benzotriazole (Compound 38) was obtained. 14 H 13 N3O2. Melting point: 126-127°C. According to the method of Example 1-4, but using 2-(2-hydroxy-phenyl)-5-methoxy-benzotriazole (Compound 38) instead of (UV-P) as the starting material, compound (15) was obtained. 29 H 30 N4O6.

[0200] Example 16, Preparation of methyl 3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-((ethyl(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)amino)methyl)-4-hydroxybenzoate (Compound 16)

[0201]

[0202] According to the method of Example 13, 4-hydroxybenzoic acid was used instead of 4-tert-octylphenol to obtain 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid. Thionyl chloride was added, and the temperature was raised to reflux for 2 hours. The thionyl chloride was evaporated, and n-hexanol was added to reflux for 1 hour. Samples were taken to monitor the reaction. 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid hexyl ester (Compound 39) was obtained. 19 H 21 N3O3, melting point: 83-84°C. According to the method of Example 1-4, but using compound (39) instead of UV-P as the starting material, compound (16) was obtained. 34 H 38 N4O7.

[0203] Example 17, Preparation of dimethyl 2-((1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-3a,7α-dihydro-1H-indol-3-yl)methylene)malonate (Compound 17)

[0204]

[0205] According to the method of Example 1-4, 3-indolecarboxaldehyde (Compound 40) was substituted for N-methylaniline to obtain Compound (41). According to the method of Example 4, Compound (41) was substituted for Compound (34), and the mixture was separated by column chromatography to obtain Compound (17), C 28 H 26 N4O5. m / z:498.2[M] + 3-Indolecarboxaldehyde is an industrial raw material and can be prepared in the following manner (Vilsmeier reaction): 16 g of POCl3 is added dropwise to 30 g of DMF in an ice bath within 30 minutes. 11 g of DMF solution of indole compound is slowly added, the temperature is raised to 35°C and stirred for 1 hour. 50 g of crushed ice is added to the obtained paste and stirred, and 0.1 M NaOH is slowly added under stirring. After washing with water, it is recrystallized from ethanol to obtain compound (40), C9H7NO. Melting point: 196-197°C.

[0206] Example 18, Preparation of ethyl 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)phenyl)-2-cyano-3-phenylacrylate (Compound 18)

[0207]

[0208] According to the method of Example 2, except that 4-methylaminobenzophenone was used instead of N-methylaniline, compound (42) was obtained. Then according to the method of Example 4, compound (42) was used instead of compound (34), and the mixture was separated by column chromatography to obtain compound (18), C 33 H 29 N5O3. m / z:543.2[M] + .

[0209] Example 19, Preparation of Tetraethyl 2,2'-((2-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)-1,4-phenylene)di(methylidene))dimalonate (Compound 19)

[0210]

[0211] The method of Example 2 was used, but 5-(ethylamino)dimethyl isophthalate (Compound 43, melting point 118°C) was used instead of N-methylaniline. The mixture was separated by column chromatography to obtain ((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)dimethyl isophthalate (Compound 44).

[0212]

[0213] 24g of compound (44) was dissolved in 100ml of toluene. At -78°C, under an argon atmosphere, 120ml of a 1M toluene solution of diisobutylaluminum hydride (DIBAL-H) ​​was added dropwise to the solution of compound (44). After adding DIBAH, stirring was continued for 2 hours. Methanol was added, and then the mixture was moved to room temperature, 1M HCl was added, and stirred for 5 minutes, and extracted with ethyl acetate. After washing with a saturated aqueous NaCl solution and drying with MgSO4, the mixture was filtered and the solvent was removed under reduced pressure to obtain compound (45). According to the method of Example 4, compound (45) was used instead of compound (34), and compound (19) was obtained by column chromatography. 38 H 42 N4O9. m / z:698.3[M] + .

[0214]

[0215] Example 20, Preparation of 3-(4-(3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)-N-methylpropionamido)phenyl)-2-cyanoacrylate (Compound 20)

[0216]

[0217] 5.2 g of methyl 3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoate (Compound 46) was dissolved in toluene and heated to reflux at 110°C in a flask equipped with a condenser and water separator. 3.7 g of ethyl 2-cyano-3-(4-(methylamino)phenyl)acrylate (Compound 47) was added to the toluene solution. The reaction was monitored by HPLC. After the reaction was completed, vacuum distillation was performed. After column chromatography, compound (20) was obtained, C 45 H 47 N5O4. m / z:721.4[M] + .

[0218]

[0219] Preparation method of compound (46) (according to CN201710949552.0), briefly, 16g of 2-chloro-4,6-di(2′,4′-phenyl)-1,3,5-triazine (compound 48) and 15g of methyl 3-(3-(tert-butyl)-4-hydroxyphenyl)propionate (compound 49) were dissolved in 150mL of chlorobenzene, 10g of anhydrous aluminum chloride was added, and the mixture was heated and stirred to dissolve. The temperature was raised to 90°C, and the reaction was monitored by HPLC. After the reaction was completed, the mixture was distilled under reduced pressure, and after silica gel column chromatography, compound (46) was obtained.

[0220] Preparation of ethyl 2-cyano-3-(4-(methylamino)phenyl)acrylate (Compound 47): Dissolve 20 g of dimethyl malonate and 13.6 g of 4-methylaminobenzaldehyde in dichloromethane. Add molecular sieves to remove water and install a calcium chloride tube to prevent water. Add 1 ml of piperidine and 0.6 ml of acetic acid, and heat to reflux temperature for 2 hours. Fresh molecular sieves are added during the reaction. After the reaction is completed, remove the solvent, acid wash and dry to obtain compound (47).

[0221] Example 21, Preparation of dimethyl 2-(4-((3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(methyl)-4-hydroxybenzyl)(methyl)amino)benzylidene)malonate (Compound 21)

[0222]

[0223] The method of Example 2 was used, but 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-6-(methyl)-4-(chloromethyl)phenol (Compound 50) was used instead of Compound (32), and 2-(4-(methylamino)benzylidene)malonate (Compound 51) was used instead of N-methylaniline. After column chromatography, Compound (21) was obtained. 40 H 40 N4O5. m / z:656.3[M] + .

[0224]

[0225] Compound 50 was prepared as in Example 20, except that 4-(chloromethyl)-2-methylphenol was used instead of methyl 3-(3-(tert-butyl)-4-hydroxyphenyl)propionate (49). Dimethyl 2-(4-(methylamino)benzylidene)malonate (Compound 51) was prepared as in Example 20, except that dimethyl malonate was used instead of ethyl 2-cyanoacetate.

[0226] Example 22, Preparation of a mixture of dimethyl 2-(4-((2,4-di-tert-butyl-3-hydroxy-6-((2,4-di-tert-butylphenoxy)carbonyl)benzyl)(methyl)amino)benzylidene)malonate and dimethyl 2-(4-((3,5-di-tert-butyl-2-((3,5-di-tert-butyl-4-hydroxybenzoyl)oxy)benzyl)(methyl)amino)benzylidene)malonate (22)

[0227]

[0228] The method of Example 21 was used, but 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-6-(methyl)-4-(chloromethyl)phenol (compound 50) was replaced with 3,5-di-tert-butyl-2-(chloromethyl)-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester and 2,4-di-tert-butyl-6-(chloromethyl)phenyl 3,5-di-tert-butyl-4-hydroxybenzoate mixture (52) to obtain mixture (22). Preparation of a mixture of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-2-(chloromethyl)-4-hydroxybenzoate and 2,4-di-tert-butyl-6-(chloromethyl)phenyl 3,5-di-tert-butyl-4-hydroxybenzoate: as in Example 2, except that 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutec co., Eusorb UV-120) was used instead of UV-P.

[0229] Example 23, Preparation of dimethyl (4-((5-benzoyl-4-hydroxy-2-(octyloxy)benzyl)(methyl)amino)benzylidene)malonate (Compound 23)

[0230]

[0231] The same method as in Example 21 was used, but 5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (Compound 53) was used instead of (Compound 50) to obtain Compound (23), C 35 H 41 NO7. m / z:587.3[M] + .

[0232]

[0233] The preparation method of 5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (Compound 53) was as described in Example 2, except that 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutec co., Eusorb UV-120) was used instead of UV-P.

[0234] Example 24, Preparation of dimethyl 2-(4-(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzyl)amino)benzylidene)malonate (Compound 24)

[0235]

[0236] The same method as in Example 21 was used, except that 2-(4-(chloromethyl)phenyl)-4H-benzo[d][1,3]oxazin-4-one (Compound 54) was used instead of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-6-(methyl)-4-(chloromethyl)phenol (Compound 50) to obtain dimethyl 2-(4-(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzyl)amino)benzylidene)malonate (Compound 24), C 28 H 24 N2O6. m / z:484.2[M] + .

[0237]

[0238] Preparation of 2-(4-(Chloromethyl)phenyl)-4H-benzo[d][1,3]oxazin-4-one (Compound 54): 14 g of 2-aminobenzoic acid (Compound 55) and 11 g of triethylamine were added to 100 ml of dichloroethane, and 19 g of 4-chloromethylbenzoyl chloride (Compound 56) was added dropwise and stirred to obtain (Compound 54). Preparation of Compound (56): 4-(Hydroxymethyl)benzoic acid (57) was chlorinated in dichloromethane with thionyl chloride under reflux to obtain Compound (56) Melting point: 28°C.

[0239]

[0240] Example 25, Preparation of dimethyl 2-(4-(methyl((4-oxo-2-(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)phenyl)-4H-benzo[d][1,3]oxazin-6-yl)methyl)amino)benzylidene)malonate (Compound 25)

[0241]

[0242] 40 g of 2-amino-5-(((4-(3-methoxy-2-(methoxycarbonyl)-3-oxoprop-1-en-1-yl)phenyl)(methyl)amino)methyl)benzoic acid (Compound 59) and 11 g of triethylamine were added to 200 ml of toluene, and 29 g of 4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzoyl chloride (Compound 58) was added and stirred. The product was separated by column chromatography to obtain (Compound 25), C 36 H 27 N3O8. m / z:629.2[M] + .

[0243]

[0244] Preparation of compound (58): The same method as Example 24 was used, except that 4-(chlorocarbonyl)benzoic acid methyl ester (60) was used instead of compound (56) to obtain compound (58).

[0245]

[0246] Preparation of compound (59): The same method as Example 21 was used, except that methyl 4-(chlorocarbonyl)benzoate (compound 61) was used instead of compound (54) to obtain compound (59).

[0247]

[0248] Example 26, Preparation of dimethyl 2-(4-(((2,4-dihydroxyquinolin-3-yl)methylene)amino)benzyl)(methyl)amino)benzyl)malonate (Compound 26, L-3701)

[0249]

[0250] The same method as in Example 21 was used, but 3-(((4-(chloromethyl)phenyl)imino)methyl)quinoline-2,4-diol (Compound 62) was used instead of Compound (51) to obtain Compound (26), C 30 H 27 N3O6. m / z:525.2[M] + .

[0251]

[0252] The preparation method of 3-(((4-(chloromethyl)phenyl)imino)methyl)quinoline-2,4-diol (62) was as described in Example 2, except that 3-((phenylimino)methyl)quinoline-2,4-diol (UA-3701, melting point 194°C) was used instead of UV-P.

[0253] Example 27, Preparation of dimethyl 2-(4-((4-(N'-(4-(ethoxycarbonyl)phenyl)-N-methylcarboimido)benzyl)(methyl)amino)benzylidene)malonate (Compound 27, UV-1)

[0254]

[0255] The same method as in Example 21 was used, but N1-(4-(chloromethyl)-2-ethoxyphenyl)-N2-(2-ethylphenyl)oxalamide (Compound 62) was used instead of Compound (54) to obtain Compound (27). 31 H 33 N3O6. m / z:543.24[M] + .

[0256]

[0257] Preparation of N1-(4-(chloromethyl)-2-ethoxyphenyl)-N2-(2-ethylphenyl)oxalamide (Compound 62): As in Example 2, except that N1-(2-ethoxyphenyl)-N2-(2-ethylphenyl)oxalamide (Eutec co., UV-1, melting point 137°C) was used instead of UV-P.

[0258] Example 28, Preparation of dimethyl 2-(4-((3-ethoxy-4-(2-((2-ethylphenyl)amino)-2-oxoacetylamino)benzyl)(methyl)amino)benzylidene)malonate (Compound 28)

[0259]

[0260] The same method as in Example 21 was used, but ethyl 4-((((4-(chloromethyl)phenyl)(methyl)amino)methylene)amino)benzoate (Compound 63) was used instead of Compound (54) to obtain Compound (28). 32 H 35 N3O7. m / z:573.3[M] + .

[0261]

[0262] The preparation method of ethyl 4-((((4-(chloromethyl)phenyl)(methyl)amino)methylene)amino)benzoate (Compound 63) was as described in Example 2, except that ethyl 4-(((methyl(phenyl)amino)methylene)amino)benzoate (Eutec co., UV-312, melting point 120°C) was used instead of UV-P.

[0263] Example 29, Preparation of dimethyl 2-(4-(((9H-carbazol-3-yl)methyl)(methyl)amino)benzylidene)malonate (Compound 29)

[0264]

[0265] The same method as in Example 21 was used, but 3-(chloromethyl)-9H-carbazole (Compound 64) was used instead of Compound (54) to obtain Compound (29). 26 H 24 N2O4. m / z:428.2[M] + .

[0266]

[0267] The preparation method of 3-(chloromethyl)-9H-carbazole (Compound 64) was as described in Example 2, except that 9H-carbazole was used instead of UV-P.

[0268] Example 30, Preparation of ethyl 2-cyano-3-(4-(N-methyl-9H-carbazole-1-carboxamido)phenyl)acrylate (Compound 30)

[0269]

[0270] The same method as in Example 20 was used, but 9H-carbazole-1-carboxylic acid methyl ester (Compound 65) was used instead of Compound (54) to obtain Compound (30). 26 H 21 N3O3. m / z:423.2[M] + .

[0271]

[0272] Preparation of 9H-carbazole-1-carboxylic acid methyl ester: 9H-carbazole-1-carboxylic acid was refluxed in excess methanol with concentrated sulfuric acid as a catalyst to obtain compound (65).

[0273] Example 31, Preparation of dimethyl 2-(4-((dibenzo[b,d]thiophen-2-ylmethyl)(methyl)amino)benzylidene)malonate (Compound 31)

[0274]

[0275] The same method as in Example 21 was used, but 2-(chloromethyl)dibenzo[b,d]thiophene (Compound 66) was used instead of Compound (54) to obtain Compound (31). 26 H 23 NO4S. m / z:445.1[M] + .

[0276]

[0277] Preparation of 2-(chloromethyl)dibenzo[b,d]thiophene: The method is the same as Example 2, but dibenzo[b,d]thiophene is used instead of UV-P.

[0278] Example 32 Thermal Stability Analysis

[0279] UV-blocking or blue-light blocking agents often need to be processed at high temperatures or used outdoors. However, general UV-blocking or blue-light blocking agents cannot withstand high temperatures. Therefore, high stability is a very important condition. Commercial UV-blocking compounds UV-P and blue-light blocking agents (blue-1) were used as control groups and compared with the example compounds to measure thermal stability using a thermogravimetric analyzer (TGA). The greater the weight loss, the worse the stability.

[0280]

[0281] The results are shown in Table 1. The control group absorbs ultraviolet light, UV-P, and the temperature of 5% weight loss is 190°C. The control group absorbs blue light, blue-1, and the temperature of 5% weight loss is 178.3°C. It cannot be used in plastic thermal processing. Surprisingly, the attached Figure 5The TGA of Example 4 of the present invention (L-486) ​​shows that the thermal weight loss is less than 1% when the temperature is raised to 300°C. Figure 6 The TGA shows that the temperature of the compound of Example 5 (L-500) of the present invention reaches 300°C, and the thermal weight loss is less than 1%. It can be used in polycarbonate (PC) processing. The temperature of the compound of the present invention, which loses 5% of its weight, reaches above 200°C. It can be used for plastic processing.

[0282] Table 1 Hot workability

[0283]

[0284] Example 33 Blue Light Absorption Analysis

[0285] UVA (about 320-400nm) ultraviolet light can penetrate glass and is the main indoor ultraviolet light band. UVB (about 290-320nm) ultraviolet light is the main ultraviolet light band that causes photobiological effects on the skin due to solar radiation. In many applications, it is expected to absorb UVA, UVB and blue light at the same time. As shown in Table 2, the performance comparison of the compounds of the embodiments of the present invention is shown.

[0286] For example, Figure 1-4 10 mg / L of compounds (4), (5), (6), (9) in chloroform. ... Figure 1-4 The results show that compounds (4), (5), (6) and (9) absorb both ultraviolet light and blue light, and gradually absorb less long-wavelength blue light (indicating that the blue light that penetrates has a better color visual effect).

[0287] Table 2

[0288]

[0289]

[0290] The present invention has been disclosed above with preferred embodiments, but they are not intended to limit the present invention. Any technical solutions obtained by adopting equivalent replacement or equivalent transformation solutions fall within the protection scope of the present invention.

Claims

1. A blue light protection compound, characterized in that , having the structure of formula (II): wherein R1 is selected from H, Cl, OMe; R2 is selected from -CH2N(CH3)-, -CH2N(CH2CH3)-; R3 is selected from -CH=, -CPh=; R4 is independently selected from H, OH, a linear or branched C1-C8 alkyl group, -COOR5, wherein R5 is a linear or branched C1-C8 alkyl group; at least one of R4 is OH; X is independently selected from COOR8, CN, and includes at least one COOR8; R8 is selected from a linear or branched C1-C 18 Alkyl, linear or branched C1-C8 alkenyl; p=1-3; Z is a carbon atom, and Z is connected to R3 via a double bond; Z and X are linked via a single bond, n=2; m=1-3.

2. The anti-blue light compound according to claim 1, characterized in that: The following structural formula:

3. A composition for preventing blue light and / or ultraviolet light, characterized in that , Including the blue light blocking compound as claimed in claim 1.

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