Ultraviolet light absorber and application thereof

Abstract

The invention relates to an ultraviolet absorber and an application thereof. The ultraviolet light absorber comprises a compound with a structure as shown in a formula (I) or a formula (II), in the formula (I) and the formula (II), R1 is selected from C1-C20 straight-chain or branched-chain alkyl groups, R2 is selected from C1-C8 straight-chain or branched-chain alkyl groups, and n is selected from an integer from 1 to 3. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of light stabilizers, and in particular relates to ultraviolet absorbers. Background Art

[0002] Polymer materials are indispensable basic materials in today's social production and life. Their aging problems will inevitably affect their performance, resulting in reduced lifespan and waste of resources. The factors that cause polymer aging are mainly light and heat, among which ultraviolet rays in natural sunlight have a particularly significant impact on the long-term performance of polymers. At present, the main way to prevent outdoor light aging is to add light stabilizers. Such light stabilizers include ultraviolet absorbers and hindered amine light stabilizers. As polymer materials gradually penetrate and extend from general and basic materials to special functional types. There are also some special application scenarios for the anti-aging of polymer materials, and traditional light stabilizers can no longer fully meet the needs.

[0003] Although traditional UV absorbers have a relatively comprehensive coverage in most of the UV region (wavelength 280-400nm), their absorption efficiency will be significantly reduced at wavelengths above 380nm. When encountering application fields with special requirements in the long-wave (red-shift region), traditional UV absorbers are difficult to meet the requirements.

[0004] Carbon fiber is an emerging material that has attracted much attention. Among them, carbon fiber reinforced epoxy resin composite materials are currently the most widely used carbon fiber reinforced materials (CFRM) with the highest comprehensive indicators such as strength and modulus. However, epoxy resin itself is easily damaged by ultraviolet visible light below 420nm, which causes degradation and affects its performance. Ultraviolet absorbers with high absorption efficiency at 380-420nm can effectively protect it.

[0005] Polyethylene naphthalate (PEN) is a polymer material with excellent comprehensive properties such as chemical stability, mechanical properties, and heat resistance, and has good application prospects in the fields of optical components. However, ultraviolet rays of 360-400nm can easily cause damage to PEN and composite materials containing PEN, leading to material degradation.

[0006] In addition, there are some fields that require special shielding requirements for light in the 360-430nm band. For example, special polarizers are required to absorb as completely as possible in the 380nm and below bands, or at least absorb 75-85% of ultraviolet rays, and transmit as much as possible above 410nm, for example, at least more than 95% of them. There are also some glass coatings and films, such as those used in car windshields and special architectural glass, which require shielding of ultraviolet rays below 400nm as much as possible to meet higher health requirements for people exposed to this environment. In the face of such demands, ultraviolet absorbers must be red-shifted to higher wavelength bands to meet better absorption efficiency in the 380-410nm band. For example, optical lenses, display screen devices, etc., need to have relatively high absorption of high-energy blue light in the 400nm-445nm band to protect the vision health of electronic product users.

[0007] There is an urgent need in the art for an ultraviolet absorber that has a good absorption effect on most of the ultraviolet region (280-400nm) while maintaining a good absorption effect on light with a wavelength above 380nm, especially light in the red-shifted region toward the long wave. Summary of the invention

[0008] In order to solve one of the above technical problems existing in the prior art, the present invention provides a method of introducing a sulfide or sulfone group into a conventional benzotriazole absorber to red-shift the cutoff wavelength of the conventional benzotriazole absorber from 400-410nm to a long-wave direction to a maximum of 430nm. In addition, by selecting a suitable alkyl segment, it is ensured that the new structure has a suitable melting point, solubility and better system compatibility, so that it can be applied to a variety of material systems.

[0009] One aspect of the present invention provides a compound having a structure as shown in formula (I) or formula (II),

[0010]

[0011] Wherein, in formula (I) and formula (II), R1 is selected from C1-C20 straight chain or branched alkyl, R2 is selected from C1-C8 straight chain or branched alkyl, and n is selected from an integer of 1-3.

[0012] In some embodiments, in formula (I) and formula (II), R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc. In some embodiments, in formula (I) and formula (II), R1 is selected from C5-C20 straight chain or branched alkyl, preferably selected from C7-C15 straight chain or branched alkyl.

[0013] In some embodiments, in formula (I) and formula (II), R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethyl-propyl, etc. In some embodiments, in formula (II), R2 is selected from C2-C6 straight chain or branched alkyl.

[0014] In some embodiments, the compound has a structure shown in formula (III) or formula (IV),

[0015]

[0016]

[0017] Wherein, in formula (III) and formula (IV), R1 is selected from C1-C20 straight chain or branched chain alkyl, and R2 is selected from C1-C8 straight chain or branched chain alkyl.

[0018] In some embodiments, in formula (III) and formula (IV), R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc. In some embodiments, in formula (III) and formula (IV), R1 is selected from C5-C20 straight chain or branched alkyl, preferably selected from C7-C15 straight chain or branched alkyl.

[0019] In some embodiments, in formula (III) and formula (IV), R2 is selected from a C2-C6 straight chain or branched alkyl group. In some specific embodiments, R2 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethyl-propyl, etc.

[0020] In some embodiments, the compound of formula (III) exemplarily includes:

[0021]

[0022] In some embodiments, the compound of formula (IV) exemplarily includes:

[0023]

[0024] In some preferred embodiments, the compound has the structure shown in RSUV-1 or RSUV-2:

[0025]

[0026] In some embodiments, the compound has an absorption wavelength range of 280-430 nm.

[0027] When the compounds of the present invention, especially the compounds RSUV-1 or RSUV-1, are used as ultraviolet absorbers, compared with traditional ultraviolet absorbers, especially compared with conventional benzotriazole ultraviolet absorbers, the absorption in the ultraviolet region can be shifted to the long-wave direction as a whole, wherein the absorption cutoff wavelength of RSUV-2 can be red-shifted to 430nm, satisfying the polymer material with absorption requirements of 280-430nm. In addition, the compounds of the present invention also have a suitable melting point, good solubility, better compatibility with oligomer resin systems, and lighter chroma, and excellent comprehensive performance.

[0028] Another aspect of the present invention provides a method for preparing the above compound, which comprises: using a compound having a structure as shown in formula (V) as a raw material and reacting it with an alkylthiol to prepare a compound having a structure as shown in formula (I).

[0029]

[0030] in,

[0031] In formula (V), X is selected from halogen, such as F, Cl, Br or I, preferably Cl, R4 is selected from C1-C8 straight chain or branched alkyl, preferably selected from C2-C6 straight chain or branched alkyl, and n is selected from an integer of 1-3.

[0032] In some embodiments, the alkylthiol has a structure represented by HS-R3, wherein R3 is selected from C1-C20 straight chain or branched chain alkyl, preferably selected from C5-C20 straight chain or branched chain alkyl, and more preferably selected from C7-C15 straight chain or branched chain alkyl.

[0033] In some embodiments, the preparation method further comprises oxidizing the compound with a structure as shown in formula (I) with an oxidant to obtain a compound with a structure as shown in formula (II).

[0034] In some embodiments, the oxidant may be a common oxidant in the art, such as hydrogen peroxide.

[0035] In some embodiments, the preparation method comprises: using a compound having a structure as shown in formula (VI) as a raw material, reacting with an alkylthiol to obtain a compound having a structure as shown in formula (III),

[0036]

[0037] In formula (VI), X is selected from halogen, such as F, Cl, Br or I, preferably Cl, and R4 is selected from C1-C8 straight chain or branched chain alkyl, preferably C2-C6 straight chain or branched chain alkyl.

[0038] In some embodiments, the preparation method further comprises oxidizing the compound with a structure as shown in formula (III) with an oxidant to obtain a compound with a structure as shown in formula (IV).

[0039] Another aspect of the present invention provides a composition comprising the above-mentioned compound.

[0040] In some embodiments, the composition further comprises one or more additives.

[0041] In some embodiments, the additives include, but are not limited to, one or more of hindered amine light stabilizers, other UV absorbers, antioxidants, emulsifiers, nucleating agents, toughening agents, lubricants, opening agents, fillers, dyes, pigments, fluorescent brighteners, flame retardants, antistatic agents or foaming agents.

[0042] In some embodiments, the hindered amine light stabilizer is a hydroxyalkoxy amine stabilizer.

[0043] In some embodiments, the hindered amine light stabilizer is not limited to: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; 1,2,2,6,6-pentamethyl-4-aminopiperidine; sebacate bis(1-acyl-2,2,6,6-tetramethylpiperidin-4-yl); sebacate bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl); sebacate bis(1,2,2,6,6-pentamethyl-4-yl); sebacate mono(1,2,2,6,6-pentamethyl-4-yl); N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3 ,5-triazine linear or cyclic condensation product (UV-944); 2-[2,2,6,6-tetramethyl-4-(3,5,5-trimethyl-hexanoyloxy)-piperidinyl]-3,5,5-trimethylhexanoic acid ethyl ester; [[3,5-di-tert-butyl-4-hydroxyphenyl]methyl]butylmalonic acid di(1,2,2,6,6-pentamethyl-4-yl) ester; poly[1-(2'-hydroxyethyl)-2.2.6.6-tetramethyl-4-hydroxypiperidinyl succinate]; 1,5,8,12-tetra[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-6-yl]-1,5,8,12-tetraazadodecane.

[0044] In some embodiments, the other UV absorbers include benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers, substituted acrylonitrile ultraviolet absorbers, triazine ultraviolet absorbers, oxalic acid anilide ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, etc.

[0045] In some embodiments, the benzotriazole ultraviolet absorber includes but is not limited to 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octyl)-2H-benzotriazole, 2-(2-hydroxy-3-cumyl-5-tert-octylbenzene)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2 -(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole, dodecyl 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, -ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2'-methylene-bis(4-tert-octyl-(6-2H-benzotriazol-2-yl)phenol), 2-(2-hydroxy-3-α-isopropylphenyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-α-isopropylphenylphenyl)-2H-benzotriazole.

[0046] In some embodiments, the antioxidant includes a phenolic antioxidant, an amine antioxidant, a phosphite antioxidant, a thioester antioxidant, or a benzofuranone antioxidant.

[0047] In some embodiments, the mass percentage of the compound in the composition is 0.1-6%, for example, about 0.1%, about 0.5%, about 1%, about 1.5%, about 2%, about 3%, about 4%, about 4.5%, about 5%, about 5.5%, about 6% or any value therebetween.

[0048] In some embodiments, the composition is present in one or more of: epoxy resin-based products and their composite products (such as epoxy-reinforced carbon fiber composites), polyethylene naphthalate-based products, optical adhesives, optical elements, optical films (such as optical films based on triacetyl cellulose, polycarbonate, polyacrylate or polyethylene naphthalate), optical lenses, anti-blue light products (such as anti-blue light lenses, anti-blue light display devices, etc.), car windows and their films, car cover films, automotive paints (i.e., automotive coatings, such as cathode electrophoretic primers and coatings composited therewith), and adhesives.

[0049] In some embodiments, the composition is present in a laminate or multilayer structure.

[0050] In some embodiments, the composition is a laminate or multilayer material. In some embodiments, the laminate or multilayer material can be reflective sheeting and conformal marking sheeting, solar control films, solar reflectors, reflective printed labels, UV absorbing glass and glass coatings, electrochromic devices, film / glass windows, windshields and interlayers, etc.

[0051] Another aspect of the present invention provides a polymer material, which comprises the above-mentioned compound or composition, and an organic material susceptible to degradation induced by oxygen, heat or light.

[0052] In some embodiments, the organic material in the polymer material includes but is not limited to polyester, polyurethane, polyacrylic acid, polycarbonate, epoxy and modified resins thereof, phenolic resin, polyamide, polyimide, polystyrene and derivatives thereof, polysilane, polysiloxane and modified thereof, poly(vinyl butyral), aminoacrylic acid, hydroxy acrylic acid, acrylic polyurethane, polycyanoacrylate, polyacrylate, ethylene / acrylic acid copolymers and salts thereof (ionomers), poly(vinyl alcohol), cellulose triacetate, polycarbonate, polyethylene naphthalate, polyethylene terephthalate, polyvinyl alcohol, polymethyl methacrylate, polycyclopentene, aliphatic isocyanate, polymethyl methacrylate, fluorine / silicon modified polyacrylic acid, at least one resin of polyisocyanate / polythioether.

[0053] In some embodiments, the mass percentage of the compound in the polymer material is 0.1-6%, for example, about 0.1%, about 0.5%, about 1%, about 1.5%, about 2%, about 3%, about 4%, about 4.5%, about 5%, about 5.5%, about 6% or any value therebetween.

[0054] Another aspect of the present invention provides a product, which comprises the above compound, the above composition or the above polymer material.

[0055] In some embodiments, the products include but are not limited to: epoxy resin-based products and composite products thereof, polyethylene naphthalate-based products, optical adhesives, optical elements, optical films (e.g., optical films based on cellulose triacetate, polycarbonate, polyacrylate or polyethylene naphthalate), optical lenses, anti-blue light products (e.g., anti-blue light lenses, anti-blue light display devices, etc.), reflective sheets and conformal marking sheets, car windows and their films, car cover films, car paints (e.g., cathode electrophoretic primer coatings and coatings composited therewith), sunlight control films, solar reflectors, reflective printed labels, UV absorbing glass and glass coatings, electrochromic devices, films / glass windows, windshields and intermediate layers, etc.

[0056] In some embodiments, the product is an epoxy reinforced carbon fiber composite material, which includes epoxy reinforced carbon fiber and a coating on its outer layer, wherein the coating includes a resin coating and the above-mentioned compound. Preferably, the coating is selected from at least one of amino acrylic resin coating, hydroxy acrylic resin coating, polyester resin coating, acrylic polyurethane coating, polyurethane resin coating, epoxy modified resin coating, and polysiloxane modified resin coating.

[0057] In some embodiments, the article is an optical film or an optical element, which includes a coating resin substrate and the above compound. Preferably, the resin substrate is selected from at least one of triacetyl cellulose (TAC), polycarbonate, polyacrylate, polyethylene naphthalate, polyethylene terephthalate, polyvinyl alcohol, polymethyl methacrylate, cyclopentene, polyimide, polystyrene and its derivatives, polyvinyl alcohol, epoxy resin, polyurethane, and polysilane.

[0058] In some embodiments, the product is a blue light blocking lens, which includes a resin substrate and the above compound. Preferably, the resin substrate is selected from at least one of aliphatic isocyanate (ADI), polymethyl methacrylate, polycarbonate, polyamide, polymethyl methacrylate, fluorine / silicon modified polyacrylic acid, and polyisocyanate / polythioether.

[0059] In some embodiments, the article is an automotive paint, which includes a cathode electrophoretic primer and a coating compounded therewith, wherein the electrophoretic paint or the coating compounded therewith includes a resin coating and the above-mentioned compound. Preferably, the cathode electrophoretic primer coating is based on epoxy resin, and the cathode electrophoretic primer coating also includes polyester resin, polyurethane resin, epoxy / polyester hybrid resin, acrylic resin, polysiloxane resin, amino acrylic resin, hydroxy acrylic resin, polysiloxane modified resin, epoxy modified resin.

[0060] Another aspect of the present invention provides use of the above compound, the above composition or the above polymer material as an ultraviolet absorber.

[0061] In some embodiments, the compounds of the present invention have a significant red-shift effect and are used in application fields that are sensitive to the 280-430nm ultraviolet-visible band, especially in application fields that have special shielding requirements for the 360-430nm band. The ultraviolet absorber can be used in, for example, epoxy resin-based products and composite products thereof, polyethylene naphthalate-based products, optical adhesives, optical elements, optical films (for example, optical films based on triacetyl cellulose, polycarbonate, polyacrylate or polyethylene naphthalate), optical lenses, anti-blue light products (for example, anti-blue light lenses, anti-blue light display devices, etc.), reflective sheets and conformal marking sheets, car windows and films thereof, car clothing films, automotive paints (for example, cathode electrophoretic primers and coatings composited therewith), sunlight control films, solar reflectors, reflective printed labels, UV absorbing glass and glass coatings, electrochromic devices, films / glass windows, windshields and interlayers, and other fields.

[0062] The above technical solution provided by the present invention has the following advantages:

[0063] (1) Compared with traditional ultraviolet absorbers, the compounds provided by the present invention can shift the absorption in the ultraviolet region to the long-wave direction through novel structural modification, causing a significant red shift in the absorption band, and have good light absorption effect in the visible light band range of 360-430nm.

[0064] (2) The compounds provided by the present invention have excellent solubility in common oligomer resins or active monomers, have better compatibility with the solvent-free cross-linking system used in the preparation of optical devices such as optical films and optical lenses, and have better convenience and stronger operability in processing and use.

[0065] (3) The compounds provided by the present invention also have a lighter color and can be used in light-colored polymer material products.

[0066] (4) The preparation method of the compound provided by the present invention is simple and convenient, and the yield of the target product is high.

[0067] (5) The compounds provided by the present invention are very suitable for use as ultraviolet absorbers in the field of polymer materials. They have excellent protection and shielding effects on visible light in the 280-430nm band, better application performance, and a wider application range. They are helpful for the anti-light aging of polymer materials, and therefore have very important economic and social value. DETAILED DESCRIPTION

[0068] The present invention provides a compound having a structure as shown in formula (I) or formula (II),

[0069]

[0070] Wherein, in formula (I) and formula (II), R1 is selected from C1-C20 straight chain or branched alkyl, R2 is selected from C1-C8 straight chain or branched alkyl, and n is selected from an integer of 1-3.

[0071] The present invention further provides a compound having the structure shown below as RSUV-1 (referred to as RSUV-1 in the present invention) or a compound having the structure shown below as RSUV-2 (referred to as RSUV-2 in the present invention):

[0072]

[0073] The RSUV-1 or RSUV-2 retains the main structure of benzotriazole, introduces a sulfide bond or a sulfone group on one side of its benzene ring, and fixes a substituent on the benzene ring with a hydroxyl group to a methyl group to obtain a modified structure, which moves the absorption region of benzotriazole as an ultraviolet absorber as a whole to the long-wave direction, and the ultraviolet absorption cutoff long-wave wavelength of the modified structure RSUV-2 with a sulfone group is red-shifted from 400-410nm to 430nm in the long-wave direction, and also improves the solubility and compatibility in special systems.

[0074] The compound of the present invention is used for polymer materials sensitive to the ultraviolet visible band of 280-430nm, such as epoxy resin-based products, epoxy-reinforced carbon fiber coatings, polyethylene naphthalate (PEN), PEN copolymers, and modified products.

[0075] The compound of the present invention is also used in application fields with special shielding requirements for the 280-430nm ultraviolet visible band, such as car windows and their films, car clothing films, optical adhesives, optical elements, optical films, automotive coatings and other fields.

[0076] The present invention also provides an epoxy reinforced carbon fiber composite material, which includes epoxy reinforced carbon fiber and a coating on its outer layer, wherein the coating includes a resin coating and the above-mentioned compound; preferably, the coating is selected from at least one of amino acrylic resin coating, hydroxy acrylic resin coating, polyester resin coating, acrylic polyurethane coating, polyurethane resin coating, epoxy modified resin coating, and polysiloxane modified resin coating.

[0077] Carbon fiber is an emerging material that has attracted much attention. Among them, carbon fiber reinforced epoxy resin composite materials are currently the most widely used carbon fiber reinforced materials (CFRM) with the highest comprehensive indicators such as strength and modulus. However, epoxy resin itself is easily damaged by ultraviolet visible light below 420nm, which degrades and affects its performance. Ultraviolet absorbers with high absorption efficiency in the 380-420nm band can effectively protect it.

[0078] Carbon fiber reinforced polymers (CFRP), also known as carbon fiber reinforced materials (CFRM), are used in aerospace applications, for example, due to their high strength / weight ratio. Carbon fiber compositions typically contain carbon fibers embedded in a thermosetting aromatic epoxy matrix. These components are also suitable for automotive parts, sporting goods, acoustic components, ship parts, aircraft parts, etc. The epoxy-reinforced carbon fiber material can be used in interior and exterior parts such as rearview mirrors, tail wings, spoilers, etc.

[0079] Carbon fiber reinforced polymer parts can be prepared, for example, by known molding, vacuum bagging or compression molding techniques. In these methods, prepregs can be used. The polymer matrix can, for example, account for about 15-50% by weight of the carbon fiber reinforced polymer part (uncoated).

[0080] The present invention also provides an optical film or optical element, which includes a resin substrate and the above-mentioned compound; preferably, the resin substrate is selected from at least one of triacetyl cellulose (TAC), polycarbonate, polyacrylate, polyethylene naphthalate, polyethylene terephthalate, polyvinyl alcohol, polymethyl methacrylate, cyclopentene, polyimide, polystyrene and its derivatives, polyvinyl alcohol, epoxy resin, polyurethane, and polysilane.

[0081] If necessary, the optical film or optical device may further include additives such as catalysts such as crosslinking accelerators, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, antistatic agents, dispersion stabilizers, defoamers, thickeners, dispersants, surfactants, lubricants, etc.

[0082] Polyethylene naphthalate (PEN) is a polymer material with excellent comprehensive properties such as chemical stability, mechanical properties, and heat resistance, and has good application prospects in the fields of optical components. However, ultraviolet rays in the 360-400nm band can easily cause damage to PEN and composite materials containing PEN, leading to material degradation. The benzotriazole absorber of the present invention can effectively protect against this problem caused by light. In addition to protecting the substrate of the optical film itself, more importantly, the photosensitive materials in the optical device also need to be protected in a very wide band. For example, the dyes in the polarizer need to be well protected in the ultraviolet band of 280-400nm.

[0083] The present invention also provides a blue light blocking lens, which includes a resin substrate and the above-mentioned compound; preferably, the resin substrate is selected from at least one of aliphatic isocyanate (ADI), polymethyl methacrylate, polycarbonate, polyamide, polymethyl methacrylate, fluorine / silicon modified polyacrylic acid, and polyisocyanate / polythioether.

[0084] Electronic products are used more and more in modern life. The display light source emits a very wide spectrum, among which the high-energy blue light in the 400nm-445nm band can cause certain damage to the user's vision. The benzotriazole derivatives of the present invention can absorb as much of this spectrum as possible to reduce vision damage.

[0085] The present invention also provides an automobile paint, which includes a cathode electrophoretic primer and a coating composited therewith, wherein the cathode electrophoretic primer layer or the coating composited therewith (or adhered thereto) includes a resin coating and the above-mentioned compound; preferably, the cathode electrophoretic primer coating is based on epoxy resin, and the cathode electrophoretic primer coating also includes polyester resin, polyurethane resin, epoxy / polyester hybrid resin, acrylic resin, polysiloxane resin, amino acrylic resin, hydroxy acrylic resin, polysiloxane modified resin, epoxy modified resin.

[0086] The coatings compounded with the cathode electrophoretic primer include clearcoat coating systems, systems of pigmented basecoat and clearcoat, and pigmented single coating systems. Among them, the system of pigmented basecoat and clearcoat can be a process system in which the basecoat is baked separately; or it can be a process system in which the two coatings are baked together by "wet to wet" spraying.

[0087] The resin used in the cathode electrophoretic primer is usually a thermosetting resin used in combination with a crosslinking agent and / or a curing catalyst. Suitable thermosetting resins include epoxy resins, polyester resins, polyurethane resins, epoxy / polyester hybrid resins, acrylic resins, polysiloxane resins, amino acrylic resins, hydroxy acrylic resins, polysiloxane modified resins, and epoxy modified resins.

[0088] Epoxy resins can be cured with dicyandiamide or anhydrides. Hydroxy-functional polyester resins can be cured with polyfunctional isocyanates to form polyurethane polyesters. Acid-functional polyester resins can be cured with isocyanurates. Epoxy polyester hybrids can be cured by reacting with each other. Hydroxy-functional acrylic resins can be cured with polyfunctional isocyanates. The amount of crosslinking agent or curing agent depends on the resin and can be, for example, about 3-20% by weight based on the weight of the resin. Curing is performed, for example, thermally. Acrylate resins are prepared, for example, from glycidyl acrylate or glycidyl methacrylate.

[0089] The present invention provides a coating composition comprising: a coating resin, the above compound, a hindered amine light stabilizer, and optionally a UV absorber, a phenolic antioxidant and an organic or inorganic pigment compound.

[0090] Most advantageously, the coatings of the present invention are clear coatings. In addition to clear coat coatings, the present invention may also be pigmented and tinted coatings. Clear coatings are defined as being substantially free of pigment.

[0091] Other conventional additives may be included in the coating composition, such as fluidizing agents, lubricants, and the like.

[0092] The coating resin is present in the coating formulation in an amount of about 20-98 wt %, preferably about 30-96 wt %, and more preferably about 50-96 wt %, based on the total amount of the coating formulation.

[0093] The preparation and application of coatings are well known. Coating formulations can be applied by spraying (including electrostatic spraying), dipping, or rolling.

[0094] The coating can be applied in one coat to achieve a coating thickness of about 5-200 microns, for example, 20 microns, 40 microns, 50 microns, 60 microns, 80 microns, 100 microns, 120 microns, 150 microns, 180 microns and any value in between; preferably the coating thickness is 10-100 microns, more preferably about 20-40 microns.

[0095] The coatings of the present invention exhibit improved durability and excellent exterior weathering properties.

[0096] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation of the present invention. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concepts of the present disclosure. Such structures and technologies are also described in many publications.

[0097] the term:

[0098] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly used in the field to which the present invention belongs. For the purpose of interpreting this specification, the following definitions will apply, and where appropriate, terms used in the singular will also include the plural form, and vice versa.

[0099] The term "C1-Cn" as used herein includes C1-C2, C1-C3, ... C1-Cn. For example, the "C1-C8" group refers to a group having 1-8 carbon atoms in the moiety, i.e., the group contains 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms or 8 carbon atoms. Thus, for example, "C1-C4 alkyl" refers to an alkyl group containing 1-4 carbon atoms, i.e., the alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0100] Numeric ranges herein, such as "1-3" refer to each integer, ie, 1, 2, or 3, in the given range.

[0101] The term "alkyl" as used herein refers to an optionally substituted straight chain or optionally substituted branched saturated aliphatic hydrocarbon. The "alkyl" herein preferably may have 1-8 carbon atoms, or 1-6 carbon atoms, or 1-5 carbon atoms, or 1-4 carbon atoms, or 1-3 carbon atoms. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl, as well as longer alkyl groups such as heptyl and octyl, etc. When a group defined herein, such as “alkyl”, appears in a numerical range, for example, “C1-C6 alkyl” refers to an alkyl group that may be composed of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms or 6 carbon atoms. The alkyl group herein also includes the case where a numerical range is not specified.

[0102] Sunlight, especially UV radiation from 280 nm to 400 nm, can cause degradation of plastics, which in turn causes color changes and deterioration of optical and mechanical properties. Inhibition of photooxidative degradation is important for outdoor applications where long-term durability is mandatory. For example, the absorption of UV light by polyethylene terephthalate begins around 360 nm, increases significantly below 320 nm, and is very prominent below 300 nm. Polyethylene naphthalate strongly absorbs UV light in the range of 310-370 nm, with an absorption tail extending to about 410 nm and absorption maxima occurring at 352 nm and 337 nm. Chain cleavage occurs in the presence of oxygen, and the main photooxidative products are carbon monoxide, carbon dioxide and carboxylic acids. In addition to the direct photolysis of ester groups, oxidation reactions must also be considered, which likewise form carbon dioxide via peroxide radicals.

[0103] The UV absorbing layer can protect the multilayer optical film by reflecting UV light, absorbing UV light, scattering UV light, or a combination thereof. Generally, the UV absorbing layer can comprise any polymer composition capable of withstanding UV radiation for a long period of time while reflecting, scattering, or absorbing UV radiation. Examples of such polymers include PMMA, CoPMMA, silicone thermoplastics, fluoropolymers, and copolymers thereof, and blends thereof. An exemplary UV absorbing layer comprises a PMMA / PVDF blend.

[0104] Various optional additives may be incorporated into the optical layer to make it absorb UV light. Examples of such additives include at least one of a UV absorber, a hindered amine light stabilizer, or an antioxidant thereof.

[0105] Particularly desirable UV absorbers are red-shifted UV absorbers (RUVAs), which absorb at least 70% (in some embodiments, at least 80%, particularly preferably greater than 90%) of UV light in the wavelength region of 180 nm to 400 nm.

[0106] UV absorbers need to meet the following conditions: good thermal stability, no change due to heat even during processing, low thermal volatility; can strongly absorb ultraviolet rays (especially wavelengths of 290-400nm), good chemical stability, no adverse reactions with material components in the product; good miscibility, can be evenly dispersed in the material, no frost, no seepage; the absorber itself has good photochemical stability, no decomposition, no discoloration; colorless, non-toxic, odorless; resistant to immersion; cheap and easy to obtain. UV absorbers can be divided into the following categories according to their chemical structure: salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines and other categories.

[0107] Ultraviolet absorber UV-326 is one of them. Ultraviolet absorber UV-326 is a benzotriazole light stabilizer, and its chemical name is 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole. UV-326 can absorb ultraviolet rays of 280-370nm, has good stability, low toxicity, and is non-irritating to the human body. It is widely used in coatings, synthetic rubbers, synthetic fibers, photosensitive materials, etc. It can effectively improve the light resistance of these materials and reduce yellowing and aging caused by ultraviolet excitation in sunlight. Ultraviolet absorber UV-326 has the following structure:

[0108]

[0109] Basf's commercially available red-shifted UV absorber Carboprotect also belongs to the benzotriazole (BTZ) class of UV absorbers. It is solid, has a melting point of 132-136°C, and a molecular weight (g / mol): 560. It is a red-shifted UV absorber that protects aromatic hydrocarbon epoxy resin systems; it is recommended for carbon or glass fiber reinforced composites; it can be red-shifted to 420nm wavelength. Carboprotect has the following features:

[0110] BRIEF DESCRIPTION OF THE DRAWINGS

[0111] Figure 1 The synthetic routes of the target products RSUV-1 and RSUV-2 are shown.

[0112] Figure 2 This is the LC-MS spectrum of the target product RSUV-1.

[0113] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the target product RSUV-1.

[0114] Figure 4 This is the LC-MS spectrum of the target product RSUV-2.

[0115] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the target product RSUV-2.

[0116] Example

[0117] The following examples use the following three groups of existing products as comparative products, including:

[0118] ①Comparison product 1: traditional ultraviolet absorber (hereinafter referred to as UV-326);

[0119] ②Comparative product 2: Carboprotect, a red-shifted UV absorber commercially available from Basf Co.;

[0120] ③Comparison product 3: The structure is as follows (hereinafter referred to as EX16)

[0121]

[0122] The reagents used in the examples without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0123] Example 1: Synthesis method

[0124] according to Figure 1 The synthetic route shown in the figure yields two target products, RSUV-1 and RSUV-2. The details are as follows:

[0125] Step 1:

[0126] UV326 (200.0 g, 0.63 mol), dodecyl mercaptan (NDM, 154.5 g, 0.76 mol), potassium carbonate (121.5 g, 0.89 mol) and N,N-dimethylformamide (DMF, 1000 ml) were added to a 2000 ml four-necked round-bottom flask in sequence, and the temperature was raised to reflux. After reacting for 5-7 hours, the raw materials reacted completely and the reaction was terminated; the temperature was lowered to 110-120°C, the inorganic salts in the reaction solution were removed by suction filtration, and the mother liquor was subjected to reduced pressure distillation to evaporate DMF; then 1000 ml of xylene was added to dissolve the material, a small amount of acetic acid was added at 80-90°C, the pH of the solution was adjusted to neutral, and washing water was added for washing, 200 ml each time, and washing was performed 3-4 times; after the reaction was completed, the temperature was raised, and refluxed for dehydration until no more water was evaporated. If the sulfonation product RSUV-2 is to be produced, the product of this step can be directly used for the next step reaction without purification; if the sulfide product RSUV-1 is to be obtained, distill under reduced pressure to remove xylene, then cool to 50°C, add 1000ml of methanol / xylene mixed solution for crystallization, cool to room temperature and keep warm for 3 hours for crystallization, filter and dry to obtain 303.5g of yellow solid powder, with a yield of 97%. LC-MS test results: [M+1] = 482.2, [M-1] = 480.2, the spectrum is as follows Figure 2 The H NMR spectrum is shown in Figure 3 shown.

[0127] Step 2

[0128] The above reflux dehydrated solution was cooled to room temperature, formic acid (66.4g, 1.27mol) and sodium tungstate (catalytic amount) were added, and then hydrogen peroxide (194g, 2.86mol) was added dropwise. After the addition was completed, the temperature was raised to 50-70°C, and the reaction was kept warm for 3-5 hours to terminate the reaction. After standing, the lower aqueous phase was separated, and a small amount of sodium sulfite aqueous solution was added to remove the remaining hydrogen peroxide. Then, the solution was washed with saturated brine and pure water for 3 times each, and the temperature was raised to 110-140°C. The xylene was removed by vacuum distillation, and then the temperature was lowered to 50°C. 1000ml of methanol was added for crystallization, and the temperature was lowered to room temperature and the crystallization was kept warm for 3 hours. After suction filtration and drying, 264g of yellow solid powder was obtained, with a yield of 76%. LC-MS detection results: [M+1] = 514.2, [M-1] = 512.2, the spectrum is as follows Figure 4 The H NMR spectrum is shown in Figure 5 shown.

[0129] Example 2 Absorption spectrum

[0130] Comparative product 1 (UV-326) and RSUV-1 and RSUV-2 prepared by the present invention were dissolved in chloroform respectively, and uniformly prepared into 10 mg / L chloroform solution. The absorption spectrum was tested using an ultraviolet visible spectrophotometer, the instrument model is (UV-2600, Shimadzu Corporation, Japan). The absorption spectrum comparison is shown in Table 1 below.

[0131] Table 1

[0132]

[0133] As can be seen from Table 1, the UV absorbers of the products RSUV-1 and RSUV-2 prepared by the present invention have overall red-shifted to the long-wave direction. Among them, the absorption of RSUV-1 in the 360-450nm band is significantly stronger than that of conventional products (Comparative Product 1). The cutoff wavelength of RSUV-2 is at 430nm, which can provide more anti-light aging protection for sensitive substrates in the 360-430nm band.

[0134] Example 3 Solubility / Compatibility Test

[0135] For many optical devices, such as optical films and optical lenses, a solvent-free cross-linking system is used during production. This system can avoid problems such as reduced precision due to shrinkage and solvent contamination of devices. However, for additives such as UV absorbers, they can only be dissolved by oligomer resins or active monomers. Therefore, there are high requirements for the solubility or compatibility of UV absorbers in these substances.

[0136] The solubility of comparative product 3 (EX16) and RSUV-1 and RSUV-2 prepared by the present invention in typical oligomer resins (cyclohexane dimethylene diisocyanate (H6XDI, purity ≥99.7%, Wanhua Chemical), hexamethylene diisocyanate (HDI) trimer (Desmodur N3300, Covestro), tripropylene glycol diacrylate (≥80% (GC), Aladdin Reagent) was tested.

[0137] Test method: The mass of UV absorber that can be dissolved in 100 grams of oligomer at an ambient temperature of 20°C. The test results are shown in Table 2 below.

[0138] Table 2 Solubility test results

[0139]

[0140] It can be seen from Table 2 that in terms of solubility, compared with the comparative compound EX16, the RSUV-1 and RSUV-2 prepared by the present invention have better solubility as UV absorbers in several typical oligomer resins, and thus have better compatibility with solvent-free cross-linking systems, better convenience in addition and use, and stronger operability.

[0141] Example 4 Color Test

[0142] 2 grams of comparative product 2 (Carboprotect) and RSUV-1 and RSUV-2 prepared by the present invention were dissolved in 18 grams of dimethylformamide (DMF) solvent, and the completely dissolved solution was transferred to a cuvette to test the Gardner color value of the solvent transmission. The instrument was a Ci7600 desktop spectrophotometer (X-rite, USA). The test results are shown in Table 3 below.

[0143] Table 3

[0144] Gardner Chroma Carboprotect 11.5 RSUV-1 3.0 RSUV-2 5.2

[0145] As shown in Table 3, the commercially available red-shifted UV absorber Carboprotect is very dark in color, which has a significant impact on the final products, especially light-colored products. However, the colors of RSUV-1 and RSUV-2 prepared by the present invention as UV absorbers are significantly lighter, especially RSUV-1, so it has a relatively large advantage in application.

[0146] It can be found from Examples 2-4 that, compared with the traditional ultraviolet absorber UV-326, the commercially available red-shifted ultraviolet absorber Carboprotect, and EX16 with a similar structure, the ultraviolet absorber provided by the present invention has significantly better comprehensive properties, especially in terms of light absorption performance, solubility performance, chromaticity, etc., and therefore has a broader application prospect.

[0147] Example 5 Application of UV absorber in epoxy reinforced carbon fiber coating

[0148] This embodiment relates to a coating applied to the surface of epoxy reinforced carbon fiber. The coating is a two-component acrylic varnish system based on isocyanate curing: different ultraviolet absorbers are added to the A component (see Table 4) of the two-component acrylic varnish; Desmodur N3300 (Covestro) is used for the B component. When used, the two components are mixed evenly and sprayed according to the weight percentage of A component: B component = 100:21. Under this ratio, the isocyanate group: hydroxyl group = 1.09:1 in molar calculation.

[0149] Table 4A Component formulation

[0150]

[0151]

[0152] Note: DBTDL (dibutyltin dilaurate) is a catalyst, which is prepared into a 5% methyl amyl ketone solution.

[0153] Test method:

[0154] (1) The coating materials in Table 4 were mixed in the specified proportions and sprayed on epoxy reinforced carbon fiber plates (purchased from Weisheng New Materials Technology Co., Ltd.) with a film thickness of 30-35 μm; baked in an oven at 80°C for 45 minutes until cured into a film; and the test plates were placed at room temperature away from light for one week for testing.

[0155] (2) The test panel was placed in a xenon lamp aging test chamber (model: Atlas Ci4400), and the test standard was referenced to SAEJ2527. The test panel was taken out every 2000 hours to measure the 20-degree gloss of the coating. The colorimeter was: BYK tri-angle gloss meter (model: micro-TRI-gloss). After the test was completed for 6000 hours, the adhesion was tested, and the reference standard was ISO 2409-2013. The test results are shown in Table 5 below.

[0156] Table 5

[0157]

[0158] As shown in Table 5, compared with the traditional UV absorber UV-326, the RSUV-1 and RSUV-2 prepared by the present invention can effectively improve the glossiness and adhesion of the epoxy reinforced carbon fiber coating as UV absorbers. RSUV-1 has a certain improvement in the protective effect compared with UV-326, and the protective effect of RSUV-2 is significantly improved. At the same time, RSUV-2 has a lighter color, less impact on coatings or other polymer products, and can be applied in a wider range of fields.

[0159] Example 6 Application of UV absorber in optical film

[0160] Optical film is a relatively wide application field. As the main carrier substrate of optical film, polymer film needs to have excellent optical properties. Such polymers include triacetyl cellulose (TAC), polycarbonate, polyacrylate, polyethylene naphthalate (PEN), etc. In order to achieve certain optical properties, such as full blocking of the ultraviolet region (280-400nm), or to protect certain special devices from being damaged by ultraviolet light of a specific wavelength (such as the sensitive wavelength of PEN film at 360-400nm as mentioned above), ultraviolet absorbers are usually added. This example examines the ultraviolet blocking performance of ultraviolet absorbers.

[0161] (1) Prepare the ingredients according to the following formula:

[0162]

[0163] (2) Add all materials according to the above formula ratio, seal and stir for 3 hours until a uniform and transparent glue solution is formed. Apply the glue solution into a film, and then put it into a 125°C oven to dry for 30 minutes. A 200 μm TAC film is prepared.

[0164] (3) Testing the UV absorption value of optical film

[0165] The optical film prepared above was cut into test pieces of 25 mm*60 mm, and the absorption spectrum was tested using an ultraviolet visible spectrophotometer (UV-2600, Shimadzu Corporation, Japan). The absorption characteristic values ​​of the optical film are shown in Table 6 below.

[0166] Table 6

[0167]

[0168] It can be seen from Table 6 that RSUV-1 and RSUV-2 prepared by the present invention can better cover the wavelength range required by optical films as ultraviolet absorbers, and at the same time have no negative absorption to higher wavelengths and do not affect normal optical requirements.

[0169] Example 7 Application of UV absorber in anti-blue light lenses

[0170] In the visible light wavelength range, the wavelength region of blue light is 380nm-500nm. Studies have shown that short-wave blue light between 400-455nm is harmful to retinal pigment epithelial cells due to its short wavelength and high energy, and can cause visual damage such as macular degeneration. However, medium- and long-wave blue light between 445-500nm is beneficial blue light because it participates in the mechanism of biological rhythm called "circadian rhythm cycle". If the high-energy blue light between 400-445nm can be shielded in the display or eye lenses, it will bring direct health benefits to users of electronic products. Taking anti-blue light lenses as an example, blue light can generally be effectively filtered by coating and adding blue-violet light absorbers. Although most blue light can be effectively filtered by film reflection, the filtering effect on low-wavelength (380nm-420nm) blue-violet light is relatively limited. Then, red-shifted ultraviolet absorbers with better absorption effect at 380-420nm can play a better anti-blue light effect.

[0171] There are many types of lens resins, including polycarbonate, polymethacrylate, and polyurethane. Among them, polyurethane optical resins have excellent comprehensive performance and are an important development direction of new optical resins in recent years. This example verifies the effect of the red-shifted ultraviolet absorber of the present invention in polyurethane resin.

[0172] (1) Raw material ratio

[0173]

[0174] (2) Lens manufacturing process

[0175] Dibutyltin dichloride, ultraviolet absorber UV-329, test sample, and cyclohexane dimethylene diisocyanate (H6XDI) were added under stirring according to the above formula ratio, and mixed and dissolved.

[0176] After the dissolution is completed, 2,3-dithio (2-mercapto)-1-propanethiol and pentaerythritol tetrakis (3-mercaptopropionic acid) are added, all the materials are stirred and mixed, filtered through a filter membrane, and then injected into a lens-specific mold and degassed under reduced pressure for 1 hour. The molar ratio of NCO to SH groups in the resin is 1:1.

[0177] The degassed liquid resin is placed in an oven and slowly heated to 120°C to polymerize and solidify it. The temperature is maintained at 120°C for 2 hours to fully solidify the resin. After the first solidification, the resin is naturally cooled to room temperature and a secondary solidification is performed at room temperature. After 48 hours, the resin lens is demolded to obtain the resin lens.

[0178] (3) Blue light blocking rate test

[0179] The transmittance of the lenses prepared above was tested in each band with reference to GB / T 38120-2019 "Technical Requirements for Optical Health and Light Safety Application of Blue Light Protection Films". The results are shown in Table 7 below.

[0180] Table 7

[0181]

[0182] It can be seen from Table 7 that after adding the RSUV-2 prepared by the present invention as an ultraviolet absorber, the absorption of the lens in the blue light region is significantly enhanced, and high-energy harmful blue light can be effectively blocked.

[0183] Example 8 Application of UV absorber in cathode electrophoretic paint and its composite coating

[0184] Cathodic electrophoretic paint (Electro-coat) is widely used in industrial equipment, automobiles and other fields, providing excellent corrosion resistance and chemical resistance for metal substrates in these fields. The main resin of the cathode electrophoretic paint generally includes epoxy resin, polyester resin, polyurethane resin, and epoxy / polyester mixed resin. Among them, epoxy esters or epoxy modified resins are the core components. Epoxy resins are very sensitive to ultraviolet rays, not only limited to conventional ultraviolet bands, but even near-ultraviolet bands can cause damage to epoxy resins. The RSUV-2 absorption band provided by the present invention exceeds the coverage wavelength of conventional ultraviolet absorbers, especially in the range of 380-430nm, it can also provide a better ultraviolet shielding effect, and can provide a better protection effect for the cathode electrophoretic paint.

[0185] (1) Raw material ratio

[0186] Select a typical one-component solvent-based varnish (the composition formula is shown in Table 8 below):

[0187] Table 8 Composition of acrylic amino varnish for automobiles

[0188] Material Name blank Control group 1 Experimental Group 1 Setalux 1766 32 32 32 Setalux 1795 10 10 10 Setalux 91795 6.6 6.6 6.6 Setal 168 2.5 2.5 2.5 Cymel 303 2 2 2 Cymel 1168 7 7 7 BYK 378 0.5 0.5 0.5 BYK 306 0.3 0.3 0.3 UV-326 / 1.4 / RSUV-2 / / 1.4 UV-123 / 0.6 0.6 Methyl amyl ketone 6 6 6 Butyl acetate 15.5 14.5 14.5 100# solvent oil 17.4 16.4 16.4 Nacure 5225 0.2 0.2 0.2

[0189] Note: Setalux 1766, Setalux 1795, Setalux 91795, Setal 168: hydroxy acrylic resin, anti-sagging resin, purchased from Allnex Resins (China) Co., Ltd.; Cymel 303, Cymel 1168: amino resin, purchased from Changxin Resins (Guangdong) Co., Ltd.; BYK 378, BYK 306: silicone leveling agent, purchased from BYK Additives (Shanghai) Co., Ltd.; Nacure5225: acid catalyst, purchased from King Industries Inc., USA.

[0190] (2) Test method

[0191] Based on the above acrylic amino varnish formula, different types of light stabilizers were added to obtain the following three groups of test coating samples. The coating test samples were sprayed in the following way: the substrate was uniformly a steel plate with an electrophoretic coating (purchased from ACTTest Panels LLC., USA, specification ECOAT: U32AD800), and the above three groups of varnishes were sprayed respectively, with a film thickness of 40 microns, leveled at room temperature for 10 minutes, and baked in a 140°C oven for 30 minutes.

[0192] The xenon lamp test conditions are as follows: the test panel is placed in a xenon lamp aging test chamber (model: Atlas Ci4400 xenon lamp aging test chamber), and the test standard refers to ISO 11341 (2004). The test panel is taken out every 7 days to test the adhesion of the coating, and the reference standard is ISO 2409-2013. The test results are shown in Table 9 below.

[0193] Table 9 Adhesion test results after xenon lamp aging

[0194] 7 days 14 days 21 days 28 days blank Level 5, most out of / / / Control group 1 Level 1 Level 3 Level 5, most out of / Experimental Group 1 Level 1 Level 1 Level 1 Level 3

[0195] It can be seen from the results in Table 9 that the RSUV-2 prepared by the present invention can maintain the adhesion between the varnish and the cathodic electrophoretic paint for a long time.

[0196] It can be seen from Examples 5-8 that the RSUV-1 and RSUV-2 provided by the present invention can be well utilized as ultraviolet absorbers in various fields, have a wide range of applications, and are highly industrially applicable.

Claims

1. A compound having a structure as shown in formula (I) or formula (II), in, In formula (I) and formula (II), R1 is selected from C1-C20 straight chain or branched alkyl, R2 is selected from C1-C8 straight chain or branched alkyl, and n is selected from an integer of 1-3.

2. The compound according to claim 1, characterized in that The compound has a structure shown in formula (III) or formula (IV), Wherein, in formula (III) and formula (IV), R1 is selected from C1-C20 straight chain or branched chain alkyl, and R2 is selected from C1-C8 straight chain or branched chain alkyl.

3. The compound according to claim 1 or 2, characterized in that In formula (I), formula (II), formula (III) and / or formula (IV), R1 is selected from C5-C20 straight chain or branched chain alkyl, preferably selected from C7-C15 straight chain or branched chain alkyl, R2 is selected from C2-C6 straight chain or branched chain alkyl, Preferably, the compound has the structure shown in RSUV-1 or RSUV-2:

4. The compound according to claim 1, characterized in that The absorption wavelength range of the compound is 280-430 nm.

5. A composition comprising the compound according to any one of claims 1 to 4.

6. The composition according to claim 5, characterized in that The composition further comprises one or more additives; preferably, the additives comprise one or more of hindered amine light stabilizers, other UV absorbers, antioxidants, emulsifiers, nucleating agents, toughening agents, lubricants, opening agents, fillers, dyes, pigments, fluorescent brighteners, flame retardants, antistatic agents or foaming agents.

7. A polymer material, characterized in that: The invention comprises a compound as claimed in any one of claims 1 to 4 or a composition as claimed in claim 5 or 6; and an organic material susceptible to oxygen, heat or light-induced degradation; preferably, the organic material is at least one of polyester, polyurethane, polyacrylic acid, polycarbonate, epoxy and modified resins thereof, phenolic resin, polyamide, polyimide, polystyrene and derivatives thereof, polysilane, polysiloxane and modified resins thereof, poly(vinyl butyral), aminoacrylic acid, hydroxyacrylic acid, acrylic polyurethane, polycyanoacrylate, polyacrylate, ethylene / acrylic acid copolymers and salts thereof (ionomers), poly(vinyl alcohol), cellulose triacetate, polycarbonate, polyethylene naphthalate, polyethylene terephthalate, polyvinyl alcohol, polymethyl methacrylate, polycyclopentene, aliphatic isocyanate, polymethyl methacrylate, fluorine / silicon modified polyacrylic acid, and polyisocyanate / polythioether.

8. A product, comprising the compound according to any one of claims 1 to 4, the composition according to claim 5 or 6, or the polymer material according to claim 7.

9. The product according to claim 8, characterized in that The product is selected from epoxy resin-based and composite products thereof, polyethylene naphthalate-based products, optical adhesives, optical elements, optical films, optical lenses, anti-blue light products, reflective sheets and conformal marking sheets, car windows and films thereof, car cover films, car paints, sunlight control films, solar reflectors, reflective printed labels, UV absorbing glass and glass coatings, electrochromic devices, films / glass windows, windshields or interlayers; Preferably, the product is an epoxy reinforced carbon fiber composite material, which includes epoxy reinforced carbon fiber and a coating on its outer layer, wherein the coating includes a resin coating and a compound according to any one of claims 1 to 4; the coating is preferably selected from at least one of amino acrylic resin coating, hydroxy acrylic resin coating, polyester resin coating, acrylic polyurethane coating, polyurethane resin coating, epoxy modified resin coating, and polysiloxane modified resin coating; Preferably, the article is an optical film or an optical element, which comprises a coating resin substrate and the compound according to any one of claims 1 to 4; the resin substrate is preferably selected from at least one of triacetyl cellulose, polycarbonate, polyacrylate, polyethylene naphthalate, polyethylene terephthalate, polyvinyl alcohol, polymethyl methacrylate, polycyclopentene, polyimide, polystyrene and its derivatives, epoxy resin, polyurethane, and polysilane; Preferably, the product is a blue light blocking lens, which comprises a resin substrate and the compound according to any one of claims 1 to 4; the resin substrate is preferably selected from at least one of aliphatic isocyanate, polymethyl methacrylate, polycarbonate, polyamide, polymethyl methacrylate, fluorine / silicon modified polyacrylic acid, polyisocyanate / polythioether; Preferably, the product is an automotive paint, which includes a cathode electrophoretic primer and a coating composited therewith, wherein the electrophoretic primer or the coating composited therewith includes a resin coating and a compound according to any one of claims 1 to 5; the cathode electrophoretic primer coating is based on epoxy resin, and the cathode electrophoretic primer coating also includes polyester resin, polyurethane resin, epoxy / polyester hybrid resin, acrylic resin, polysiloxane resin, amino acrylic resin, hydroxy acrylic resin, polysiloxane modified resin, and epoxy modified resin.

10. Use of the compound according to any one of claims 1 to 4, the composition according to claim 5 or 6, or the polymer material according to claim 7 as an ultraviolet absorber.

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