Blue-violet light-absorbing composition comprising phenylacrylonitrile compound, preparation method therefor, and product comprising same

Abstract

Provided is a blue-violet light-absorbing composition. The blue-violet light-absorbing composition comprises a polymer and a blue-violet light absorbent, the blue-violet light absorbent being a compound of formula (I) shown below, wherein R1 is a five- or six-membered heterocycloalkyl containing one or two heteroatoms selected from a group consisting of an oxygen atom and a nitrogen atom, which heterocycloalkyl is unsubstituted or substituted with at least one of C1-8 alkyl, -OH, -N＝O, -CN, or halogen; and R2 and R3 are each independently selected from H or C1-8 alkyl. Further provided are a method for preparing the blue-violet light-absorbing composition, a blue-violet light-absorbing product and a preparation method therefor.

Description

Blue-violet light absorbing composition including benzyl acrylonitrile compound, preparation method thereof, and product including the same

Technical field

[0002] The present disclosure relates to a blue-violet light-absorbing composition comprising a phenyl acrylonitrile compound, which can be applied to fields such as optical films and coatings. The present disclosure also relates to a method for preparing the blue-violet light-absorbing composition, a blue-violet light-absorbing product, and a preparation method. [Background Technology]

[0003] Visible light is categorized as red, orange, yellow, green, blue, indigo, and violet. Red light has the longest wavelength, while violet light has the shortest. The shorter the wavelength, the higher the energy. A research report by German ophthalmologist Professor Richard Funk indicates that continuous exposure to "inappropriate light" can cause eye dysfunction, particularly high-energy, short-wavelength blue-violet light with irregular frequencies, such as those emitted by trichromatic lamps and computer screens. This high-energy short-wavelength blue-violet light can penetrate the lens and reach the retina, causing photochemical damage. This can directly or indirectly damage cells in the macula, leading to long-term macular degeneration.

[0004] A high-quality blue-violet light absorber must meet two basic requirements: 1. be able to filter blue-violet light; 2. be inherently light-colored; 3. be resistant to high-temperature processing and operating environments; and 4. have a long optical lifespan. For high-end applications, the absorbance of a blue-violet light absorber for a specific wavelength of blue light must gradually decrease with increasing wavelength, and it must have high penetration at longer wavelengths. For example, an optical lens must have a gradually increasing penetration of blue light from 50% to 100% within the 420nm to 460nm wavelength range to create a better visual experience. Therefore, the requirements for a blue-violet light absorber are extremely stringent. Furthermore, the blue-violet light absorber added to plastics must undergo high-temperature processing or be used outdoors at high temperatures. Therefore, preparing a material that can withstand high-temperature processing is crucial.

[0005] [Summary of the invention]

[0006] This disclosure relates to a blue-violet light-absorbing composition comprising a compound with a specific structure of acrylonitrile, which can be applied in fields such as optical films and coatings. The optical films and coatings are made from a blue-violet light-absorbing polymer that absorbs blue-violet light to protect the eyes and selectively absorbs long-wavelength blue light, resulting in a good visual effect for the penetrating light. The disclosed composition has the unique advantages of being light-colored and absorbing blue-violet light. It can be applied in technical fields such as plastics, coatings, inks, display devices, lighting, optical films, optical lenses, eyewear, textiles, pressure-sensitive adhesives, or sunscreen products. It has particular potential in screen protectors for mobile phones, computers, televisions, and other applications, as well as in eyewear.

[0007] One aspect of the present disclosure provides a blue-violet light absorbing composition comprising a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) shown below:

[0008] wherein R1 is a five-membered or six-membered heterocycloalkyl group containing 1 or 2 heteroatoms selected from the group consisting of oxygen atoms and nitrogen atoms, which is unsubstituted or C 1-8 alkyl, -OH, -N=O, -CN, or halogen; and R2 and R3 are each independently selected from H or C 1-8 alkyl.

[0009] In one embodiment, R1 is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, Oxazolidinyl, isocyanate Oxazolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, 1,2- Azinyl, and 1,3- A group consisting of azininyl.

[0010] In one embodiment, R1 is selected from 4-morpholinyl, 1-piperidinyl, pyrrolidin-1-yl; R2 is selected from H, methyl, ethyl; and R3 is selected from H, methyl, ethyl.

[0011] In one embodiment, the blue-violet light absorber is selected from one of the following compounds or any combination thereof:

[0012] In one embodiment, the polymer is a curable transparent or translucent polymer.

[0013] In one embodiment, the polymer is selected from the group consisting of cellulose ester, polyamide, polyimide, polyurethane, epoxy resin, amino resin, polycarbonate, polyester, polyolefin, acrylic resin, polyoxymethylene, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyethylene oxide, polysilicone, liquid crystal polymer, or any combination thereof.

[0014] In one embodiment, the blue-violet light-absorbing composition further includes one or more additional additives selected from the group consisting of: antistatic agents, defoaming agents, leveling and wetting agents, thickeners, dispersants, waxes, matting agents, antimicrobial agents, metal oxide light-shielding agents, light stabilizers, heat stabilizers, antioxidants, peroxide scavengers, free radical scavengers, fillers, rubbers, food preservatives, flame retardants, plasticizers, dyes, pigments, brighteners, fluorescent whitening agents, anti-aging agents, metal stabilizers, acid absorbers, anti-hydrolysis agents, and any combination of at least two of the foregoing additives.

[0015] In one embodiment, the blue-violet light absorbing composition further comprises one or more additional light absorbers selected from the group consisting of an infrared light absorber, an ultraviolet light absorber, a blue light absorber, and any combination of at least two of the aforementioned light absorbers.

[0016] In one embodiment, the content of the blue-violet light absorber accounts for about 0.01% to about 20% of the total weight of the blue-violet light absorbing composition.

[0017] Another aspect of the present disclosure provides a method for preparing a blue-violet light-absorbing composition, comprising: mixing a polymer and a blue-violet light-absorbing agent represented by formula (I) to obtain the blue-violet light-absorbing composition. In one embodiment, the method for preparing the blue-violet light-absorbing composition comprises mixing about 0.01 to about 20 parts by weight of the blue-violet light-absorbing agent with about 80 to about 100 parts by weight of the polymer.

[0018] In one embodiment, the method further includes heating the polymer to a temperature of about 200° C. to about 280° C. to melt the polymer, and cooling the polymer to solidify the polymer.

[0019] Another aspect of the present disclosure provides a blue-violet light absorbing product, which includes the blue-violet light absorbing composition according to the present disclosure.

[0020] In one embodiment, the blue-violet light absorbing product is selected from plastics, coatings, inks, sunscreens, display devices, lighting devices, optical films, optical lenses, glasses, textiles, and pressure-sensitive adhesives.

[0021] Another aspect of the present disclosure provides a method for preparing a blue-violet light absorbing product, comprising: providing a blue-violet light absorbing composition according to the present disclosure; and disposing the blue-violet light absorbing composition on an article to obtain the blue-violet light absorbing product.

[0022] In one embodiment, the blue-violet light absorbing composition is processed by a method selected from the group consisting of: dipping, granulation, extrusion, laminating, injection molding, calendaring, casting, film blowing, coating, melt blowing, spinning, and any combination thereof.

[0023] [Implementation Method]

[0024] The technical features of this disclosure, including specific features, are disclosed in the claims. For a better understanding of the technical features of this disclosure, the disclosure is described in detail below, along with the specification, embodiments based on the principles of this disclosure, and the accompanying drawings. Furthermore, the contents disclosed in this specification can be understood and implemented by those skilled in the art, and all equivalent changes and modifications that do not depart from the inventive concept are intended to be covered by the claims.

[0025] All technical and scientific terms described in the specification and claims, unless otherwise defined, are definitions that can be known to those with ordinary knowledge in the technical field to which this disclosure belongs. The singular terms "one", "an", "the", or similar terms, unless otherwise specified, can refer to more than one object. "Or", "and", "and" used in this specification, unless otherwise specified, all refer to "or / and". In addition, the terms "including" and "comprising" are not open conjunctions with any restrictions. The above definitions only illustrate the references of the term definitions and should not be interpreted as limitations on the subject matter. Unless otherwise specified, the materials used in this disclosure are all commercially available and easily obtained.

[0026] Any numerical values ​​described herein, such as concentrations or concentration ranges, should be understood as being modified in all instances by the term "about." "About" means within an acceptable error range for the particular value, as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. Unless expressly stated otherwise in the examples or elsewhere in the specification in the context of a particular assay, result, or example, "about" means within one standard deviation, or up to 1%, 2%, 3%, 4%, or 5%, whichever is greater, according to practice in the art.

[0027] According to the present disclosure, "alkyl" refers to an unbranched saturated hydrocarbon chain or a branched saturated hydrocarbon chain. As used herein, an alkyl group has 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), 1 to 4 carbon atoms (i.e., C1-C4 alkyl), or 1 to 3 carbon atoms (i.e., C1-C3 alkyl). Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl. When an alkyl substituent having a particular number of carbon atoms is designated by a chemical name or identified by a molecular formula, all isomers having that number of carbon atoms are included; thus, for example, "propyl" refers to n-propyl (i.e., -(CH2)2CH3)) or isopropyl (i.e., -CH(CH3)2); and "butyl" refers to n-butyl (i.e., -(CH2)3CH3), isobutyl (i.e., -CH2CH(CH3)2), sec-butyl (i.e., -CH(CH3)CH2CH3), or t-butyl (i.e., -C(CH3)3).

[0028] As used herein, the term "heterocycloalkyl" refers to a saturated cyclic alkyl group having one or more heteroatoms independently selected from nitrogen and oxygen. The heterocycloalkyl group may have one or more substituents, for example, selected from alkyl, OH, -N=O, -ONH2, CN, halogen. The heterocycloalkyl group may be a five-membered or six-membered heterocycloalkyl group having 1 nitrogen heteroatom, or 1 oxygen heteroatom, or 1 nitrogen heteroatom and 1 oxygen heteroatom. Therefore, according to the present disclosure, the heterocycloalkyl group includes a ring structure having 1 nitrogen atom and 4 carbon atoms, having 1 oxygen atom and 4 carbon atoms, having 1 nitrogen atom and 1 oxygen atom and 3 carbon atoms, having 1 nitrogen atom and 5 carbon atoms, having 1 oxygen atom and 5 carbon atoms, or having 1 nitrogen atom and 1 oxygen atom and 4 carbon atoms.

[0029] The term "halogen," by itself or as part of another group, refers to fluorine, chlorine, bromine, or iodine.

[0030] The term "cyano" refers to the group -CN.

[0031] As used herein, the term "optionally" means that the subsequently described event or circumstance may or may not occur. The term "optionally substituted" means that any one or more hydrogen atoms on a particular atom or group may or may not be replaced with a moiety other than hydrogen. For example, the compounds of Formula (I) disclosed herein have R1 that is an optionally substituted five- or six-membered heterocycloalkyl group, and optionally substituted R2 and R3.

[0032] The substitutable group may be substituted with one or more substituents (e.g., 1, 2, 3, 4, or 5 substituents). In some embodiments, the substituents are selected from the functional groups provided herein. In some embodiments, the substituents are selected from C 1-8 Alkyl, -OH, -N=O, -ONH2, -CN, and halogen.

[0033] In some embodiments, the substituent is C 1-8 Alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl.

[0034] In some embodiments, the substituent is a halogen, such as fluorine, chlorine, bromine, or iodine.

[0035] Unless otherwise indicated, the compounds disclosed herein include all possible geometric isomers, such as Z and E isomers (cis and trans isomers), and all possible optical isomers of the compounds, such as diastereomers and enantiomers. Therefore, the compounds provided in the embodiments of the present disclosure all include their geometric isomers or optical isomers. In addition, the scope of the present disclosure includes individual isomers and any mixtures thereof, such as racemic mixtures. Individual isomers can be prepared using the corresponding isomers of the starting materials, or they can be separated according to conventional separation methods after preparing the final compound. When separating optical isomers, such as enantiomers, from their mixtures, conventional analytical methods can be used, such as fractional crystallization.

[0036] The term "curable transparent or translucent polymer" herein refers to a polymer that is transparent or translucent after curing. The term "transparent polymer" refers to a polymer that absorbs almost no visible light; the term "translucent polymer" refers to a polymer that only reduces the transmittance of visible light.

[0037] One aspect of the present disclosure provides a blue-violet light absorbing composition comprising a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a phenyl acrylonitrile compound of formula (I) shown below:

[0038] in

[0039] R1 is a five-membered or six-membered heterocycloalkyl group containing 1 or 2 heteroatoms selected from the group consisting of oxygen atoms and nitrogen atoms, which is unsubstituted or C 1-8 Substituted by at least one of alkyl, -OH, -N=O, -ONH2, -CN, or halogen;

[0040] R2 and R3 are each independently selected from H or C 1-8 alkyl.

[0041] Accordingly, the heterocyclic structure of R1 includes 1 oxygen atom, or includes 1 nitrogen atom, or includes 1 oxygen atom and 1 nitrogen atom.

[0042] In one embodiment, R1 is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, Oxazolidinyl, isocyanate isoxazolidinyl, tetrahydropyran, piperidinyl, morpholinyl, 1,2- 1,2-oxazinanyl, and 1,3- The group consisting of 1,3-oxazinanyl.

[0043] In a specific embodiment, R1 is selected from the group consisting of unsubstituted or substituted pyrrolidinyl, piperidinyl, and morpholinyl.

[0044] In further embodiments, R1 is selected from the group consisting of pyrrolidin-1-yl, 1-piperidinyl, and 4-morpholinyl.

[0045] According to this disclosure, C 1-8 Alkyl refers to a straight or branched C 1-8 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl.

[0046] In a specific embodiment, C 1-8 Alkyl groups include straight or branched C 1-4 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, or tertiary butyl. In a specific embodiment, C 1-8 The alkyl group is methyl or ethyl.

[0047] Therefore, in one embodiment, R1 is C 1-8 The alkyl-substituted five-membered or six-membered heterocycloalkyl group is, for example, substituted with at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl.

[0048] In one embodiment, the ring structure of R1 is substituted by halogen, wherein the halogen is selected from fluorine, chlorine, bromine, or iodine.

[0049] In one embodiment, the ring structure of R1 has no substituent. In another embodiment, the ring structure of R1 has at least one substituent, for example, one, two, or three substituents.

[0050] In one embodiment, R2 and R3 are the same or different H or C 1-8 Alkyl, for example, R2 and R3 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl.

[0051] In one embodiment of the compound of formula (I), R1 is a five-membered or six-membered heterocycloalkyl group which is unsubstituted or substituted with at least one methyl or ethyl group, and R2 and R3 are each H, methyl, or ethyl.

[0052] In one embodiment, the blue-violet light absorbing composition includes a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) disclosed herein, wherein R1 is selected from 4-morpholinyl, 1-piperidinyl, pyrrolidin-1-yl; and R2 and R3 are H, methyl, or ethyl, respectively.

[0053] According to this aspect, the compound of formula (I) includes its cis-trans isomers or optical isomers. In one embodiment, the cis-trans isomers of the compound of formula (I) include isomers of formula (Ia) or formula (Ib):

[0054] In a specific embodiment, the compound of formula (I) disclosed herein is selected from any one of the following compounds or their isomers:

[0055] In one embodiment, the blue-violet light absorber of the present invention includes at least one compound covered by formula (I) in any proportion. For example, the blue-violet light absorber includes one, two, three, four, or more compounds covered by formula (I).

[0056] In one embodiment, the blue-violet light absorber absorbs blue-violet light having a wavelength range of 380 nm to 460 nm, particularly 380 nm to 450 nm, more preferably 380 nm to 440 nm, and even more preferably 390 nm to 420 nm.

[0057] In one embodiment, the polymer is a curable transparent or translucent polymer. Preferably, the refractive index of the cured polymer is at least 1.45, more preferably at least 1.5, or more preferably at least 1.6. Preferably, the transparent or translucent polymer has a transmittance greater than 80%, more preferably greater than 90%, more preferably greater than 95%, and most preferably greater than 99%. Furthermore, the polymer preferably has a haze of less than 2%, more preferably less than 1%.

[0058] The polymer is preferably soluble in a solvent. If the polymer is a curable polymer and is soluble in a solvent, the solvent can be removed when the polymer is applied to a substrate, and the polymer can be cured to form a cured blue-violet light absorbing composition. Alternatively, the polymer can be melted and liquefied, then mixed with the blue-violet light absorber, and then cooled to form a cured polymer.

[0059] Curable transparent or translucent polymers useful in the present disclosure include, for example, inorganic materials such as cellulose esters, such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, levulinyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy resins; amino resins; polycarbonates; polyesters, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), poly(1,4-cyclohexane-dimethylene) terephthalate, and polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate.

[0060] -dicarboxylate); polyolefins such as polystyrene, polyethylene, polypropylene, polymethylpentene (PMP), and acrylonitrile-butadiene-styrene copolymer (ABS); polyvinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethacrylate, polymethyl methacrylate, and polyacrylate copolymers; polyoxymethylene; polysulfone; polyethersulfone; polyetherketone; polyetherimide (PEI); polyethylene oxide; polysilicone; liquid crystal polymers, etc.; or any combination thereof.

[0061] Therefore, in one embodiment, the polymer is selected from cellulose ester, polyamide, polyimide, polyurethane, epoxy resin, amino resin, polycarbonate, polyester, polyolefin, acrylic resin, polyoxymethylene, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyethylene oxide, polysilicone, liquid crystal polymer, or any combination thereof.

[0062] In a more preferred embodiment, the polymer is selected from the group consisting of polyurethane, polycarbonate, acrylic resin, and any combination thereof.

[0063] In one embodiment, the blue-violet light-absorbing composition disclosed herein further includes one or more other additives selected from antistatic agents (such as graphene or carbon nanotubes), defoamers, leveling agents, wetting agents, thickeners, dispersants, waxes, matting agents, antimicrobial agents, metal oxide light-shielding agents, light stabilizers, thermal stabilizers, antioxidants (such as phenols, phosphorus-containing oxidants, or thioether oxidants), peroxide scavengers, free radical scavengers, fillers, rubbers (such as silicone rubber), food preservatives, flame retardants, plasticizers, dyes, pigments (such as titanium dioxide or carbon black), brighteners, fluorescent whitening agents, anti-aging agents, metal stabilizers, acid absorbers, anti-hydrolysis agents, and any combination of at least two of the foregoing additives.

[0064] In one embodiment, the blue-violet light absorbing composition disclosed herein further includes other light absorbers, such as infrared light absorbers, ultraviolet light absorbers, blue light absorbers, or other colorants.

[0065] Examples of ultraviolet light absorbers include, but are not limited to, triazine compounds, benzotriazole compounds, diphenyl ketone compounds, merocyanine compounds, cyanine compounds, dibenzoylmethane compounds, cinnamic acid compounds, cyanoacrylate compounds, and benzoate compounds.

[0066] More specific examples of ultraviolet light absorbers include, for example, 2-(2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylbenzene)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylbenzene)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-tert-octylbenzene)benzotriazole, 2-(2′-hydroxy-3′,5′-diisopropylbenzene)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole, 2,2′-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, 2-(2-hydroxy-4-octyloxybenzene)-4,6-di( s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2,4-bis(2-hydroxy-4-octyloxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-s-triazine, 2-hydroxydiphenyl ketone, 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone, and 5,5′-methylenebis(2-hydroxy-4-methoxydiphenyl ketone).

[0067] The UV absorbers may also include compounds disclosed in US Pat. No. 10,894,873 B2 and US Pat. No. 10,717,714 B2, which are incorporated herein by reference in their entirety.

[0068] Examples of infrared light absorbers include, but are not limited to, pentamethine cyanine derivatives, such as pentamethine benzoindolium compounds, pentamethine benzoindolium compounds, Benzoxazolium compounds, and pentamethine benzothiazolium; heptamethine cyanine derivatives, such as heptamethine indole compounds, heptamethine benzindole compounds, heptamethine Azolium compounds, heptamethine benzo azolium compounds, heptamethinethiazolium compounds, and heptamethinebenzothiazolium compounds; diimmonium compounds, aminium compounds, squarylium derivatives; nickel complexes, such as nickel bis(stilbenedithiolato) compounds, nickel bis(benzenedithiolato) compounds, and nickel bis(camphordithiolato) compounds; azo dye derivatives, phthalocyanine derivatives, porphyrin derivatives, and dipyromethene compounds, etc.

[0069] The cured polymer surface can be treated in various ways, such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, UV irradiation, microwave irradiation, glow discharge treatment, active plasma treatment, laser treatment, acid solution treatment, ozone oxidation, or others.

[0070] In one embodiment, the blue-violet light absorber can be added to the blue-violet light absorbing composition in a specific proportion. For example, the content of the blue-violet light absorber is about 0.01% to about 20% of the total weight of the composition, preferably about 0.05% to about 10%, and more preferably about 0.1% to about 5%.

[0071] In a specific embodiment, the blue-violet light-absorbing composition disclosed herein comprises: from about 0.01% to about 20%, preferably from about 0.05% to about 10%, and more preferably from about 0.1% to about 5% of the blue-violet light-absorbing agent, and from about 80% to about 100%, preferably from about 90% to about 100%, and more preferably from about 95% to about 100% of the polymer. Herein, the term "about 100% of the polymer" means that the blue-violet light-absorbing composition contains only a very small amount of the blue-violet light-absorbing agent, for example, from 0.01% to 0.5% of the blue-violet light-absorbing agent, or only 0.01%, 0.05%, 0.1%, or 0.5% of the blue-violet light-absorbing agent. Herein, the percentages (%) represent only the total of the polymer and the blue-violet light-absorbing agent, and do not include other additives.

[0072] Another aspect of the present disclosure provides a method for preparing a blue-violet light absorbing composition, comprising: mixing a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) disclosed herein.

[0073] In one embodiment, the method further comprises heating the polymer to a temperature of about 200° C. to about 280° C. to melt the polymer, and cooling the polymer to solidify the polymer. In a specific embodiment, the polymer has a melting temperature of about 200° C., 210° C., 220° C., 230° C., 240° C., 250° C., 260° C., 270° C., or 280° C.

[0074] In a specific embodiment, the method further includes: providing about 0.01 to about 20 parts by mass, preferably about 0.05 to about 10 parts by mass, more preferably about 0.1 to about 5 parts by mass of the blue-violet light absorber, and about 80 to about 100 parts by mass, preferably about 90 to about 100 parts by mass, more preferably about 95 to about 100 parts by mass of the polymer, and mixing the blue-violet light absorber and the polymer to obtain the blue-violet light absorbing composition.

[0075] Another aspect of the present disclosure provides use of the blue-violet light absorbing composition of the present disclosure for preparing a blue-violet light absorbing product.

[0076] Therefore, another aspect of the present disclosure provides a blue-violet light absorbing product comprising the blue-violet light absorbing composition of the present disclosure.

[0077] In some embodiments, the blue-violet light absorbing product is selected from plastics, coatings, inks, and sunscreens.

[0078] In some embodiments, the blue-violet light absorbing product is selected from a display device, a lighting device, an optical film, an optical lens, glasses (eg, goggles or contact lenses), a textile, and a pressure-sensitive adhesive.

[0079] In some embodiments, the blue-violet light absorbing product is a lens or goggles that blocks blue-violet light and / or UV light, including lenses made of glass and polymer materials, such as polycarbonate (PC), polymethyl methacrylate (PMMA), nylon (PA), polymethylpentene terephthalate TPX (Polymethylpentene), polystyrene, or diethylene glycol dialkyl carbonate resin (PEDC).

[0080] The blue-violet light-absorbing composition disclosed herein can be used as a light-absorbing layer or film in the product. Its thickness varies depending on the desired absorption properties and its placement within the product, and is preferably between 0.1 μm and 100 μm. If the layer or film is too thin, sufficient light-absorbing properties may not be achieved. Conversely, if the layer or film is too thick, it may result in an uneven surface, uneven absorption, or cracking or wrinkling during thermal processing.

[0081] Therefore, in some embodiments, the blue-violet light absorbing product is a display device including a light absorbing layer or a light absorbing film, the blue-violet light emitted by which is absorbed by the blue-violet light absorbing composition disclosed herein, and the display device may be, for example, a liquid crystal display device (LCD), a plasma display device (PDP), an electroluminescent display device (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, and a field emission display device, but is not limited thereto. When applied to a display device, the light absorbing layer or light absorbing film is generally disposed in front of the display device. For example, the light absorbing layer or light absorbing film is directly disposed on the surface of the display device. If a front panel or an electromagnetic shield is disposed in front of the display device, the light absorbing layer or light absorbing film can be bonded to the front (outside) or rear (display device side) of the front panel or electromagnetic shield.

[0082] Another aspect of the present disclosure provides a method for preparing a blue-violet light absorbing product, wherein the blue-violet light absorbing product comprises the blue-violet light absorbing composition of the present disclosure.

[0083] In one embodiment, the method for preparing the blue-violet light absorbing product includes: providing the blue-violet light absorbing composition disclosed herein; and placing the blue-violet light absorbing composition on an object to obtain the blue-violet light absorbing product.

[0084] In another embodiment, the method for preparing a blue-violet light absorbing product includes: mixing a polymer and the blue-violet light absorber disclosed herein to obtain a blue-violet light absorbing composition.

[0085] In some embodiments, the blue-violet light absorbing composition disclosed herein is processed first, for example, the blue-violet light absorbing composition is first granulated or drawn into yarn, or granulated and then drawn into yarn.

[0086] In some embodiments, the blue-violet light absorbing composition disclosed herein is disposed on the article by processing to obtain the blue-violet light absorbing product. The method of disposition includes but is not limited to dip coating, extrusion, lamination, injection molding, calendering, casting, film blowing, coating, melt blowing, or any combination of the foregoing steps.

[0087] Examples

[0088] Preparation of compounds

[0089] Comparative Example 1: Ethyl-2-cyano-3-(4-(dimethylamino)phenyl)acrylate

[0090] Synthesis of ethyl 2-cyano-3-(4-(dimethylamino)phenyl)acrylate: Dissolve 15 g of 4-(dimethylamino)benzaldehyde and 14.5 g of ethyl 2-cyanoacetate in dichloromethane and stir. Add molecular sieves to remove water and install a calcium chloride tube to prevent water leakage. Then, add 1 ml of piperidine and 0.6 ml of acetic acid and heat to reflux for 2 hours, adding fresh molecular sieves during the reaction. After completion of the reaction, remove the solvent, acid-wash, and dry to obtain ethyl 2-cyano-3-(4-(dimethylamino)phenyl)acrylate. Yield: 95%, melting point: 124-127°C, UV-Vis (CH3CN max.): 418 nm, 10% loss by TGA in air: 235°C.

[0091] Comparative Example 2: Ethyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate

[0092] Synthesis of ethyl 2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate: A nitrogen-purged reaction flask was charged with 328 g of diethylaminobenzaldehyde, 251 g of ethyl cyanoacetate, and 500 g of ethanol. 18.7 g of triethylamine was added dropwise at 50°C, and the mixture was heated at 70°C for 2.5 hours. After cooling to room temperature, the precipitated solid was filtered, washed with ethanol, and dried under reduced pressure to obtain ethyl 2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate. This solid was an orange solid with a yield of 93%, a melting point of 96-97°C, a UV absorption peak of 421 nm, and a 10% loss of 252°C by TGA in air.

[0093] Comparative Example 3: Methyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate

[0094] Synthesis of methyl 2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate: A nitrogen-purged reaction flask was charged with 328 g of diethylaminobenzaldehyde, 220 g of methyl cyanoacetate, and 500 g of ethanol. 18.7 g of triethylamine was added dropwise at 50°C, and the mixture was heated at 70°C for 2.5 hours. After cooling to room temperature, the precipitated solid was filtered, washed with ethanol, and dried under reduced pressure to obtain methyl 2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate. This solid was an orange solid with an 81% yield, a melting point of 87-92°C, a UV absorption peak of 423 nm, and a 10% loss by TGA in air of 235°C.

[0095] Example 1: 3-[4-(dimethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile

[0096] Synthesis of 3-[4-(dimethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile: 10 g of ethyl-2-cyano-3-(4-(dimethylamino)phenyl)acrylate (Comparative Example 1) was mixed with 40 g of morpholine and reacted at 130°C for 8 hours. The mixture was then cooled and the solid filtered. The filter cake was then washed with methanol and dried to obtain 3-[4-(dimethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile as a yellow solid with a yield of 67% and a purity greater than 98.8%. The melting point was 112-118°C, the UV absorption peak was 403 nm, and the 10% loss by TGA in air was 298°C.

[0097] NMR analysis:

[0098] 1H NMR (CDCl 3 , 300 MHz) (chemical shift value of peak top in ppm; multiplicity; number of protons): 3.08 (s, 6H), 3.70-3.75 (m, 4H), 6.69 (d, 2H), 7.72 (s, 1H), 7.86 (d, 2H).

[0099] 13C NMR (CDCl3, 125MHz): 40.0, 44.5, 46.1, 66.7, 96.8, 111.5, 118.2, 120.1, 133.0, 134.2, 153.1, 153.7, 165.1.

[0100] Example 2: 3-[4-(Diethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile

[0101] Synthesis of 3-[4-(diethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile: 10 g of ethyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate (Comparative Example 2) was mixed with 40 g of morpholine and reacted at 130°C for 8 hours. The mixture was then cooled and the solid filtered. The filter cake was then washed with methanol and dried to obtain 3-[4-(ethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile. Yield: 28%, purity: greater than 99%, melting point: 88-90°C, UV absorption peak: 403 nm, TGA 10% loss: 291°C.

[0102] NMR analysis:

[0103] 1H NMR (CDCl3, 300MHz): 1.22 (t, 3H), 3.40-3.47 (q, 4H), 3.72 (d, 8H), 6.68 (d, 2H), 7.71 (s, 1H), 7.84 (d, 2H).

[0104] 13C NMR (CDCl3, 125MHz): 12.5, 44.7, 46.3, 66.7, 95.9, 111.2, 118.3, 119.5, 133.3, 150.9, 153.5, 165.2.

[0105] Example 3: 3-[4-(Diethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile

[0106] Synthesis of 3-[4-(diethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile: 10 g of ethyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate (Comparative Example 2) was mixed with 40 g of pyrrolidine and reacted at 90°C for 24 hours. The mixture was then cooled and filtered, and the solid was washed with methanol and dried to obtain 3-[4-(diethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile. Yield: 76%, purity: greater than 99%, melting point: 112-118°C, UV absorption peak: 405 nm, TGA 10% loss: 285°C.

[0107] NMR analysis:

[0108] 1H NMR (CDCl3, 300MHz): 1.20 (t, 4H), 1.91-1.94 (m, 4H), 3.40-3.45 (m, 6H), 3.58 (t, 2H), 3.77 (t, 2H), 6.65 (d, 2H), 7.86 (d, 2H), 7.90 (s, 1H).

[0109] 13C NMR (CDCl3, 125MHz): 12.6, 24.2, 26.8, 44.8, 47.6, 48.7, 97.2, 111.1, 118.6, 119.6, 133.5, 150.9, 153.5, 163.3.

[0110] Example 4: 3-[4-(dimethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile

[0111] Synthesis of 3-[4-(dimethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile: 10 g of ethyl-2-cyano-3-(4-(dimethylamino)phenyl)acrylate (Comparative Example 1) was mixed with 40 g of pyrrolidine and reacted at 90°C for 24 hours. The mixture was then cooled and the solid was filtered. The filter cake was then washed with methanol and dried. After 8 hours of reaction, the mixture was cooled and the solid was filtered. The filter cake was then washed with methanol and dried to obtain 3-[4-(dimethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile. Yield: 90%, purity: greater than 99%, melting point: 118-128°C, UV absorption peak: 395 nm, TGA 10% loss: 281°C.

[0112] NMR analysis:

[0113] 1H NMR (CDCl3, 300MHz): 1.94 (m, 4H), 3.08 (s, 6H), 3.59-3.78 (m, 4H), 6.68 (d, 2H), 7.87 (s, 1H), 7.91 (d, 2H).

[0114] 13C NMR (CDCl3, 125MHz): 24.2, 26.8, 40.0, 47.6, 48.7, 98.1, 111.5, 118.4, 120.2, 131.7, 120.2, 131.7, 133.1, 153.0, 153.5, 163.1.

[0115] Performance Testing

[0116] Thermal stability analysis

[0117] The blue-violet light absorber needs to be added to the plastic and needs to be processed at high temperature or used outdoors at high temperature. However, general blue-violet light absorbing agents cannot withstand high temperatures. Therefore, having a high degree of stability is a very important condition for the blue-violet light absorber. The melting temperature of polycarbonate (PC) is about 250-270°C, so when the plastic processing temperature is high, the TGA (thermogravimetric analysis) change of the blue-violet light absorber is less than 10%, which can effectively avoid the thermal degradation or decomposition of the blue-violet light absorber due to high temperature during the production and processing process, and prevent the loss of blue-violet light absorption function. The compounds of Examples 1-4 and Comparative Examples 1-3 were measured for thermal stability using a thermogravimetric analyzer (TGA), and the temperature of 10% thermal weight loss was tested. The higher the temperature, the better the thermal stability.

[0118] The results are shown in Table 1. The TGA 10% thermal weight loss temperature of the blue-violet light absorbers of Comparative Examples 1 and 3 is 235°C, which cannot be used for thermal processing of polycarbonate (PC). The TGA 10% thermal weight loss temperature of the blue-violet light absorber of Comparative Example 2 only reaches 252°C, and its thermal stability is also poor. The TGA of the compound of Example 1 of the present disclosure reaches 10% thermal weight loss when the temperature is raised to 292°C, which has excellent thermal stability and can be used for thermal processing of polycarbonate. In addition, the TGA 10% thermal weight loss temperatures of Examples 2, 3, and 4 are 291°C, 285°C, and 281°C, respectively, which are all better than Comparative Examples 1 to 3, so they can be used for thermal processing of plastics.

[0119] Table 1. Thermal stability analysis of TGA 10% thermal weight loss

[0120] Blue-violet light absorption analysis

[0121] Blue-violet light ranges from approximately 380 to 460 nm. Shorter wavelengths, higher energy, and greater photochemical damage to the retina. Therefore, a blue-violet light absorber's greater absorption of shorter wavelength blue-violet light (higher energy) between 380 and 420 nm indicates better protection against shorter wavelength blue-violet light. The compounds of Examples 1 to 4 and Comparative Examples 1 to 3 were measured for their maximum absorption peaks using a UV-Vis spectrophotometer.

[0122] Maximum absorption peak test

[0123] UV-Vis spectrophotometer (Varian 50, purchased from Agilent) was used to measure the maximum absorption peak (λmax, nm) of the sample.

[0124] The results are shown in Table 2. The blue-violet light absorbers of Comparative Examples 1 to 3 have maximum absorption peaks of 418 nm, 421 nm, and 423 nm, respectively. These peaks occur at longer wavelengths of blue-violet light. The blue-violet light absorbers of Examples 1 to 4 of the present disclosure have maximum absorption peaks of 403 nm, 403 nm, 405 nm, and 395 nm, respectively. These peaks occur at shorter wavelengths of blue-violet light, indicating better protection against shorter wavelengths of blue-violet light.

[0125] Table 2. UV-Vis maximum absorption peak analysis

[0126] Light life test of blue-violet light-blocking composition and blue-violet light-blocking film

[0127] 30g of CY499 resin containing 1wt% of a blue-violet light absorber and 5.5g of HDT-90B hardener were coated on PET to form a 50μm dry film thickness. Weathering tests were conducted using a xenon lamp (ASTM G155). The shortest wavelength at which light transmittance (T%) reached 1% was measured over time and observed.

[0128] Weathering test-xenon lamp

[0129] The samples were placed in a xenon lamp aging test chamber (model: Q-SUN Xenon Test Chamber, purchased from Q-Lab) and weathering tests were performed under the following conditions: blackboard temperature of 60°C, irradiance of 0.5 W / m2, and 2 )@340 nm.

[0130] Table 3 discloses the 1% transmission wavelength of the blue-violet light blocking films containing the blue-violet light absorbers of Comparative Examples 1 to 3 and Examples 1 to 4 and the negative control group without the blue-violet light absorber.

[0131] The 1% transmission wavelengths of the compounds in each example tested at 0 hours were as follows: Example 1: 442 nm; Example 2: 448 nm; Example 3: 448 nm; Example 4: 435 nm. Compared to Comparative Examples 1 to 3, Examples 1 to 4 absorbed shorter wavelength blue-violet light. After 117 hours of xenon lamp irradiation, the 1% transmission wavelengths of Comparative Examples 1 and 2 declined to 316 nm and 315 nm, respectively, indicating a loss of blue-violet light absorption. After 134 hours of xenon lamp irradiation, the 1% transmission wavelength of Comparative Example 3 declined to 315 nm, indicating a loss of blue-violet light absorption. In contrast, after 134 hours of xenon lamp irradiation, the 1% transmission wavelengths of Examples 1 to 4 of the present disclosure were 393 nm, 413 nm, 411 nm, and 398 nm, respectively, indicating that even after prolonged xenon lamp irradiation, the present examples still maintained excellent blue-violet light protection.

[0132] Table 3. Light life test of blue-violet light-blocking film

[0133] According to the present disclosure, the compound of formula (I) can be mixed with another polymer and used to prepare blue-violet light-absorbing products. Its applications include, but are not limited to, plastics, coatings, inks, display devices, lighting, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, or sunscreen products. In particular, it has potential application prospects in the manufacture of screen protectors for mobile phones, computers, televisions, and other devices, as well as in the manufacture of glasses.

[0134] The embodiments disclosed in this specification are intended to be illustrative and non-limiting. Those skilled in the art will readily appreciate that the embodiments are illustrative only and non-limiting. Those skilled in the art can implement the present disclosure through various modifications and substitutions without departing from the technical features of the present disclosure. Based on the embodiments, the present disclosure can be implemented with various modifications without impeding its implementation. The claims set forth in this specification define the scope of the present disclosure and encompass any equivalent inventions.

Claims

1. A blue-violet light absorbing composition, comprising a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) as shown below: in R1 is a five-membered or six-membered heterocycloalkyl group containing 1 or 2 heteroatoms selected from the group consisting of oxygen atoms and nitrogen atoms, which is unsubstituted or C 1-8 The group is substituted with at least one of alkyl, -OH, -N=O, -CN, or halogen; and R2 and R3 are each independently selected from H or C 1-8 alkyl.

2. The blue-violet light absorbing composition as claimed in claim 1, wherein R1 is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, Oxazolidinyl, isocyanate Oxazolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, 1,2- Azinyl, and 1,3- The group consisting of azininyl.

3. The blue-violet light absorbing composition according to claim 1, wherein R1 is selected from 4-morpholinyl, 1-piperidinyl, or pyrrolidin-1-yl; R2 is selected from H, methyl, or ethyl; and R3 is selected from H, methyl, or ethyl.

4. The blue-violet light absorbing composition as claimed in claim 1, wherein the blue-violet light absorber is selected from any one of the following compounds or any combination thereof:

5. The blue-violet light absorbing composition as claimed in claim 1, wherein the polymer is a curable transparent or semi-transparent polymer.

6. The blue-violet light absorbing composition as claimed in claim 1, wherein the polymer is selected from the group consisting of: cellulose ester, polyamide, polyimide, polyurethane, epoxy resin, amino resin, polycarbonate, polyester, polyolefin, acrylic resin, polyoxymethylene, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyethylene oxide, polysilicone, liquid crystal polymer, and any combination thereof.

7. The blue-violet light absorbing composition as claimed in claim 1, further comprising one or more additional additives selected from the group consisting of: antistatic agent, defoamer, leveling agent, wetting agent, thickener, dispersant, wax, matting agent, antibacterial agent, metal oxide light shielding agent, light stabilizer, heat stabilizer, antioxidant, peroxide scavenger, free radical scavenger, filler, rubber, food preservative, flame retardant, plasticizer, dye, pigment, brightener, fluorescent whitening agent, anti-aging agent, metal stabilizer, acid absorbent, anti-hydrolysis agent, and any combination of at least two of the aforementioned additives.

8. The blue-violet light absorbing composition as claimed in claim 1, further comprising one or more additional light absorbers selected from the group consisting of infrared light absorbers, ultraviolet light absorbers, blue light absorbers, and any combination of at least two of the aforementioned light absorbers.

9. The blue-violet light absorbing composition as claimed in claim 1, wherein the content of the blue-violet light absorber accounts for 0.01% to 20% of the total weight of the blue-violet light absorbing composition.

10. A method for preparing a blue-violet light absorbing composition, comprising: A polymer and a blue-violet light absorber are mixed to obtain the blue-violet light absorbing composition, wherein the blue-violet light absorber is a compound of formula (I) as shown below: in R1 is a five-membered or six-membered heterocycloalkyl group containing 1 or 2 heteroatoms selected from the group consisting of oxygen atoms and nitrogen atoms, which is unsubstituted or C 1-8 At least one of alkyl, -OH, -N=O, -CN, or halogen replaced by; and R2 and R3 are each independently selected from H or C 1-8 alkyl.

11. The method of claim 10, wherein R1 is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, Oxazolidinyl, isocyanate Oxazolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, 1,2- Azinyl, and 1,3- The group consisting of azininyl.

12. The method of claim 10, wherein R1 is selected from 4-morpholinyl, 1-piperidinyl or pyrrolidin-1-yl; R2 is selected from H, methyl or ethyl; and R3 is selected from H, methyl or ethyl.

13. The method of claim 10, wherein the blue-violet light absorber is selected from any one of the following compounds or a combination thereof:

14. The method of claim 10, wherein 0.01 to 20 parts by mass of the blue-violet light absorber is mixed with 80 to 100 parts by mass of the polymer.

15. The method of claim 10, further comprising: The polymer is heated to 200°C to 280°C to melt, and cooled to solidify.

16. A blue-violet light absorbing product, comprising the blue-violet light absorbing composition according to claims 1 to 9.

17. The blue-violet light absorbing product of claim 16, which is selected from the group consisting of plastics, coatings, inks, sunscreens, display devices, lighting devices, optical films, optical lenses, glasses, textiles, and pressure-sensitive adhesives.

18. A method for preparing a blue-violet light absorbing product, comprising: Providing a blue-violet light absorbing composition as described in claims 1 to 9; as well as The blue-violet light absorbing composition is disposed on an article to obtain the blue-violet light absorbing product.

19. The method of claim 18, wherein the blue-violet light absorbing composition is processed by a method selected from the group consisting of: dip coating, granulation, extrusion, lamination, injection molding, calendering, casting, film blowing, coating, melt blowing, drawing, and any combination thereof.

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