TWI866600B - Blue-violet light-absorbing composition comprising phenylacrylonitrile compound, the method of producing the same, and the product comprising the same - Google Patents

Abstract

The present disclosure relates to a composition comprising a phenylacrylonitrile compound of formula (I) for the use in absorbing blue-violet light, the method of producing the same, and the product comprising the same.

Description

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

The present invention relates to a blue-violet light absorbing composition, comprising a phenyl acrylonitrile compound, which can be applied to the fields of optical films and coatings.

Visible light is divided into red, orange, yellow, green, blue, indigo and violet. Red light has the longest wavelength and violet light has the shortest wavelength. The shorter the wavelength, the higher the energy. A research report by Professor R.H.W. Funk, a German ophthalmologist, pointed out that continuous exposure to "inappropriate light" can cause dysfunction in the eyes, especially high-energy short-wave blue-violet light with a large amount of irregular frequencies emitted by trichromatic lamps and computer screens. Short-wave blue-violet light has higher energy and can penetrate the lens directly to the retina, causing photochemical damage to the retina, directly or indirectly causing damage to macular cells, and causing macular degeneration in the long term.

An excellent blue-violet light absorber must have two basic conditions: 1. It can filter blue-violet light and 2. It is light-colored. In addition, it must also have the characteristics of 3. High-temperature processing resistance and high-temperature use environment resistance, and 4. Good light life. In high-end applications, the absorption of blue-violet light absorbers for specific blue light bands needs to gradually decrease with the increase of wavelength, and it must have greater penetration in longer-wavelength blue light. For example, in the wavelength range of 420 nm to 460 nm, the blue light transmitted by optical lenses needs to have a gradually increasing penetration of 50% to 100%, which can create a better visual experience. Therefore, the conditions for being a blue-violet light absorber are extremely strict. In addition, the addition of blue-violet light absorbers to plastics requires high-temperature processing or outdoor high-temperature use. Therefore, it is very important to prepare plastics that are resistant to high-temperature processing.

The present disclosure relates to a blue-violet light absorbing composition, which includes a compound of a specific structure of acrylonitrile, and can be applied to the fields of optical films and coatings. The optical films and coatings are made of blue-violet light absorbing polymers, which can absorb blue-violet light to protect the eyes; they can also selectively absorb long-wavelength blue light so that the penetrating light has a good visual effect. The composition disclosed in the present disclosure has the special advantages of light color and absorption of blue-violet light, and can be applied to technical fields such as plastics, coatings, inks, display devices, lighting, optical films, optical lenses, glasses, textiles, pressure-sensitive adhesives or sunscreen products, especially in the screen protection film or glasses industry of mobile phones, computers, televisions, etc., and has potential application prospects.

One aspect of the present disclosure is a blue-violet light absorbing composition, which includes a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) as shown below: Formula (I) wherein R ₁ 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 substituted with at least one of C _1-8 alkyl, -OH, -N=O, -CN, or halogen; and R ₂ and R ₃ are each independently selected from H or C _1-8 alkyl.

In one embodiment, R ₁ is selected from the group consisting of unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, oxazolidinyl, isoxazolidinyl, tetrahydropyranyl, piperidinyl, oxolinyl, 1,2-oxazolidinyl, and 1,3-oxazolidinyl.

In one embodiment, R ₁ is selected from 4-morpholinyl, 1-piperidinyl, pyrrolidin-1-yl; R ₂ is selected from H, methyl, ethyl; and R ₃ is selected from H, methyl, ethyl.

In one embodiment, the blue-violet light absorber is selected from one or any combination of the following compounds: , , ,and .

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

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, polysilicon, liquid crystal polymer, or any combination thereof.

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 wetting agents, thickeners, dispersants, waxes, matting agents, antibacterial 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 aforementioned additives.

In one embodiment, the blue-violet light absorbing composition further comprises 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.

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.

Another aspect of the present disclosure is a method for preparing a blue-violet light absorbing composition, which includes: mixing a polymer and a blue-violet light absorbing agent as shown in formula (I) to obtain the blue-violet light absorbing composition. In one embodiment, the method for preparing the blue-violet light absorbing composition includes 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.

In one embodiment, the method further comprises: heating the polymer to about 200 ºC to about 280 ºC to melt, and cooling to solidify.

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

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.

Another aspect of the present disclosure is a method for preparing a blue-violet light absorbing product, which includes: providing a blue-violet light absorbing composition according to the present disclosure; and placing the blue-violet light absorbing composition in an article to obtain the blue-violet light absorbing product.

In one embodiment, 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 spraying, spinning, and any combination thereof.

The technical features of the present disclosure, including specific features, are disclosed in the claims. For a better understanding of the technical features of the present disclosure, the present disclosure is described in detail below with the help of the specification, the embodiments based on the principles of the present disclosure, and the drawings. In addition, the contents disclosed in the specification can be understood and implemented by those with ordinary knowledge in the field, and all equivalent changes or modifications that do not deviate from the concept of the invention can be covered by the claims.

Unless otherwise defined, all technical and scientific terms used in the specification and claims are definitions known to those with ordinary knowledge in the technical field to which the present disclosure belongs. The singular terms "one", "an", "the", or similar terms, unless otherwise specified, may refer to more than one object. "Or", "and", and "and" used in this specification refer to "or/and" unless otherwise specified. In addition, the terms "include" and "include" are open conjunctions without 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 the present disclosure are all commercially available and easily available.

Any numerical values such as concentrations or concentration ranges described herein are to 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 otherwise expressly stated in the examples or elsewhere in the specification in the context of a particular assay, result, or embodiment, "about" means within one standard deviation, or up to 1%, 2%, 3%, 4%, or 5%, whichever is greater, according to practice in the art.

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, t-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 carbons is named by chemical name or identified by molecular formula, all isomers having that number of carbons 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 ).

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, -ONH ₂ , CN, halogen. The heterocycloalkyl group may be a five-membered or six-membered heterocycloalkyl group having one nitrogen heteroatom, or one oxygen heteroatom, or one nitrogen heteroatom and one oxygen heteroatom. Therefore, according to the present disclosure, heterocycloalkyl includes ring structures having 1 nitrogen atom and 4 carbon atoms, 1 oxygen atom and 4 carbon atoms, 1 nitrogen atom, 1 oxygen atom and 3 carbon atoms, 1 nitrogen atom and 5 carbon atoms, 1 oxygen atom and 5 carbon atoms, or 1 nitrogen atom, 1 oxygen atom and 4 carbon atoms.

The term "halogen", by itself or as part of another group, means fluorine, chlorine, bromine or iodine.

The term "cyano" refers to the group -CN.

As used herein, the term "optionally" means that the event or situation described subsequently 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 by a moiety other than hydrogen. For example, the compound of formula (I) disclosed herein has R _{1 which} is an optionally substituted five-membered or six-membered heterocycloalkyl group, and R ₂ and R ₃ which are optionally substituted.

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, -ONH ₂ , -CN, and halogen.

In some embodiments, the substituent is a C _1-8 alkyl group, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, 2-ethylhexyl, heptyl, isoheptyl, octyl, or isooctyl.

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

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 disclosed herein 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, such as segmented crystallization, can be used.

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 hardly absorbs any visible light; the term "translucent polymer" refers to a polymer that only reduces the transmittance of visible light.

One aspect of the present disclosure provides a blue-violet light absorbing composition, which includes a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a benzyl acrylonitrile compound of formula (I) as shown below: Formula (I) wherein R ₁ 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 substituted with at least one of C _1-8 alkyl, -OH, -N=O, -ONH ₂ , -CN, or halogen; R ₂ and R ₃ are each independently selected from H or C _1-8 alkyl.

Accordingly, the heterocyclic structure of R ₁ includes 1 oxygen atom, or includes 1 nitrogen atom, or includes 1 oxygen atom and 1 nitrogen atom.

In one embodiment, R ₁ is selected from the group consisting of unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl, oxazolidinyl, isoxazolidinyl, tetrahydropyran, piperidinyl, oxolinyl, 1,2-oxazinanyl, and 1,3-oxazinanyl.

In a specific embodiment, R ₁ is selected from the group consisting of unsubstituted or substituted pyrrolidinyl, piperidinyl, and morpholinyl.

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

According to the present disclosure, _C1-8 alkyl refers to a linear or branched _C1-8 alkyl, examples of which include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, di-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.

In a specific embodiment, C _1-8 alkyl includes linear or branched C _1-4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, or tertiary butyl. In a specific embodiment, C _1-8 alkyl is methyl or ethyl.

Therefore, in one embodiment, _R is a five-membered or six-membered heterocycloalkyl substituted with a C _1-8 alkyl group, for example, substituted with at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a dibutyl group, a tertiary butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a neopentyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, a 3-methylpentyl group, a 2-ethylhexyl group, a heptyl group, an isoheptyl group, an octyl group, or an isooctyl group.

In one embodiment, the ring structure of R ₁ is substituted by a halogen, wherein the halogen is selected from fluorine, chlorine, bromine, or iodine.

In one embodiment, the ring structure of R ₁ has no substituent. In another embodiment, the ring structure of R ₁ has at least one substituent, for example, 1, 2, or 3 substituents.

In one embodiment, _R2 and _R3 are the same or different H or _C1-8 alkyl, for example, _R2 and _R3 are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, di-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.

In one embodiment of the compound of formula (I), R ₁ is a five-membered or six-membered heterocycloalkyl group which is unsubstituted or substituted with at least one methyl or ethyl group, and R ₂ and R ₃ are H, methyl, or ethyl, respectively.

In one embodiment, the blue-violet light absorbing composition comprises a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) disclosed herein, wherein R ₁ is selected from 4-morpholinyl, 1-piperidinyl, pyrrolidin-1-yl; and R ₂ and R ₃ are H, methyl, or ethyl, respectively.

According to the present disclosure, 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): Formula (Ia), Formula (Ib).

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

In one embodiment, the blue-violet light absorber disclosed herein includes at least one compound covered by formula (I) in any ratio. For example, the blue-violet light absorber includes one, two, three, four, or more compounds covered by formula (I).

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

In one embodiment, the polymer is a curable transparent or translucent polymer. Preferably, the refractive index of the polymer after curing is at least 1.45, preferably at least 1.5, or more preferably at least 1.6. Preferably, the light transmittance of the transparent or translucent polymer is higher than 80%, more preferably higher than 90%, more preferably higher than 95%, and most preferably higher than 99%. In addition, the haze of the polymer is preferably less than 2%, more preferably less than 1%.

The polymer is preferably soluble in a solvent. If the polymer is a curable polymer and is soluble in a solvent, when it is applied to a substrate, the solvent can be removed 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 absorbing agent, and then cooled to form a cured polymer.

Curable transparent or translucent polymers that can be used in the present disclosure include, for example, inorganic materials such as cellulose esters, such as diacetyl cellulose, triacetyl cellulose (TAC), propylene cellulose, butyryl cellulose, acetylacetyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxies; amines; polycarbonates; polyesters, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), poly(1,4-cyclohexanedimethylene) terephthalate, and polyethylene-1,2-diphenylene oxide; ethane-4,4′-dicarboxylate (polyethylene-1,2-diphenoxyethane-4,4′-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; polysilicon; liquid crystal polymers, etc.; or any combination thereof.

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, polysilicon, liquid crystal polymer, or any combination thereof.

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

In one embodiment, the blue-violet light absorbing composition disclosed herein further comprises 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, antibacterial agents, metal oxide light shielding agents, light stabilizers, heat stabilizers, antioxidants (such as phenols, phosphorus-containing oxygen Chemical agent, or thioether oxidant), peroxide scavenger, free radical scavenger, filler, rubber (such as silicone rubber), food preservative, flame retardant, plasticizer, dye, pigment (such as titanium white or carbon black, etc.), 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.

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.

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

More specific examples of ultraviolet light absorbers include, for example, 2-(2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-methylbenzene)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylbenzene)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylbenzene)-5-chlorobenzotriazole, -(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( 2,4-dimethylbenzene)-s-triazine, 2-(2-hydroxy-4-hexyloxybenzene)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylbenzene)-4,6-bis(2,4-dimethylbenzene)-s-triazine, 2-(2-hydroxy-4-hexyloxybenzene)-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).

The ultraviolet light absorber may also include compounds disclosed in US Pat. No. 10,894,873 B2 and US Pat. No. 10,717,714 B2, the entire contents of which are incorporated herein by reference.

Examples of infrared light absorbers include, but are not limited to, pentamethine cyanine derivatives, such as benzoindolium compounds, benzoxazolium compounds, and benzothiazolium; heptamethine cyanine; The invention also includes a plurality of nickel compounds, such as heptamethine indolium compounds, heptamethine benzindolium compounds, heptamethine oxazolium compounds, heptamethine benzooxazolium compounds, heptamethine thiazolium compounds, and heptamethine benzothiazolium compounds; diimmonium compounds, aminium compounds, and squarylium derivatives; nickel complexes, such as bis(stilbenedithiolato) nickel compounds, bis(benzenedithiolato) nickel compounds, and bis(camphordithiolato) nickel compounds; azo dye derivatives, phthalocyanine derivatives, porphyrin derivatives, and dipyromethene compounds.

The cured polymer surface can be treated in a variety of ways, such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet light irradiation, microwave irradiation, fluorescent discharge treatment, active plasma treatment, laser treatment, acid solution treatment, ozone oxidation, or others.

In one embodiment, the blue-violet light absorber can be added to the blue-violet light absorbing composition in a specific ratio, for example, the content of the blue-violet light absorber accounts for 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%.

In a specific embodiment, the blue-violet light absorbing composition disclosed herein includes: about 0.01% to about 20%, preferably about 0.05% to about 10%, more preferably about 0.1% to about 5% of the blue-violet light absorbing agent, and about 80% to about 100%, preferably about 90% to about 100%, more preferably about 95% to about 100% of the polymer. Here, the term "about 100% of the polymer" means that the blue-violet light absorbing composition contains only a very small amount of blue-violet light absorbing agent, for example, only 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. Here, the percentage (%) only represents the total of the polymer and the blue-violet light absorbing agent, and does not include other additives.

Another aspect of the present disclosure is to provide a method for preparing a blue-violet light absorbing composition, which comprises: mixing a polymer and a blue-violet light absorber, wherein the blue-violet light absorber is a compound of formula (I) of the present disclosure.

In one embodiment, the method further comprises: heating the polymer to about 200 ºC to about 280 ºC to melt, and cooling to solidify. In a specific embodiment, the melting temperature of the polymer is about 200 ºC, 210 ºC, 220 ºC, 230 ºC, 240 ºC, 250 ºC, 260 ºC, 270 ºC, or 280 ºC.

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, and 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, and 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.

Another aspect of the present disclosure is to provide the use of the blue-violet light absorbing composition of the present disclosure for preparing a blue-violet light absorbing product.

Therefore, another aspect of the present disclosure is to provide a blue-violet light absorbing product comprising the blue-violet light absorbing composition of the present disclosure.

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

In some embodiments, the blue-violet light absorbing product is selected from display devices, lighting devices, optical films, optical lenses, glasses (e.g., goggles or contact lenses), textiles, and pressure-sensitive adhesives.

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

The blue-violet light absorbing composition disclosed herein can be a light absorbing layer or a light absorbing film in the product, and its thickness varies according to the required absorption properties or the location in the product, preferably 0.1 μm to 100 μm. If the layer or film is too thin, the light absorbing performance cannot be fully obtained; on the contrary, if the layer or film is too thick, it may lead to uneven surface, uneven absorption, or brittle cracks or wrinkles during thermal processing.

Therefore, in some embodiments, the blue-violet light absorbing product is a display device including a light absorbing layer or a light absorbing film, and the blue-violet light emitted by the display device is absorbed by the blue-violet light absorbing composition disclosed herein. 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 the light absorbing film is generally disposed in front of the display device. For example, the light absorbing layer or the light absorbing film is directly disposed on the surface of the display device. If there is a front panel or an electromagnetic shield disposed in front of the display device, the light absorbing layer or the light absorbing film can be bonded to the front (outside) or rear (display device side) of the front panel or the electromagnetic shield.

Another aspect of the present disclosure is to provide 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.

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 in an object to obtain the blue-violet light absorbing product.

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

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, or granulated and then drawn.

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 disposing includes but is not limited to dip coating, extrusion, lamination, injection molding, calendering, casting, film blowing, coating, melt spraying, or any combination of the above steps. Preparation of Example Compounds

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

Synthesis of compound ethyl-2-cyano-3-(4-(dimethylamino)phenyl)acrylate: Dissolve 15g of 4-(dimethylamino)benzaldehyde and 14.5g of ethyl 2-cyanoacetate in dichloromethane and stir, add molecular sieve to remove water and install calcium chloride tube to prevent water. Then add 1ml piperidine and 0.6ml acetic acid, heat to reflux temperature for 2 hours, and add fresh molecular sieve during the reaction. After the reaction is completed, remove the solvent, acid wash, and dry to obtain ethyl-2-cyano-3-(4-(dimethylamino)phenyl)acrylate. Yield: 95%, melting point: 124-127ºC, UV-Vis (CH ₃ CN max.): 418 nm, 10% loss of TGA in air: 235ºC.

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

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

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

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

Example 1 : 3-[4-(dimethylamino)phenyl]-2-(oxoline-4-carbonyl)prop-2-enenitrile 3-[4-(Dimethylamino)phenyl]-2-(pyroline-4-carbonyl)prop-2-enenitrile

Synthesis of compound 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) and 40 g of morpholine were mixed and reacted at 130°C for 8.0 hours, then the temperature was lowered and the solid was filtered. The filter cake was then washed with methanol and dried to obtain 3-[4-(dimethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile. Yellow solid, yield: 67%, purity: greater than 98.8%, melting point: 112-118°C, UV absorption peak: 403nm, 10% loss of TGA in air: 298°C.

NMR analysis: 1H NMR (CDCl3, 300 MHz) (chemical shift value of peak top 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) 13C NMR (CDCl3, 125 MHz): 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

Example 2 : 3-[4-(Diethylamino)phenyl]-2-(oxoline-4-carbonyl)prop-2-enenitrile 3-[4-(Diethylamino)phenyl]-2-(pyroline-4-carbonyl)prop-2-enenitrile

Synthesis of compound 3-[4-(diethylamino)phenyl]-2-(morpholine-4-carbonyl)prop-2-enenitrile: 10g of ethyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate (Comparative Example 2) and 40g of morpholine were mixed and reacted at 130ºC for 8.0 hours, then the temperature was lowered and the solid was 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: 88~90ºC, UV absorption peak: 403nm, 10% loss of TGA: 291ºC.

NMR analysis: 1H NMR (CDCl3, 300 MHz): 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) 13C NMR (CDCl3, 125 MHz): 12.5, 44.7, 46.3, 66.7, 95.9, 111.2, 118.3, 119.5, 133.3, 150.9, 153.5, 165.2

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

Synthesis of compound 3-[4-(diethylamino)phenyl]-2-(pyrrolidine-4-carbonyl)prop-2-enenitrile: 10g of ethyl-2-cyano-3-(4-(ethylmethylamino)phenyl)acrylate (Comparative Example 2) was mixed with 40g of pyrrolidine and reacted at 90ºC for 24 hours, then the solid was filtered after cooling, and then the filter cake 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: 112~118ºC, UV absorption peak: 405nm, 10% loss of TGA: 285ºC.

NMR analysis: 1H NMR (CDCl3, 300 MHz): 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) 13C NMR (CDCl3, 125 MHz): 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

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

Synthesis of compound 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, then cooled and filtered, and then the filter cake was washed with methanol and dried. After reacting for 8.0 hours, the solid was cooled and filtered, and then the filter cake was 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: 118~128ºC, UV absorption peak: 395nm, 10% loss of TGA: 281ºC.

NMR analysis: 1H NMR (CDCl3, 300 MHz): 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) 13C NMR (CDCl3, 125 MHz): 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, 163.1Performance test

Thermal stability analysis

The blue-violet light absorber added to the plastic needs to be processed at high temperature or used at high temperature outdoors. However, general blue-violet light absorbers 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 250-270ºC, 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 blue-violet light absorber from thermal degradation or decomposition due to high temperature during the production process, and prevent the loss of blue-violet light absorption function. The thermal stability of the compounds of Example 1-4 and the compounds of Comparative Example 1-3 was measured in a thermogravimetric analyzer (TGA), and the temperature of 10% thermal weight loss was checked. The higher the temperature, the better the thermal stability.

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

Table 1. Thermal stability analysis of TGA 10% thermal weight loss Test Results Comparison Example 1 Comparison Example 2 Comparison Example 3 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 TGA-10% temperature 235°C 252°C 235°C 292°C 291°C 285°C 281°C

Blue-violet light absorption analysis

The range of blue-violet light is between about 380-460nm. The shorter the wavelength, the higher the energy, and the greater the photochemical damage to the retina. Therefore, the greater the absorption of blue-violet light absorbers for shorter wavelength blue-violet light (higher energy) between 380-420nm, the better the protective effect against shorter wavelength blue-violet light. The maximum absorption peak of the compounds of Examples 1 to 4 and the compounds of Comparative Examples 1 to 3 was measured on a UV-Vis spectrophotometer.

Maximum absorption peak test

A UV-Vis spectrophotometer (model: Varian Cary® 50, purchased from Agilent) was used to measure the maximum absorption peak (λmax, nm) of the samples.

The results are shown in Table 2. The maximum absorption peaks of the blue-violet light absorbers of Comparative Examples 1 to 3 are 418nm, 421nm, and 423nm, respectively, and the peak values of the maximum absorption peaks are blue-violet light with a longer wavelength. The maximum absorption peaks of the blue-violet light absorbers of Examples 1 to 4 of the present disclosure are 403nm, 403nm, 405nm, and 395nm, respectively, and the peak values of the maximum absorption peaks are blue-violet light with a shorter wavelength, indicating that the protection effect against blue-violet light with a shorter wavelength is better.

Table 2. UV-Vis maximum absorption peak analysis Test Results Comparison Example 1 Comparison Example 2 Comparison Example 3 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 λmax, nm 418 421 423 403 403 405 395

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

30 g of CY499 resin containing 1 wt% blue-violet light absorber and 5.5 g of HDT-90B hardener were coated on PET to prepare a coating with a dry film thickness of 50 μm. A weathering test was performed using a xenon lamp (ASTM G155). The shortest wavelength at which the light transmittance (T%) = 1% was continuously measured and observed over time.

Weathering test-Xenon lamp

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

Table 3 discloses the 1% penetration wavelength of the blue-violet light-proof film 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.

The 1% penetration wavelength of each example compound tested at 0 hours is as follows: Example 1: 442nm; Example 2: 448nm; Example 3: 448nm; Example 4: 435nm. Compared with Comparative Examples 1 to 3, Examples 1 to 4 absorb shorter wavelength blue-violet light. After 117 hours of xenon lamp irradiation, the 1% penetration wavelength test of Comparative Examples 1 and 2 decayed to 316nm and 315nm, and the blue-violet light absorption function was lost; after 134 hours of xenon lamp irradiation, the 1% penetration wavelength test of Comparative Example 3 decayed to 315nm, and the blue-violet light absorption function was lost. In contrast, after 134 hours of xenon lamp irradiation, the 1% penetration wavelengths of Examples 1 to 4 of the present disclosure were tested to be 393nm, 413nm, 411nm, and 398nm, respectively, indicating that after long-term xenon lamp irradiation, the present disclosure Examples still maintain excellent blue-violet light protection effects.

Table 3. Light life test of blue-violet light protection film Time/1% shortest penetration wavelength (nm) Negative control group Comparison Example 1 Comparison Example 2 Comparison Example 3 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 0hr 316 457 462 462 442 448 448 435 68hr 316 444 453 454 414 426 420 412 94hr 316 433 444 448 406 419 419 408 117hr 316 316 315 437 401 416 414 401 134hr 316 - - 315 393 413 411 398 Evaluation - X X X O O O O

According to the present disclosure, the compound of formula (I) can be mixed with another polymer and used to prepare a blue-violet light absorbing product, and its application includes but is not limited to plastics, coatings, inks, display devices, lighting, optical films, optical lenses, goggles, glasses, contact lenses, textiles, pressure-sensitive adhesives, or sunscreen products, especially in the manufacture of screen protective films or glasses for mobile phones, computers, televisions, etc., and therefore has potential application prospects.

In the contents disclosed in the embodiments of this specification, it is obvious to those with ordinary knowledge in the field to which this disclosure belongs that the aforementioned embodiments are only illustrative and not limiting; those with ordinary knowledge in the technical field to which this disclosure belongs can implement it through many changes and substitutions, which do not differ from the technical features of this disclosure. According to the embodiments of the specification, this disclosure can be implemented in many ways without hindering its implementation. The claims provided in this specification define the scope of this disclosure and cover inventions equivalent to them.

without

Claims (18)

A blue-violet light absorbing composition comprises a polymer and a blue-violet light absorbing agent, wherein the blue-violet light absorbing agent is a compound of formula (I) as shown below:

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 substituted by 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; 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, polyoxyethylene, polysilicon, liquid crystal polymer, and any combination thereof. The blue-violet light absorbing composition of claim 1, wherein R ₁ is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl,

Oxazolidinyl, isocyanate

Oxazolidinyl, tetrahydropyranyl, piperidinyl, oxolinyl, 1,2-

Alkyl, and 1,3-

A group composed of alkyl groups. The blue-violet light absorbing composition of claim 1, wherein R ₁ is selected from 4-morpholinyl, 1-piperidinyl, or pyrrolidin-1-yl; R ₂ is selected from H, methyl, or ethyl; and R ₃ is selected from H, methyl, or ethyl. The blue-violet light absorbing composition of claim 1, wherein the blue-violet light absorber is selected from any one of the following compounds or any combination thereof:

As claimed in claim 1, the blue-violet light absorbing composition, wherein the polymer is a curable transparent or translucent polymer. The blue-violet light absorbing composition of claim 1 further comprises one or more additional additives selected from the group consisting of: antistatic agent, defoaming agent, 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. The blue-violet light absorbing composition of claim 1 further comprises 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. As in claim 1, the content of the blue-violet light absorbing composition is 0.01% to 20% of the total weight of the blue-violet light absorbing composition. A method for preparing a blue-violet light absorbing composition comprises: mixing a polymer and a blue-violet light absorbing agent to obtain the blue-violet light absorbing composition, wherein the blue-violet light absorbing agent is a compound of formula (I) as shown below:

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 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. The method of claim 9, wherein R ₁ is selected from unsubstituted or substituted pyrrolidinyl, tetrahydrofuranyl,

Oxazolidinyl, isocyanate

Oxazolidinyl, tetrahydropyranyl, piperidinyl, oxolinyl, 1,2-

Alkyl, and 1,3-

A group composed of alkyl groups. The method of claim 9, wherein R ₁ is selected from 4-morpholinyl, 1-piperidinyl or pyrrolidin-1-yl; R ₂ is selected from H, methyl or ethyl; and R ₃ is selected from H, methyl or ethyl. The method of claim 9, wherein the blue-violet light absorber is selected from any one of the following compounds or a combination thereof:

The method of claim 9, wherein 0.01 to 20 parts by weight of the blue-violet light absorber is mixed with 80 to 100 parts by weight of the polymer. The method of claim 9 further comprises: heating the polymer to 200°C to 280°C to melt it, and cooling it to solidify it. A blue-violet light absorbing product, which includes the blue-violet light absorbing composition as claimed in claims 1 to 8. The blue-violet light absorbing product of claim 15 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. A method for preparing a blue-violet light absorbing product, comprising: providing a blue-violet light absorbing composition as claimed in claims 1 to 8; and placing the blue-violet light absorbing composition on an article to obtain the blue-violet light absorbing product. The method of claim 17, 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 spraying, spinning, and any combination of the foregoing.