Light absorber

Abstract

Provided is a light absorber that exhibits exceptionally superior heat resistance and absorption of light having a wavelength of about 410 nm as compared with conventional ultraviolet absorbers.　A light absorber according to the present invention comprises a 2-phenylbenzotriazole derivative which has two or more sulfur-containing groups and in which a sulfur atom of each of the sulfur-containing groups is bonded to a phenyl group or benzotriazole.

Description

Light absorber

[0001] This invention relates to a light absorber comprising a benzotriazole compound.

[0002] Resin components degrade under the influence of ultraviolet light, causing discoloration, reduced mechanical strength, and other quality deteriorations that hinder long-term use. To prevent such quality deterioration or to control the wavelength of transmitted light, it is common practice to incorporate ultraviolet absorbers into resin components.

[0003] Ultraviolet absorbers are substances that possess the ability to absorb ultraviolet light and are effective in preventing the degradation of various organic materials caused by ultraviolet radiation. Ultraviolet light is one of the causes of various types of degradation, such as fading or weakening, in paints, polymer resins (films for electronic materials, optical lenses, automobile parts, etc.), dyes, and textiles. It also causes damage to the human body, such as skin aging like sunburn and hair weakening. For these reasons, ultraviolet absorbers are applied in a wide range of fields, including cosmetics, pharmaceuticals, polymer compositions (films for electronic materials, optical lenses, automobile parts, etc.), food, paints, and photography.

[0004] Furthermore, in recent years, it has been pointed out that not only ultraviolet light below 250-400 nm in sunlight, but also light in the short-wavelength visible light range of approximately 400-420 nm, can damage organic matter and the human body. Regarding its effects on the human body, it has been found that light in the short-wavelength visible light range penetrates deep into the skin, causing not only skin aging but also inducing skin cancer. In addition, the light sources used in electronic image display devices, which have become widespread in recent years, are being replaced from cold cathode fluorescent lamps to LEDs from the perspective of energy saving. Compared to cold cathode fluorescent lamps, these LED backlights have a higher intensity of light with wavelengths around 385-495 nm, so-called blue light. It has been pointed out that this blue light may cause symptoms such as eye strain and dry eyes in people who look at display devices for long periods of time. In particular, the short-wavelength band from 380 nm to 420 nm, known as high-energy visible light (HEV), is prone to damaging lutein, a pigment in the eye, and is said to potentially be one of the causes of age-related macular degeneration in the long term. Therefore, it is considered important to cut out this band, and there is a demand for light absorbers that can absorb light in the short-wavelength range of visible light.

[0005] Conventionally, known organic ultraviolet absorbers include benzotriazole, benzophenone, triazine, cyanoacrylate, and salicylate types. The present inventors have proposed a 2-phenylbenzotriazole derivative having a sulfur-containing group as an ultraviolet absorber that efficiently and sufficiently absorbs harmful light up to around 380-400 nm and suppresses the absorption of light with wavelengths above 400 nm, which is a cause of initial yellowing (Patent Documents 1-4). This 2-phenylbenzotriazole derivative is particularly effective at sufficiently absorbing light with wavelengths around 400-420 nm and suppressing the absorption of light with wavelengths longer than 420 nm, thereby suppressing the yellowing of the resin.

[0006] International Publication No. 2016 / 021664, International Publication No. 2016 / 174788, International Publication No. 2019 / 087983, International Publication No. 2020 / 137819

[0007] Patent documents 1 to 4 disclose 2-phenylbenzotriazole derivatives having a sulfur-containing group in which a sulfur atom is bonded to a hydrocarbon group such as an aliphatic or aromatic group, but there was room for improvement in the absorption of light around 410 nm. Therefore, there is a need for a light absorber that has excellent absorption ability even for light around 410 nm.

[0008] This invention has been made in view of the above circumstances, and aims to provide a light absorber that is particularly superior to conventional ultraviolet absorbers in terms of heat resistance and absorption of light around a wavelength of 410 nm.

[0009] The inventors diligently conducted research to solve the above problems. As a result, they discovered that by introducing multiple sulfur-containing groups into the molecular structure of a 2-phenylbenzotriazole derivative, the absorption wavelength shifts significantly to longer wavelengths, making it possible to absorb light in a longer wavelength region, thus completing the present invention. That is, the light absorber of the present invention is characterized by having two or more sulfur-containing groups and consisting of a 2-phenylbenzotriazole derivative in which the sulfur atoms of the sulfur-containing groups are bonded to a benzotriazole or phenyl group. The composition of the present invention is characterized by comprising the light absorber and an organic material and / or an inorganic material. The method of imparting light absorption ability of the present invention is characterized by adding the light absorber to an organic material and / or inorganic material composition to impart light absorption ability including a wavelength of 410 nm to the composition.

[0010] The light absorber of the present invention has a shift in absorption wavelength to longer wavelengths compared to conventional ultraviolet absorbers, making it possible to effectively cut light around 410 nm. Furthermore, it has a high molar extinction coefficient, allowing for efficient light absorption even in small amounts. It also exhibits excellent heat resistance. According to the composition and method for imparting light absorption ability of the present invention, using the light absorber makes it possible to effectively cut light around 410 nm. Moreover, the light absorber has a high molar extinction coefficient, allowing for efficient light absorption even in small amounts.

[0011] These are the ultraviolet-visible absorption spectra (UV charts) of Compound 1 and Compound 2, which are examples of the present invention, and Compound 3 and Compound 4, which are comparative examples.

[0012] The present invention will be described in detail below. [Substituents, etc.] In the present invention, "monovalent or divalent groups selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms" include groups that can adjust heat resistance, refractive index, melting point, stability, light resistance, compatibility with resins, etc., and examples include the following.

[0013] Examples of hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and groups combining these. Examples of aliphatic hydrocarbon groups include linear or branched alkyl groups, linear or branched alkenyl groups, and linear or branched alkynyl groups. Examples of aromatic hydrocarbon groups include groups containing aromatic rings such as benzene rings, naphthalene rings, and anthracene rings. The number of carbon atoms in aromatic hydrocarbon groups is not particularly limited, but is preferably 6 to 18, more preferably 6 to 14. Examples of alicyclic hydrocarbon groups include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, and groups containing these as a skeleton. The number of carbon atoms in alicyclic hydrocarbon groups is not particularly limited, but is preferably 3 to 10, more preferably 3 to 8.

[0014] Unsaturated groups include carbon-carbon or carbon-heteroatom unsaturated bonds such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds (carbonyl group, aldehyde group, ester group, carboxyl group, carbamate group, urea group, amide group, imide group, carbamoyl group, urethane group, etc.), carbon-nitrogen double bonds (isocyanate group, etc.), and carbon-nitrogen triple bonds (cyano group, cyanate group, etc.). Unsaturated groups are not particularly limited, but examples include acryloyl group, metacroyl group, maleic acid monoester group, styryl group, allyl group, vinyl group, alkenyl group, alkynyl group, carbonyl group, aldehyde group, ester group, carboxyl group, carbamate group, urea group, amide group, imide group, carbamoyl group, acrylonitrile group, cyano group, cyanate group, isocyanate group, and urethane group. The number of carbon atoms in the unsaturated group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 8.

[0015] The nitrogen-containing group includes a cyano group, a nitro group, or a primary to tertiary amino group, and preferably has 0 to 18 carbon atoms. The nitrogen-containing group is not particularly limited, but examples include cyano group, cyanato group, isocyanate group, nitro group, nitroalkyl group, amide group, urea group, urethane group, imide group, carbodiimide group, azo group, pyridine group, imidazole group, benzotriazole group, 2-phenylbenzotriazole group, triazine group, amino group, primary amino group, secondary amino group, tertiary amino group, aminoalkyl group, 3,4,5,6-tetrahydrophthalimidylmethyl group, and groups containing these.

[0016] The sulfur-containing group includes a thiol group, thioether group, sulfide group, disulfide group, thioester group, thioamide group, sulfonyl group, sulfo group, thiocarbonyl group, or thiourea group, and preferably has 0 to 10 carbon atoms. The sulfur-containing group is not particularly limited, but examples include a thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n-butoxy group, thio-t-butoxy group, thiophenoxy group, p-methylthiophenoxy group, p-methoxythiophenoxy group, thiophene group, thiazole group, thiol group, thioether group, sulfo group, sulfide group, disulfide group, thioester group, thioamide group, sulfonyl group, thiocarbonyl group, thiourea group, thiocarbamate group, dithiocarbamate group, and groups containing these.

[0017] The oxygen-containing group preferably has 6 to 12 carbon atoms if it includes an aromatic ring group or an alicyclic group, and preferably has 0 to 18 carbon atoms if it does not include an aromatic ring group or an alicyclic group. The oxygen-containing group is not particularly limited, but examples include hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, methylphenoxy group, dimethylphenoxy group, naphthoxy group, phenylmethoxy group, phenylethoxy group, acetoxy group, acetyl group, aldehyde group, carboxyl group, ether group, carbonyl group, ester group, oxazole group, morpholine group, carbamate group, carbamoyl group, urea group, amide group, imide group, urethane group, polyoxyethylene group, and groups containing these.

[0018] The phosphorus-containing group includes a phosphine group, phosphite group, phosphonic acid group, phosphinic acid group, phosphoric acid group, or phosphoric acid ester group. If it includes an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 6 to 22. If it does not include an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 0 to 6.

[0019] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0020] In the present invention, the 2-phenylbenzotriazole derivative is represented, for example, by the following formula (I).

[0021] In the formula, R 1 ~R 9 Each of these independently represents a monovalent or divalent group selected from a sulfur-containing group, hydrogen atom, hydrocarbon group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, and halogen atom, represented by the following formula (i) (if it is a divalent group, R 1 ~R 9 Any two of them come together to form a ring. 1 ~R 9 Two or more of these are the sulfur-containing groups represented by formula (I) above.

[0022] In equation (i), R 10 When m is 2 or greater, each represents a divalent hydrocarbon group having 1 to 20 carbon atoms, in which case hydrogen atoms may be independently substituted or carbon atoms may be interrupted. 11 represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms where hydrogen atoms may be substituted or carbon atoms may be interrupted, and m represents an integer from 0 to 3.

[0023] The monovalent or divalent groups that substitute hydrogen atoms or interrupt carbon atoms are not particularly limited, but examples include unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and monovalent or divalent groups selected from halogen atoms. Specific examples of these are those exemplified in the [Substituents, etc.] section above. In the case of a divalent group, any two carbon atoms (preferably two adjacent ones) of the hydrocarbon come together to form a ring.

[0024] In formula (i), R 10 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms. R 10 includes the aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like exemplified in the above [Substituents and the like] section. When a divalent hydrocarbon group is substituted with the above-mentioned monovalent or divalent group where a hydrogen atom is substituted or a carbon atom is interrupted, the number of the above-mentioned monovalent or divalent groups is not particularly limited, but examples thereof include 2 or less, or 1 or less. In formula (i), m is preferably 0.

[0025] In formula (i), R 11 has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. R 11 includes the aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like exemplified in the above [Substituents and the like] section. When a divalent hydrocarbon group is substituted with the above-mentioned monovalent or divalent group where a hydrogen atom is substituted or a carbon atom is interrupted, the number of the above-mentioned monovalent or divalent groups is not particularly limited, but examples thereof include 2 or less, or 1 or less.

[0026] In formula (i), in a preferred example, R 11 is a divalent aliphatic hydrocarbon group in which no hydrogen atom is substituted. In another preferred example, R 11 is a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group in which no hydrogen atom is substituted.

[0027] In the present invention, the 2-phenylbenzotriazole derivative may be a compound in which, in the above formula (I), R in formula (i) is replaced with R' instead of R 11 instead of R 11 to form R' 11 . Wherein R' is -(R 11 ) 12 -R n is a group represented by -R 13 . Where R 12R represents a divalent hydrocarbon group having preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms, where hydrogen atoms may be substituted or carbon atoms may be interrupted. 13 n represents a substituent containing one skeleton selected from benzotriazole, benzophenone, benzoic acid ester, and triazine. n represents an integer of 0 or 1.

[0028] R 13 Among these, a substituent containing benzotriazole is, for example, the group represented by the following formula (A); a substituent containing benzophenone is, for example, the group represented by the following formula (B); a substituent containing benzoic acid ester is, for example, the group represented by the following formula (C); and a substituent containing triazine is, for example, the group represented by the following formula (D).

[0029] In equation (A), R 16a ~R 24a One of the following is R 12 Alternatively, it indicates a monovalent bond portion bonded to a terminal sulfur atom, and other R 16a ~R 24a Each of these independently represents a hydrogen atom or a substituent.

[0030]

[0031] In equation (B), R 15b ~R 24b One of the following is R 12 Alternatively, it indicates a monovalent bond portion bonded to a terminal sulfur atom, and other R 15b ~R 24b Each of these independently represents a hydrogen atom or a substituent.

[0032] In equation (C), R 15c ~R 24c One of the following is R 12 Alternatively, it indicates a monovalent bond portion bonded to a terminal sulfur atom, and other R 15c ~R 24c Each of these independently represents a hydrogen atom or a substituent.

[0033] In equation (D), R 20d ~R 22d This indicates either [1] or [2] below. [1] R 20d ~R 22d At least one of them is R 12 Alternatively, it indicates a monovalent bond portion bonded to a terminal sulfur atom, and other R 20d ~R 22d Each of these is independently a hydrogen atom, a substituent, or a group represented by the following formula (d):

[0034] (In the formula, R 23d ~R 27d Each of these independently represents a hydrogen atom or a substituent. ) That is, one to three groups represented by formula (I) may be bonded to the triazine ring. [2] R 20d ~R 22d At least one of them is a base represented by the following formula (d'):

[0035] (In the formula, R 28d ~R 32d At least one of them is R 3 Alternatively, it indicates a monovalent bond portion bonded to a terminal sulfur atom, and other R 28d ~R 32d Each of these independently represents a hydrogen atom or a substituent. ) and other R 20d ~R 22d Each of these independently represents a hydrogen atom or a substituent. That is, the benzene ring represented by formula (d') may have 1 to 5 groups represented by formula (I) bonded to it.

[0036] R 12In formulas (A) to (D), (d) and (d'), the substituents are not particularly limited, but include, for example, a monovalent or divalent group selected from hydrocarbon groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, and halogen atoms. Specific examples of these are those exemplified in the [Substituents, etc.] section above. When a hydrogen atom is substituted with a divalent group, the two carbon atoms that bond together (preferably two adjacent carbon atoms) form a ring.

[0037] In equation (i), more specifically, R 11 One example of a base is represented by the following equation (j). In the above formula, X is a divalent aliphatic hydrocarbon group which may be substituted with a hydrogen atom, Y is a divalent aromatic hydrocarbon group which may be substituted with a hydrogen atom, or an alicyclic hydrocarbon group, and Z is a divalent heteroatom-containing group Z selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, and phosphorus-containing groups. 1 Or a divalent heteroatom Z selected from an oxygen atom and a sulfur atom. 2 This represents one of the following, where o, p, and q are integers greater than or equal to 0. The o X, p Y, and q Z elements are independent of each other, and the order of X, Y, and Z is arbitrary. In one example, if there are two or more of at least one of X, Y, or Z elements, no X elements are adjacent to each other, no Y elements are adjacent to each other, and no Z elements are adjacent to each other. At least one of o and p is an integer greater than or equal to 1.

[0038] The divalent aliphatic hydrocarbon group X has 1 to 20 carbon atoms, preferably 1 to 12, and includes linear or branched alkylene groups, linear or branched alkenylene groups, linear or branched alkynylene groups, etc. While not particularly limited, specific examples include methylene groups, ethane-1,2-diyl groups, propane-1,3-diyl groups, 1-methylethane-1,2-diyl groups, butane-1,4-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, pentane-1,5-diyl groups, pentane-1,4-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nona Examples include n-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-yl group, tetradecane-1,14-yl group, pentadecane-1,15-yl group, hexadecane-1,16-yl group, heptadecane-1,17-yl group, octadecane-1,18-yl group, nonadecane-1,19-yl group, and eicosane-1,20-yl group. Among these, aliphatic hydrocarbon groups in which hydrogen atoms are not substituted are preferred, alkylene groups are more preferred, and linear alkylene groups are even more preferred.

[0039] Among the divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y, the aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 14. The aromatic hydrocarbon group includes aromatic rings such as benzene rings, naphthalene rings, and anthracene rings, and the hydrogen atoms of the aromatic rings may be substituted with aliphatic hydrocarbon groups or the like. While not particularly limited, specific examples include phenylene groups (1,4-phenylene, 1,3-phenylene, 1,2-phenylene, etc.), naphthylene groups (1,8-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,3-naphthylene, etc.), and anthracenylene groups (9,10-anthracenylene, 1,8-anthracenylene, 2,7-anthracenylene, 2,6-anthracenylene, 1,4-anthracenylene, 1,3-anthracenylene, etc.). Among these, aromatic hydrocarbon groups in which hydrogen atoms are not substituted are preferred, and phenylene groups are more preferred.

[0040] Among the divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y, the alicyclic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8. It may contain an aliphatic ring, and the hydrogen atoms of the aliphatic ring may be substituted with an aliphatic hydrocarbon group or the like. Specifically, examples include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene (1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene, etc.), cycloheptylene, and cyclooctylene. Among these, alicyclic hydrocarbon groups in which hydrogen atoms are not substituted are preferred, and cyclohexylene groups are more preferred.

[0041] Among Z, the divalent heteroatom-containing group Z 1 The nitrogen-containing group is selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, and phosphorus-containing groups, and examples are given in the [Substituents, etc.] column above, with nitrogen-containing groups and oxygen-containing groups having double bonds being more preferred.

[0042] A divalent group Z having a double bond 1 Examples include divalent groups having a double bond, as exemplified in the [Substituents, etc.] column above.

[0043] Examples of divalent nitrogen-containing groups having a double bond include amide groups, urea groups, urethane groups, imide groups, carbodiimide groups, azo groups, pyridine groups, imidazole groups, toluidine groups, and nitroalkyl groups.

[0044] Examples of divalent oxygen-containing groups having a double bond include carboxyl groups, carbonyl groups, ester groups, oxazole groups, carbamate groups, and carbamoyl groups.

[0045] Examples of divalent sulfur-containing groups having a double bond include thioester groups, thioamide groups, sulfonyl groups, sulfoxide groups, thiocarbonyl groups, thiourea groups, thiocarbamate groups, dithiocarbamate groups, thiophene groups, and thiazole groups.

[0046] Examples of divalent phosphorus-containing groups having a double bond include phosphate ester groups and phosphonic acid esters.

[0047] Also, among Z, the divalent heteroatom Z2 Examples include oxygen atoms and sulfur atoms, with oxygen atoms being preferred.

[0048] Substituents that may be substituted with hydrogen atoms of a divalent aliphatic hydrocarbon group X, a divalent aromatic hydrocarbon group, or an alicyclic hydrocarbon group Y include aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms. Specific examples of these are those exemplified in the [Substituents, etc.] section above.

[0049] When a hydrogen atom of a divalent aliphatic hydrocarbon group X, a divalent aromatic hydrocarbon group, or an alicyclic hydrocarbon group Y is substituted, the number of substituents is not particularly limited, but examples include two or fewer, or one or fewer.

[0050] In formula (j), when a divalent aliphatic hydrocarbon group X is included, o is preferably 1 to 3, more preferably 1 to 2, even more preferably 1; p is preferably 0 to 2, more preferably 0 to 1, even more preferably 0; and q is preferably 0 to 2, more preferably 0 to 1, even more preferably 0. Preferred examples of formula (j) include -X-H, -X-Y-H, -Y-X-H, -X-Z-H, -X-Z-X-H, -X-Z-Y-H, and -Y-Z-X-H.

[0051] In formula (j), when a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y is included, p is preferably 1 to 3, more preferably 1 to 2, even more preferably 1, o is preferably 0 to 2, more preferably 0 to 1, and q is preferably 0 to 2, more preferably 0 to 1, even more preferably 0. Preferred examples of formula (j) include -Y-H, -Y-X-H, -X-Y-H, -Y-Z-H, -Y-Z-Y-H, -Y-Z-X-H, and -X-Z-Y-H.

[0052] In formula (j), the number q of Z is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1.

[0053] In formula (j), a preferred example is R 11 However, it has a divalent aliphatic hydrocarbon group X in which no hydrogen atoms are substituted. In this case, a preferred example is R 11p and q are 0. Another preferred example is R 11 However, it has a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y in which no hydrogen atoms are substituted. In this case, a preferred example is R 11 In this example, p is 1, q is 0, and o is 0 or 1. In another preferred example, R 11 However, it has a divalent aliphatic hydrocarbon group X in which hydrogen atoms are not substituted and a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group Y in which hydrogen atoms are not substituted. In this case, a preferred example is R 11 In this example, o is 1, p is 1, and q is 0. Another preferred example is R 11 In this case, o is 1 or greater, p is 1 or greater, and q is 1 or 2. In a preferred example, R 11 However, a divalent heteroatom-containing group Z selected from nitrogen-containing groups and oxygen-containing groups 1 It holds.

[0054] 2-phenylbenzotriazole derivatives are, in formula (I), R 1 ~R 9 Two or more of these are sulfur-containing groups represented by formula (i). Among these, considering ease of actual synthesis, absorption characteristics, cost, heat resistance, etc., R 1 ~R 9 Preferably, two to four of these are sulfur-containing groups represented by formula (i), and more preferably, two of them are sulfur-containing groups represented by formula (i).

[0055] The position of the monovalent sulfur-containing group represented by formula (i) in formula (I) is not particularly limited, and the monovalent sulfur-containing group represented by formula (i) is R in formula (I). 6 ~R 9 It is preferable to have one of the following, R 6 , R 9 The position is more preferable.

[0056] In equation (I), R 1 ~R 9 If the group is not a monovalent sulfur-containing group represented by formula (i), it represents a monovalent or divalent group selected from a hydrogen atom, a hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom.

[0057] R 1 ~R 9 When the hydrocarbon group is a hydrocarbon group, examples of hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc. Among these, aliphatic hydrocarbon groups are preferred, and examples include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, etc. Among aliphatic hydrocarbon groups, linear or branched alkyl groups are preferred, with a carbon number of 1 to 10 being preferred, 1 to 6 being more preferred, and 1 to 4 being even more preferred. While not particularly limited, specifically, for example, methyl group, ethane-1-yl group, propane-1-yl group, 1-methylethane-1-yl group, butane-1-yl group, butane-2-yl group, 2-methylpropane-1-yl group, 2-methylpropane-2-yl group, pentane-1-yl group, pentane-2-yl group, 2-methylbutane-1-yl group, hexane-1-yl group, 2-methylpentane-1-yl group, 3-methylpentane-1-yl group, heptane-1-yl group, 3-ethylpentane-1-yl group, 2-methylhexane-yl group, 3-methylhexane-yl group, octane-1- Examples include yl group, 2-methylheptan-1-yl group, 3-methylheptan-1-yl group, 4-methylheptan-1-yl group, 2-ethylhesan-1-yl group, 3-ethylhexane-1-yl group, 1,1,3,3-tetramethylbutylnonane-1-yl group, 3-ethylheptan-1-yl group, 4-ethylheptan-1-yl group, 2-methyloctane-1-yl group, 3-methyloctane-1-yl group, 4-methyloctane-1-yl group, decane-1-yl group, 4-propylheptan-1-yl group, 3-ethyloctane-1-yl group, and 4-ethyloctane-1-yl group.

[0058] R 1 ~R 9 When R is a monovalent or divalent group selected from aromatic groups, unsaturated groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, specific examples include those exemplified in the [Substituents, etc.] column above. When R is a divalent group, 1 ~R 9 Any two of them (preferably two adjacent ones) come together to form a ring.

[0059] In Formula (I), R 6 , R 7 , R 8 , R 9 are preferably each a monovalent sulfur-containing group represented by Formula (i) or a hydrogen atom. In Formula (I), R 6 , R 9 are monovalent sulfur-containing groups represented by Formula (i), and R 7 , R 8 are more preferably hydrogen atoms.

[0060] Further, preferred examples of combinations of R 1 , R 2 , R 3 , R 4 , R 5 are as follows. [1] R 1 to R 5 are each independently a hydrogen atom or a substituent, and the substituent is selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms (a hydrocarbon group having 2 to 18 carbon atoms including alkenyl groups and alkynyl groups), a hydroxy group, an aromatic group having 6 to 18 carbon atoms, an ether group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an ester group having 1 to 18 carbon atoms, a (meth)acryloyloxy group, a polyoxyethylene group having 1 to 20 carbon atoms, and / or a primary to tertiary amino group having 1 to 18 carbon atoms, or a C1-C18 hydrocarbon group in which a hydrogen atom may be substituted by any of these substituents, the terminal of the group may be interrupted, or a carbon-carbon bond may be interrupted, and the substituent is at least one selected from the above. [2] In [1], R 1 to R 5 are each independently a hydrogen atom or a substituent, and the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group. [3] In [2], R 1 to R 5 are each independently a hydrogen atom or a substituent, and the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group. [4] In [3], R 1 to R 5 are each independently a hydrogen atom, a methyl group, a t-butyl group, or a hydroxy group, and R 1 to R 5It has one methyl group and one hydroxyl group. [5] [4] In R 1 R is a hydroxyl group. 2 is a t-butyl group, R 4 R is a methyl group, 3 , R 5 is a hydrogen atom. [6] In [4], R 1 R is a hydroxyl group. 4 R is a methyl group, 2 , R 3 , R 5 It is a hydrogen atom.

[0061] The light absorber of the present invention has a high molar extinction coefficient and can efficiently absorb light even in small amounts. Furthermore, it has excellent heat resistance, making it useful in manufacturing processes involving high temperatures and in high-temperature operating environments.

[0062] Regarding the effects of light, it has been pointed out that not only ultraviolet light below 250-400 nm in sunlight, but also light in the short-wavelength visible light range around 400-420 nm can damage organic materials (for example, general organic resin compositions, protection of blue light-emitting elements in organic EL display devices such as displays) and the human body. Similarly, in the field of LED lighting, there is a need for light absorbers that can absorb light up to the short-wavelength visible light range. Therefore, the light absorber of the present invention preferably has an absorption peak (maximum absorption) at 370 nm or higher in the 350-430 nm region, more preferably at 375 nm or higher, and even more preferably at 380 nm or higher. Furthermore, it is required that light above 430 nm is not absorbed but transmitted, and the light absorber of the present invention preferably has an absorption peak (maximum absorption) at 410 nm or lower in the 350-430 nm region, more preferably at 400 nm or lower, and even more preferably at 390 nm or lower. The absorption peak (maximum absorption) of the light absorber of the present invention in the 350-430 nm region is preferably in any combination of the above wavelength ranges, for example, 370 nm to 400 nm.

[0063] Furthermore, when absorbing visible light in the 400-420 nm range, it is desirable to transmit light with wavelengths exceeding 420 nm in order to suppress damage to the appearance of organic or inorganic materials, the appearance of resin components (e.g., yellowing), the display color of displays, and the emission color of LEDs. In this case, although there are various criteria, for example, in the light transmittance of a 200 μM chloroform solution, the transmittance at 410 nm is preferably 70% or less, more preferably 50% or less, and even more preferably 10% or less. The transmittance at 430 nm is preferably 60% or more, more preferably 80% or more, and even more preferably 90% or more. Moreover, in order to efficiently absorb light with a small amount, the molar extinction coefficient (maximum molar extinction coefficient: ελ) of the absorption peak (maximum absorption) in the 350-430 nm range is important. max The concentration is preferably 25,000 L / (mol·cm) or more, and more preferably 28,000 L / (mol·cm) or more.

[0064] The light absorber of the present invention has the above-described ultraviolet absorption capacity, can efficiently absorb long-wavelength ultraviolet light in the 400-420 nm range, and is effective even with a small amount of use, so it can be used in applications that require absorption of long-wavelength ultraviolet light. Depending on the application, absorption of 420 nm light may be required, or transmission of 420 nm light may be required, and the light absorber of the present invention can be applied to a wide range of applications by adjusting the addition rate or appropriately changing R in formula (I). Specific applications are not particularly limited, but for example, it can be used in the applications described below.

[0065] When additives such as UV absorbers are reacted, mixed, or kneaded with organic and inorganic materials, including resins, under heating, or when resin components containing additives such as UV absorbers are processed or molded by heating, if the thermal decomposition temperature of the additive is low, it may decompose, preventing the additive from exerting its full effect, contaminating the equipment, and in the case of transparent resin components, losing transparency. To prevent these problems, a higher thermal decomposition temperature for the additive is desirable. The light absorber of the present invention has excellent heat resistance by introducing two or more sulfur-containing groups into a 2-phenylbenzotriazole derivative. In the present invention, the 5% weight loss temperature of the 2-phenylbenzotriazole derivative is preferably 280°C or higher, more preferably 300°C or higher, and even more preferably 320°C or higher. Because its weight loss temperature is 5% higher than the typical softening temperature of resins (100-250°C, as stated in "Understanding Plastics," supervised by the Japan Plastics Industry Federation, published by Nihon Jitsugyo Publishing), it can be applied to thermosetting resins and thermoplastic resins with molding temperatures of 100-200°C, as well as thermoplastic resins that require molding temperatures higher than 200-250°C.

[0066] When producing the benzotriazole compound represented by formula (I), the following examples and known techniques are disclosed, but are not particularly limited. (Composition) In this specification, the term composition includes compositions containing the light absorber of the present invention, regardless of their properties, such as solid, fluid, gel, or sol, and includes not only components but also raw materials for producing components.

[0067] In this specification, the term "component" is not particularly limited, but includes, for example, any shaped object. Examples of applications of compositions such as components containing the light absorber of the present invention include those described below.

[0068] Examples of materials for the composition containing the light absorber of the present invention include organic materials and inorganic materials. The light absorber of the present invention has high affinity, compatibility, and adhesion with various organic and inorganic materials. When the light absorber of the present invention is mixed, dissolved, dispersed, applied, or coated, a homogeneous composition or component can be obtained. In particular, when a transparent component is used, a component with excellent transparency can be obtained.

[0069] The light-absorbing compositions of the present invention include organic material compositions and inorganic material compositions. The shape of these organic and inorganic material compositions is not particularly limited and includes, for example, coating films, laminated films, films, sheets, plates, powders, granules, pellets, tablets, molded articles, and the like.

[0070] In organic and inorganic material compositions containing the light absorber of the present invention, the light absorber of the present invention can produce organic and inorganic material compositions with excellent heat resistance and suppress degradation. Furthermore, it has good affinity with organic materials, inorganic materials, and especially organic materials.

[0071] Based on the characteristics of the light absorber of the present invention described above, organic and inorganic material compositions containing it can efficiently absorb harmful light in the wavelength range of 400 to 420 nm, have excellent appearance, the light absorber does not bleed out, and exhibit excellent heat resistance, such as no discoloration, decrease in light absorption capacity, or decrease in transparency over a long period of use.

[0072] The organic material composition contains 50% by mass or more of the organic material relative to the total amount of all materials excluding water, solvent, and the light absorber of the present invention.

[0073] The inorganic material composition contains 50% by mass or more of the inorganic material, based on the total amount of all materials excluding water, solvent, and the light absorber of the present invention.

[0074] The light-absorbing composition of the present invention may be an organic-inorganic material composition. Here, the organic-inorganic material composition is an organic material composition that includes an inorganic material as a material other than the organic material, or an inorganic material composition that includes an organic material as a material other than the inorganic material.

[0075] The composition containing the light absorber of the present invention may also be obtained by adding and mixing raw materials for ultimately forming organic materials, inorganic materials, components, etc. Furthermore, the composition containing the light absorber of the present invention may also be obtained by dispersing, dissolving, and mixing the above-mentioned organic material composition, inorganic material composition, or organic-inorganic material composition containing the light absorber of the present invention in a liquid such as water or an organic solvent.

[0076] Organic materials are not particularly limited, but examples include organic resins, materials derived from plants and animals, materials derived from crude oil, and organic compounds.

[0077] In the present invention, the organic resin composition is an organic composition comprising the light absorber of the present invention and an organic resin, and is included in the organic material composition.

[0078] The organic resin is not particularly limited and can be broadly used if it is one of the conventionally known types, such as thermoplastic resins and thermosetting resins, and each includes polymers having one type of repeating unit and copolymers containing multiple repeating units.

[0079] In this specification, the terms thermoplastic resins (polymers and copolymers) and thermosetting resins (polymers and copolymers) allow for the inclusion of 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and particularly preferably 2% by weight or less, in addition to the original repeating units in the general sense of the resin, in the individual types of resins exemplified below. Furthermore, a mixture of such a resin and other resins is also permitted, in which the content of the other resin is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and particularly preferably 2% by weight or less, based on the total amount of the mixture.

[0080] The thermoplastic resin is not particularly limited, but examples of polymers include (meth)acrylic resins, olefin resins, styrene resins, ester resins, ether resins, vinyl chloride resins, fluororesins, vinyl resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimide resins, polymaleimide resins, polyvinylpyrrolidone resins, polyurethane resins, and polysulfone resins. Examples of copolymers include butadiene-styrene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-isoprene copolymers, styrene-acrylic acid copolymers, and vinyl chloride-vinylidene chloride-acrylonitrile copolymers. These may be used individually or in combination of two or more.

[0081] The polymer of the thermoplastic resin is not particularly limited, but examples include the following:

[0082] The (meth)acrylic resin is not particularly limited, but examples include poly(meth)acrylic acid, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, and poly(meth)acrylonitrile.

[0083] The olefin resin is not particularly limited, but examples include polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene, poly(2,3-dimethylbutadiene), polycyclohexadiene, polycyclopentadiene, polydicyclopentadiene, polychloroprene, and polynorbornene.

[0084] The styrene-based resin is not particularly limited, but examples include polystyrene.

[0085] The ester resin is not particularly limited, but examples include polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycaprolactone, polyethylene succinate, polylactic acid, polymalic acid, and polyglycolic acid.

[0086] The ether resin is not particularly limited, but examples include polyacetal, polyphenylene ether, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyether sulfone, and polyether imide.

[0087] The vinyl chloride resin is not particularly limited, but examples include polyvinyl chloride, polyvinylidene chloride, and the like.

[0088] Fluorine-based resins are not particularly limited, but examples include polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride.

[0089] The vinyl resin is not particularly limited, but examples include polyvinyl acetate, polyvinyl alcohol, polyvinyl sulfonic acid, and salts thereof.

[0090] The polycarbonate resin is not particularly limited, but examples include polycarbonate.

[0091] The polyamide resin is not particularly limited, but examples include polyamide, nylon 6, nylon 66, nylon 11, nylon 12, and the like.

[0092] The polyimide resin is not particularly limited, but examples include polyimide.

[0093] The polyamide-imide resin is not particularly limited, but examples include polyamide-imide.

[0094] The polymaleimide resin is not particularly limited, but examples include polymaleimide and poly-N-phenylmaleimide.

[0095] The polyvinylpyrrolidone-based resin is not particularly limited, but examples include polyvinylpyrrolidone.

[0096] The polyurethane resin is not particularly limited, but examples include polyurethane.

[0097] The polysulfone resin is not particularly limited, but examples include polysulfone.

[0098] Examples of copolymers of thermoplastic resins include those containing multiple polymer raw material monomers as listed above, and are not particularly limited, but include the following:

[0099] The butadiene-styrene copolymer is not particularly limited, but examples include butadiene-styrene copolymers.

[0100] The acrylonitrile-styrene copolymer is not particularly limited, but examples include acrylonitrile-styrene copolymers.

[0101] The acrylonitrile-butadiene-styrene copolymer is not particularly limited, but examples include acrylonitrile-butadiene-styrene copolymers.

[0102] The styrene-isoprene copolymer is not particularly limited, but examples include styrene-isoprene copolymers.

[0103] The styrene-acrylic acid copolymer is not particularly limited, but examples include styrene-acrylic acid copolymers.

[0104] The vinyl chloride-vinylidene chloride-acrylonitrile copolymer is not particularly limited, but examples include vinyl chloride-vinylidene chloride-acrylonitrile copolymers.

[0105] The thermosetting resin is not particularly limited, but examples of polymers include phenolic resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and episulfide resins, and examples of copolymers include acrylic melamine resins and acrylic urethane resins. These may be used individually or in combination of two or more.

[0106] The polymer of the thermosetting resin is not particularly limited, but examples include the following:

[0107] Phenolic resins are not particularly limited, but examples include phenolic resins.

[0108] The urea-based resin is not particularly limited, but examples include urea resin.

[0109] The melamine resin is not particularly limited, but examples include melamine resin.

[0110] The unsaturated polyester resin is not particularly limited, but examples include unsaturated polyester resins.

[0111] Alkyd resins are not particularly limited, but examples include alkyd resins.

[0112] The epoxy resin is not particularly limited, but examples include epoxy resins.

[0113] The episulfide resin is not particularly limited, but examples include episulfide resins.

[0114] The copolymer of the thermosetting resin is not particularly limited, but examples include the following:

[0115] The acrylic melamine resin is not particularly limited, but examples include acrylic melamine resin.

[0116] The acrylic urethane resin is not particularly limited, but for example, acrylic urethane resin

[0117] The organic resin composition of the present invention preferably contains 0.001% by mass or more of organic resin, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more, based on the total amount of the organic resin composition excluding the light absorber of the present invention. The organic resin composition is, for example, obtained by mixing, dispersing, or dissolving the light absorber of the present invention and the organic resin, or by mixing, dispersing, or dissolving the light absorber in the organic resin. Inorganic compounds used as fillers, silane coupling agents, primers, etc., may be added to the organic resin composition.

[0118] Inorganic materials are not particularly limited, but examples include siliceous materials produced by the sol-gel method, glass, water glass, low-melting-point glass, quartz, silicon resin, alkoxysilane, silane coupling agent, metal, metal oxide, mineral, and inorganic compound. Glass is not particularly limited, but examples include silicon oxide, alkali-free glass, and soda glass. Water glass is not particularly limited, but examples include aqueous solutions of water-soluble alkali metal salts, such as sodium silicate and potassium silicate. Low-melting-point glass is not particularly limited, but examples include glass containing lead oxide (PbO) and boric anhydride (B2O3) as main components. Silicon resin is not particularly limited, but examples include methyl silicon resin, methylphenyl silicon resin, and organic resin-modified silicon resins modified with epoxy resin, alkyd resin, polyester resin, etc. Examples of alkoxysilanes include dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.The silane coupling agent is not particularly limited, but examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Examples include lan, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatetopropylethoxysilane, etc. The metals are not particularly limited, but examples include Zn, Fe, Cu, Ni, Ag, Si, Ta, Nb, Ti, Zr, Al, Ge, B, Na, Ga, Ce, V, Ta, P, Sb, etc. Examples of metal oxides include zinc oxide, titanium oxide, cerium oxide, iron oxide, tin oxide, indium oxide, and antimony oxide, although these are not particularly limited. Examples of minerals include smectite, bentonite, hectorite, and montmorillonite.

[0119] Shape of the component The shape of the component is not particularly limited and may be any shape, for example, coatings, adhesives, adhesives, flexible or pliable films or rigid plate-shaped components, powder-shaped, granular, pellet-shaped, tablet-shaped components, masterbatches, molded products, etc. [1] Coating Specific application examples include coating the surface of components such as resins and glass. The coating method is not particularly limited, but for example, a resin, paint, silica material, glass, solvent dispersion, etc., mixed, dissolved, or dispersed with the light absorber of the present invention may be applied, sprayed, formed into a film on the surface of the component, or a method of producing a film containing the light absorber of the present invention may be used. [2] Adhesive Specific application examples are not particularly limited, but for example, an adhesive may be obtained by mixing, dissolving, or dispersing the light absorber of the present invention in an organic adhesive (organic resin, synthetic rubber, starch, glue, etc.) or an inorganic adhesive (silica, ceramic, cement, solder, water glass, etc.) that can be applied to various materials and components. [3] Adhesives Specific application examples are not particularly limited, but include adhesives obtained by mixing, dissolving, and dispersing the light absorber of the present invention in adhesives applicable to various materials and components (organic resins, organic oligomers, rubber-based adhesives, starch, glue, silicone-based adhesives, silane coupling agent-based adhesives, etc.). [4] Films Specific application examples are not particularly limited, but include components obtained by mixing, dissolving, and dispersing the light absorber of the present invention in a flexible or pliable film-like resin, glass, silicon oxide precursor. The film may be a single-layer film, a multilayer film or film-attached substrate with one or more layers provided on a base film or substrate according to various applications, and if a multilayer film is provided, the light absorber of the present invention is contained in at least one layer. It can also be used as an interlayer of a film-like resin or glass containing the light absorber of the present invention, or a glass composite. [5] Plates Specific application examples are not particularly limited, but include components obtained by mixing, dissolving, and dispersing the light absorber of the present invention in a plate-like resin or glass.[6] Powders, granules, pellets, tablets Specific application examples are not limited to, but include, for example, components obtained by mixing, dissolving, or dispersing the light absorber of the present invention in powder form, granule form, pellet form, or tablet form of resin or glass. [7] Masterbatch Specific application examples are not limited to, but include, for example, resin compositions in the form of granules, pellets, etc., obtained by mixing, dissolving, or dispersing the light absorber of the present invention, a colorant such as a pigment, etc., in a resin, etc., as needed. Used for coloring or preparing coloring by melt-mixing with other resins, etc. [8] Molded articles Specific application examples are not limited to, but include, for example, articles molded by mixing, dissolving, or dispersing the light absorber of the present invention in a resin or glass.

[0120] Additives The compositions and components containing the light absorber of the present invention may contain various additives, not limited to, but including, for example, antioxidants, heat stabilizers, weather stabilizers, light stabilizers, pigments, dyes, fillers, plasticizers, antistatic agents, nucleating agents, wetting agents, preservatives, fungicides, defoaming agents, stabilizers, antioxidants, chelating agents, etc., in an amount that does not impair their properties.

[0121] The light absorber of the present invention is used in fields requiring high heat resistance, and the type, shape, and application of the composition and components are not limited.

[0122] Compositions and components containing the light absorber of the present invention can be light absorber-containing compositions with excellent heat resistance. For example, coating films and films for transparent resins and transparent glass containing the light absorber of the present invention can be made that do not yellow, discolor, decrease in ultraviolet absorption capacity, or decrease in transparency over a long period from manufacturing to use.

[0123] The applications of the light absorber of the present invention are not particularly limited, but it is especially suitable for applications where it may be exposed to light with wavelengths of 380 to 400 nm, and even more so, 380 to 420 nm, including sunlight or ultraviolet light.

[0124] While not particularly limited, examples include: components and articles used in residences, facilities, transportation equipment, displays, etc.; interior and exterior materials for residences and facilities, transportation equipment, etc.; interior and exterior paints and coatings formed by said paints; adhesives and sealants; precision machinery, components for electronic and electrical equipment, and films and components for shielding electromagnetic waves generated from various displays; containers or packaging materials for food, chemicals, pharmaceuticals, and cosmetics; agricultural and industrial sheets or film materials; fade inhibitors for printed materials, dyes, and dyes and pigments; resin components or protective films for various devices; glass interlayers; cosmetics, textile products and fibers for clothing; interior furnishings for homes such as curtains, carpets, and wallpaper; plastic lenses, contact lenses, artificial eyes and other medical devices; optical lenses such as optical pickup lenses, camera lenses, and lenticular lenses; optical filters; backlight display films; prisms; mirrors; photographic materials, and displays; and optical products and protection for optical products. It can also be used in films, optical materials, films having functional optical layers (various optical disc substrate protective films, reflective films, anti-reflective films, alignment films, polarizing films, polarizing layer protective films, phase difference films, light diffusion films, viewing angle improving films, electromagnetic wave shielding films, anti-glare films, light-shielding films, and brightness improving films, etc.), components, adhesives and bonding agents, optical molded products such as optical fibers or information recording substrates, surface protective films for solar cells, stationery, signs and indicators and their surface coating materials, glass substitutes or their surface coating materials, glass and glass coating materials for residences, facilities or transportation equipment, daylighting glass, components such as fluorescent lamps, mercury lamps, halogen bulbs and LED lights, components for light sources and coating materials for light source protective glass, window glass for residences, facilities and transportation equipment, window films and intermediate films for laminated glass, etc.

[0125] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 1. Synthesis of light absorbers <Synthesis Example 1> Synthesis of intermediate 1 Sodium nitrite (3.87 g, 56.1 mmol) was mixed dropwise with concentrated sulfuric acid (18 g) under ice cooling. A mixed solution of 4,5-dichloro-2-nitroaniline (10.8 g, 52.2 mmol) and acetic acid (96 g) was then added dropwise, followed by the addition of water (60 g), and the mixture was stirred for 30 minutes. A mixed solution of 2-tert-butyl-p-cresol (9.21 g, 56.1 mmol), ethanol (17.2 g), and water (6 g) was then added dropwise, followed by the addition of an aqueous solution of potassium hydroxide (48 g, 855.5 mmol) and water (78 g). After the addition of all components, the mixture was stirred under ice cooling for 12 hours. After the reaction was complete, the mixture was filtered and washed with water to obtain intermediate 1.

[0126] <Synthesis Example 2> Synthesis of Intermediate 2 Intermediate 1 (5.23 g, 15.6 mmol), zinc powder (10.68 g, 187.2 mmol), 2NNaOH aqueous solution (23.38 ml, 46.8 mmol), and toluene (26 g) were mixed and stirred at 85°C for 3.5 hours. After the reaction was complete, acid treatment, water washing, and hexane washing were performed to obtain intermediate 2 as yellow crystals.

[0127] <Synthesis Example 3> Synthesis of Compound 1 Intermediate 2 (0.5 g, 1.42 mmol) was mixed with octanthiol (1.04 g, 7.11 mmol), potassium carbonate (0.99 g, 7.11 mmol), potassium iodide (0.038 g, 0.23 mmol), and DMF (5 g), and refluxed at 140°C for 3 hours. After the reaction was complete, the mixture was treated with acid, washed with water, purified by column, and recrystallized to obtain compound 1 as yellow crystals. FT-IR (KBr): 2924 cm⁻¹ -1 : O-H stretching vibration 1435, 1358cm -1 Triazole ring stretching vibration 712cm -1 :CS stretching vibration 1 H-NMR (CDCl3 400MHz): δ 0.88 (t, 6H, CH3(CH2)7-S), 1.28 (m, 16H, CH3 (CH2)4(CH2)3-S), 1.49 (m, 13H, -Ph-OH-CH3-C(C H3 )3, CH3(CH2)4 C H2(CH2)2-S), 1.75 (m, 4H, CH3 (CH2)5 CH2CH2-S), 2.38 (s, 3H, -Ph-OH-CH3-C(CH3)3), 3.03 (t, 4H, CH3 (CH2)5CH2CH2-S), 7.16 (d, 2H), 7.67 (s, 2H), 8.02 (d, 2H), 11.59 (s, 1H, -Ph-OH-CH3-C(CH3)3) 13 C-NMR (CDCl3 400MHz): δ 14.0 (CH3(CH2)7-S), 20.9 (-Ph-OH-CH3-C(CH3)3), 22.6(-Ph-OH-CH3-C(CH3)3), 28.3-29.5 (CH3(CH2)5CH2 CH2-S), 31.8 (-Ph-OH-CH3-C(CH3)3) , 33.8 (CH3(CH2)5CH2CH2-S), 35.4 (CH3(CH2)5CH2CH2-S), 114.1, 119.2, 128.5, 141.7 (CH arom ), 125.4(C arom -N), 128.3 (C arom -CH3), 139.0(C arom -S), 139.1(C arom -C(CH3)3), 146.6(C arom -OH)

[0128] <Synthesis Example 4> Synthesis of Compound 2 Intermediate 2 (0.5 g, 1.42 mmol) was mixed with benzenethiol (0.78 g, 7.11 mmol), potassium carbonate (0.99 g, 7.11 mmol), potassium iodide (0.038 g, 0.23 mmol), and DMF (5 g), and the mixture was refluxed at 140°C for 3 hours. After the reaction was complete, the mixture was treated with acid and washed with water to obtain compound 2 as yellow crystals. FT-IR (KBr): 2924 cm⁻¹ -1 :O-H stretching vibration 1438, 1361cm -1 Triazole ring stretching vibration 683cm -1 :CS stretching vibration 1 H-NMR (CDCl) 3 400MHz): δ1.45 (s, 9H, -Ph-OH-CH3-C(CH3)3), 2.34 (s, 3H, -Ph-OH-CH3-C(CH3)3), 7.14 (d, 1H), 7.39-7.45 (m, 6H), 7.49-7.52 (m, 6H), 11.45 (s, 1H, -Ph-OH-CH3-C(CH3)3) 13 C-NMR (CDCl) 3 400MHz): δ20.9 (-Ph-OH-CH3-C(CH3)3), 29.5 (-Ph-OH-CH3-C(CH3)3), 35.4 (-Ph-OH-CH3-C(CH3)3) , 117.6, 119.2, 128.6, 128.9, 129.8, 133.1, (CH arom ), 125.2, 142.1, (C arom ), 128.3 (C arom -CH3), 138.9(S -C arom ), 139.2(C arom -C(CH3)3), 146.7(C arom -OH)

[0129] Compound 3: Synthesized in accordance with Patent Document 2.

[0130] Compound 4: Synthesized in accordance with Patent Document 2.

[0131] 2. Optical properties of the light absorber (1) Wavelength, molar extinction coefficient, and slope (absolute value) of the maximum absorption peak in the 350-430 nm wavelength range Compounds 1-4 were dissolved in 50 μM chloroform and placed in a 10 mm quartz cell. The absorption spectra from 200-700 nm were measured using a UV-Vis spectrophotometer (JASCO V-550) (Figure 1). From these spectra, the absorption peak in the 350-430 nm wavelength range (maximum absorption wavelength: λ max ), read the absorbance and the molar extinction coefficient of that peak (maximum molar extinction coefficient: ε max The molar extinction coefficient was calculated using the following formula (Table 1A, Table 1B). Molar extinction coefficient: ε max (L / (mol·cm) = A: absorbance / [c: molar concentration (mol / L) × l: optical path length of the cell (cm)]

[0132] Furthermore, from the obtained absorption spectra, the intersection of the long-wavelength absorption spectrum at the absorption peak in the 350-390 nm wavelength range and the baseline (the line where the slope of the absorption spectrum in the 430-500 nm range is 0) was defined as the peak end (see Compound 1 in Figure 1, top). The absolute value of the long-wavelength slope of the absorption peak in the 350-390 nm wavelength range was then calculated using the following formula (Tables 1A and 1B): |Long-wavelength slope of the absorption peak in the 350-390 nm wavelength range| = |(Absorbance at the peak end - Absorbance of the absorption peak in the 350-390 nm wavelength range) / (Absorbance wavelength at the peak end - Wavelength of the absorption peak in the 350-390 nm wavelength range)|

[0133] Compared to Comparative Examples 3 and 4 (compounds 1 and 2), the light absorbers in Examples 1 and 2 (compounds 1 and 2) had their maximum absorption wavelength at a longer wavelength of 380-381 nm. Compounds 1 and 2 had a large molar extinction coefficient of 28,000 L / (mol·cm) or more (high UV absorption efficiency), and the absolute value of the slope of their absorption peak on the longer wavelength side was large at 0.025 or more, indicating a sharp absorption.

[0134] Due to these properties, the light absorber of the present invention is expected to have the effect of suppressing yellowing of films and resins by efficiently absorbing harmful light with wavelengths around 400-420 nm while suppressing absorption of wavelengths above 420 nm, for example, when a small amount of the light absorber of the present invention is added to films or resins. Furthermore, in cosmetic applications, it is expected to efficiently absorb light from the UV-A region to the short wavelength range of visible light in sunscreens and other products that protect the skin from ultraviolet rays that cause blemishes, freckles, and skin cancer. In addition, because it efficiently absorbs high-energy visible light (HEV) from 380 nm to 420 nm, which is considered harmful to the eyes and is often emitted by LEDs, it is also expected to have applications in films for electronic materials and eyeglasses.

[0135] Furthermore, a comparison of Examples 1 and 2 (compounds 1 and 2) shows that Example 1 (compound 1) has a larger molar extinction coefficient for the absorption peak in the 350-430 nm wavelength range, and a larger absolute value for the slope on the longer wavelength side of the absorption peak in the 350-430 nm wavelength range. Therefore, it is expected that it will more efficiently suppress absorption at wavelengths above approximately 420 nm, and also suppress yellow discoloration.

[0136]

[0137]

[0138] (2) Transmittance (molar ratio) Using compounds 1 to 4, 200 and 1000 μM chloroform solutions were prepared as shown in Table 2, placed in a 10 mm quartz cell, and the transmission spectra were measured using an ultraviolet-visible-infrared spectrophotometer (Hitachi High-Tech Science UH4150V). From these spectra, the transmittances at 400, 410, 420, 430, 440, and 450 nm were read (Table 2).

[0139] Measurements using a 200 μM chloroform solution revealed that, compared to Comparative Examples 3 and 4 (compounds 1 and 2), the transmittance at 400 nm for compounds 1 and 2 was 0%, while that for compounds 3 and 4 was 10% or more. Furthermore, the transmittance at 410 nm for compounds 1 and 2 was 10% or less, while that for compounds 3 and 4 was 60% or more. This suggests that the light absorber of the present invention exhibits excellent absorption of light in the 400 nm to 410 nm range.

[0140] Furthermore, the transmittance at 420 nm for compound 1 was 66.5% and for compound 2 was 37.8%, confirming their usefulness in applications requiring absorption of 420 nm light. In a comparison between compound 1 and 2, compound 2 was found to have lower transmittance of light in the 410 nm to 420 nm range than compound 1. This suggests that when R in formula (I) is an aromatic hydrocarbon group, absorption of light around 410 nm to 420 nm is superior.

[0141] Regarding the measurement results of a 1000 μM chloroform solution, the transmittance at 410 nm for compounds 1 and 2 was 0%, while that for compounds 3 and 4 was 10% or more. Furthermore, the transmittance at 420 nm for compounds 1 and 2 was 15% or less, while that for compounds 3 and 4 was 70% or more. This suggests that it is possible to absorb light at 420 nm by adjusting the addition rate of the light absorber of the present invention. In addition, the transmittance at 430 nm for compounds 1 and 2 was 79.1% and 43%, respectively, suggesting that even when the light absorber of the present invention is added at a high concentration, light above 430 nm is efficiently transmitted. In particular, it was suggested that when R in formula (I) is an aromatic hydrocarbon group, it is superior in that it absorbs light at 420 nm and transmits light at 430 nm.

[0142]

[0143] (3) Transmittance (weight ratio) Solutions of compounds 1 to 4 were prepared in 0.01 to 0.1 wt% chloroform as shown in Table 3, placed in a 10 mm quartz cell, and the transmission spectra were measured using an ultraviolet-visible-infrared spectrophotometer (Hitachi High-Tech Science UH4150V). From these spectra, the transmittances at 400, 410, 420, 430, 440, and 450 nm were read (Table 3). Compared with Comparative Examples 5 and 6 (compounds 3 and 4), the transmittances of compounds 1 and 2 in a 0.01 wt% chloroform solution were 0% at 400 nm and 3% or less at 410 nm, while compounds 3 and 4 were 3% or more at 400 nm and 50% or more at 410 nm. This suggests that the light absorbers of the present invention are excellent at absorbing light below 410 nm with only a small amount added. In the case of a 0.1 wt% chloroform solution, the transmittances at 400 nm and 410 nm were almost the same for compounds 1 and 2 in the examples and compounds 3 and 4 in the comparative examples. However, the transmittance at 420 nm was less than 1% for compounds 1 and 2, and more than 30% for compounds 3 and 4. This suggests that the light absorber of the present invention can efficiently absorb light at 420 nm by adjusting the addition rate.

[0144] Furthermore, a comparison of compound 1 and compound 2 revealed that compound 2 exhibited superior absorption of light in the 400 nm to 420 nm range. This suggests that when R in formula (I) is an aromatic hydrocarbon group, it is superior in terms of absorbing light in the 400 nm to 420 nm range. Additionally, when attempting to cut light up to 400 nm, Examples 5 and 6 achieved a transmittance of 1% or less at 400 nm at a concentration of 0.01 wt%, while Comparative Examples 5 and 6 achieved a transmittance of 1% or less at 400 nm at a concentration of 0.05 wt%. In other words, when attempting to cut light up to 400 nm, the Examples can cut light up to 400 nm at a lower concentration (by weight), i.e., a smaller amount of additive, compared to the Comparative Examples. This means that when intended for use as a light absorber, it is possible to reduce the amount added to films, resins, etc.

[0145]

[0146] (4) 5% Weight Loss Temperature The weight change of the light absorber of the present invention was measured using a differential thermogravimetric analyzer (SII Corporation, TG / DTA6200) with a heating rate of 10°C / min and a measurement range of 25°C to 550°C, and the temperature at which the weight change (TG) decreased by 5% by weight was read (Table 4). Examples 7 and 8 (compounds 1 and 2), which have two sulfur-containing groups, showed a higher 5% weight loss temperature of 330°C or higher compared to comparative examples 7 and 8 (compounds 3 and 4), confirming their superior heat resistance. This suggests that introducing multiple sulfur-containing groups improves heat resistance.

[0147]

[0148] (5) Solubility The solubility of the light absorber of the present invention in hexane was evaluated. The results for Examples 9 and 10 (compounds 1 and 2) and Comparative Examples 9 and 10 (compounds 3 and 4) are shown in Table 5. Comparing compound 1 and compound 3, where R in formula (I) is an aliphatic hydrocarbon group, it was confirmed that compound 1 has high solubility in hexane. Similarly, comparing compound 2 and compound 4, where R in formula (I) is an aromatic hydrocarbon group, compound 2 had superior solubility in hexane. From this, it can be concluded that in formula (I), R 7 ~R 9It was suggested that having two or more sulfur-containing groups at any of the positions improves solubility in the solvent.

[0149]

[0150] (6) Lightfastness Evaluation Compound 1 or 2 was added to a 2.5 wt% acrylic resin chloroform solution in a weight ratio of 1:1 with the resin and mixed, and a thin film was prepared using a spin coater (Mikasa MS-B150). The ultraviolet-visible transmission spectrum of the thin film was measured using an ultraviolet-visible infrared spectrophotometer (Hitachi High-Tech Science UH4150V), and the initial (before ultraviolet irradiation) ultraviolet transmittance (%): A at 380, 390, and 400 nm was read. Next, an ultraviolet irradiation device (Atlas weatherometer Ci3000+w) was used, with a wavelength of 300-400 nm and an illuminance of 42 W / m². 2 The thin film was irradiated with ultraviolet light under conditions of a black panel temperature of 63°C. After 48 and 100 hours of irradiation, the ultraviolet-visible transmission spectrum was measured, and the transmittance (%) B at 380, 390, and 400 nm was read, and the difference in transmittance ΔT before and after irradiation was determined. uv : B - A (%) was calculated (Table 4). ΔT uv A smaller value indicates better light resistance. As a result, for both compound 1 and 2, the transmittance (%) at 380, 390, and 400 nm was measured before and after UV irradiation. uv It was confirmed that the value was small and that it had excellent lightfastness. In particular, compound 2 had a lower ΔT than compound 1. uv The low value of the element confirmed excellent lightfastness. This suggests that when R in formula (I) is an aromatic hydrocarbon group, it exhibits superior lightfastness.

[0151]

Claims

1. A light absorber comprising a benzotriazole or a 2-phenylbenzotriazole derivative having two or more sulfur-containing groups, wherein the sulfur atoms of the sulfur-containing groups are bonded to a phenyl group.

2. The 2-phenylbenzotriazole derivative is given by the following formula (I): (In the formula, R 1 ~R 9 Each of these is independent, as shown in equation (i): (In formula (i), R 10 When m is 2 or greater, each represents a divalent hydrocarbon group having 1 to 20 carbon atoms, in which case hydrogen atoms may be independently substituted or carbon atoms may be interrupted. 11 R represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms in which hydrogen atoms may be substituted or carbon atoms may be interrupted, and m is an integer from 0 to 3. R represents a group selected from the sulfur-containing group, hydrogen atom, hydrocarbon group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, and halogen atom. 1 ~R 9 Two or more of these are the sulfur-containing groups represented by formula (i) above.) The light absorber according to claim 1.

3. R 11 The light absorber according to claim 2, wherein the hydrogen atom is not substituted in a divalent aliphatic hydrocarbon group.

4. R 11 The light absorber according to claim 2, wherein the light absorber is a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group in which no hydrogen atoms are substituted.

5. The light absorber according to claim 2, wherein m in formula (i) is 0.

6. The light absorber having two of the sulfur-containing groups and having the sulfur-containing group at any position of R 6 to R 9 according to claim 2.

7. R 1 ~R 5 The light absorber according to claim 2, wherein each is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group.

8. R 1 ~R 5 Each of these is independently a hydrogen atom, a methyl group, a t-butyl group, or a hydroxyl group, and R 1 ~R 5 The light absorber according to claim 7, having one methyl group and one hydroxyl group.

9. A composition comprising a light absorber according to any one of claims 1 to 8 and an organic material and / or an inorganic material.

10. A method for imparting light absorption capacity including a wavelength of 410 nm to an organic material and / or inorganic material composition by adding the light absorber described in claim 1.

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