Lightfast, heat-resistant, and durable UV absorber

Abstract

To provide an ultraviolet absorber that is capable of efficiently absorbing harmful light in the wavelength range of 380 to 400 nm and suppressing the absorption of light with wavelengths of 400 nm or longer, which causes early yellowing, thereby producing a member with enhanced resistance to harmful light and superior appearance, while the ultraviolet absorber offers high resistance to light and heat, resulting in exceptional durability.SOLUTION: An ultraviolet absorber is used in an ultraviolet shielding film for glass or a composition for forming an ultraviolet shielding film. The ultraviolet absorber is composed of a 2-phenylbenzotriazol derivative with a thioalkyl group represented by the formula (5), (where PhBzT1e denotes a 2-phenylbenzotriazole skeleton with an attached thioalkyl group (-S-Y1e), which may have a substituent, and Y1e denotes a linear or branched C1-22 alkyl group, which may be substituted or interrupted.

Description

[Technical Field]

[0001] The present invention relates to an ultraviolet absorber, particularly one that is highly resistant to light and heat, and more specifically, to an ultraviolet absorber that is highly resistant to light and heat, i.e., durable. [Background technology]

[0002] Resin components deteriorate due to the action of ultraviolet rays, causing quality degradation such as discoloration and a decrease in mechanical strength, which hinders long-term use. Furthermore, from the viewpoint of reducing health risks such as sunburn and eye tissue damage, and from the viewpoint of imparting optical functions, various methods of incorporating ultraviolet absorbers into organic and inorganic components to block and absorb ultraviolet rays have been investigated (Patent Document 1).

[0003] In recent years, in order to further enhance the effects of suppressing quality degradation in materials and preventing health hazards, there has been a demand for UV absorbers that efficiently absorb light in the longer wavelength range (380-400 nm) while suppressing the absorption of visible light with wavelengths longer than 400 nm (~500 nm), thereby suppressing yellowing of the added material and maintaining a good initial appearance. However, conventional benzotriazole derivatives, for example, require a large amount of additive to sufficiently absorb light in the longer wavelength range (380-400 nm) because their absorption efficiency in that wavelength range is low. Furthermore, due to their optical properties, they also absorb a large amount of light with wavelengths longer than 400 nm, leading to the problem of yellowing of the added material.

[0004] 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 380-400 nm and suppresses the absorption of light with wavelengths above 400 nm, which is a cause of initial yellowing (Patent Documents 2 and 3). Due to its optical properties, this ultraviolet absorber can sufficiently absorb light in the wavelength range of 250-400 nm, and moreover, it has a high ultraviolet absorption effect (molar extinction coefficient), so it can efficiently absorb light of that wavelength with only a small amount added. Furthermore, the slope of the absorption peak at 350-390 nm is greater than that of conventional ultraviolet absorbers, so it can suppress the absorption of light with wavelengths above 400 nm and suppress the initial yellowing of the compounded material.

[0005] On the one hand, UV absorbers are desired to have excellent affinity with organic and inorganic materials, in addition to their optical properties at absorption wavelengths, and to be effective in maintaining the appearance of organic and inorganic materials, without the UV absorber bleeding out of organic and inorganic material compositions containing the UV absorber. Furthermore, UV absorbers are required to have improved light resistance so that prolonged exposure to ultraviolet light does not impede long-term use, such as by deterioration of properties such as light absorption capacity. On the other hand, they are also required to have excellent heat resistance, such as not experiencing discoloration, weight loss, or a decrease in light absorption capacity due to thermal decomposition when exposed to high-temperature environments at constant temperatures for extended periods during manufacturing processes such as molding and drying of resin materials, or during actual use. Considering the period from manufacturing to use, highly durable UV absorbers with excellent light resistance and heat resistance are desired. Moreover, UV absorbers are desired for organic and inorganic material compositions containing UV absorbers that exhibit not only excellent light resistance but also excellent heat resistance, such as not experiencing discoloration, a decrease in UV absorption capacity, or a decrease in transparency over long periods of use. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2009-184882 [Patent Document 2] International Publication No. 2016 / 021664 [Patent Document 3] International Publication No. 2016 / 174788 [Overview of the project] [Problems that the invention aims to solve]

[0007] Patent documents 2 and 3 primarily focus on solving the problems of sufficiently and efficiently absorbing light at wavelengths up to 380-400 nm and suppressing initial yellowing, using alkyl groups as the basic skeleton as sulfur-containing groups. However, the light resistance and durability, including heat resistance, of 2-phenylbenzotriazole derivatives having thioaryl or thiocyclohexyl ring groups have not been investigated at all.

[0008] The present invention has been made in view of the above circumstances, and aims to provide an ultraviolet absorber that efficiently absorbs harmful light in the wavelength range of 380 to 400 nm, suppresses the absorption of light with wavelengths above 400 nm which is a cause of initial yellowing, thereby reducing the effects of harmful light, and allows for the creation of a component with good affinity to organic materials, inorganic materials such as glass, and excellent appearance, as well as excellent light resistance and heat resistance, and furthermore, provides an ultraviolet absorber with excellent light resistance and heat resistance, i.e., durability. The present invention aims to provide an organic material composition containing an ultraviolet absorber in which the ultraviolet absorber does not bleed out, has excellent affinity to the ultraviolet absorber, has excellent appearance retention, and in particular, when the appearance is transparent, it can be a composition that suppresses yellowing and has excellent transparency retention. Furthermore, the present invention aims to provide an ultraviolet absorber that is an organic material composition in which discoloration, a decrease in ultraviolet absorption capacity, and a decrease in transparency do not occur over a long period of use, and is otherwise an organic material composition with excellent light resistance and heat resistance, i.e., durability. [Means for solving the problem]

[0009] In order to solve the above problems, [I] the highly light-resistant ultraviolet absorber of the present invention is characterized by comprising a 2-phenylbenzotriazole derivative having a thioaryl ring group or a thiocyclohexyl ring group represented by any of the following formulas (1) to (4).

[0010]

Chemical formula

[0011] (In the formula, PhBzT 1a represents a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-X 1a -…) may be bonded, X 1a represents a residue of a phenyl ring or a naphthyl ring, and l R 1a each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and l represents an integer of 0 to 5.)

[0012]

Chemical formula

[0013] (In the formula, PhBzT 1b represents a 2-phenylbenzotriazole skeleton to which a thiocyclohexyl ring group (-S-Cy-…) may be bonded, Cy represents a cyclohexyl ring residue, and m R 1b each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and m represents an integer of 0 to 5.)

[0014]

Chemical formula

[0015] (In the formula, PhBzT 1c and PhBzT 2c each independently represents a thioaryl ring group (-S-A 1cIt exhibits a 2-phenylbenzotriazole skeleton to which -S-) is attached, A 1c The equation is as follows:

[0016] [ka]

[0017] (In the formula, X 1c and X 2c Each independently represents a phenyl ring or naphthyl ring residue, and n R 1c and p R 2c Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxyl group, and n and p represent integers from 0 to 4. 2c ) represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, where a hydrogen atom may be substituted, at least one of the ends may be interrupted, or the carbon-carbon bond may be interrupted, and q represents an integer of 0 or 1. ) This represents a group represented by ) or a phenyl ring or naphthyl ring residue.

[0018] [ka]

[0019] (In the formula, PhBzT 1d and PhBzT 2d Each of these may independently have substituents, with a thioaryl ring group (-SX) on the phenyl moiety of the benzotriazole skeleton. 1d -…or -SX 2d -...) is bonded, and A is attached to the phenyl skeleton at position 2 Ph. 1d It exhibits a 2-phenylbenzotriazole skeleton to which X is attached. 1d and X 2d Each independently represents a phenyl ring or naphthyl ring residue, and r R 1d and s R 2dEach of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxyl group, and r and s represent integers from 0 to 5. 1d This refers to a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may have a hydrogen atom substituted, at least one of its ends interrupted, or a carbon-carbon bond interrupted, and is a divalent hydrocarbon group having 1 to 20 carbon atoms. As an indicator of the lightfastness of this highly lightfast UV absorber, it is preferable that at least one of the differences in transmittance (ΔTuv) at wavelengths of 380, 390, and 400 nm is 6% or less when measured under the following conditions, more preferably all are 6% or less, even more preferably all are 4% or less, and even more preferably all are 2% or less: <Measurement conditions for the difference in transmittance (ΔTuv)> Samples of soda glass coated with acrylic resin and UV absorber in a mass ratio of 0.6-3.4:0.1 and with a film thickness of 2-50 μm were tested at a wavelength of 300-400 nm and an illuminance of 42 W / m². 2 The black panel is irradiated with ultraviolet light for 70 hours at a temperature of 63°C, and the transmittance of the ultraviolet-visible transmission spectrum before irradiation (T1uv) and after irradiation (T2uv) is calculated using the following formula.

[0020]

number

[0021] [II] The heat-resistant ultraviolet absorber of the present invention is characterized by comprising a 2-phenylbenzotriazole derivative having a thioaryl ring group represented by any of the following formulas (1), (3), or (4).

[0022] [ka]

[0023] (In the formula, PhBzT 1a The thioaryl ring group (-SX) may have substituents. 1a-…) shows a 2-phenylbenzotriazole skeleton to which X 1a indicates a residue of a phenyl ring or naphthyl ring, and l R 1a Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, or a hydroxyl group, and l represents an integer from 0 to 5.

[0024] [ka]

[0025] (In the formula, PhBzT 1c and PhBzT 2c Each of these may independently have a substituent, a thioaryl ring group (-SA 1c It exhibits a 2-phenylbenzotriazole skeleton to which -S-) is attached, A 1c The equation is as follows:

[0026] [ka]

[0027] (In the formula, X 1c and X 2c Each independently represents a phenyl ring or naphthyl ring residue, and n R 1c and p R 2c Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxyl group, and n and p represent integers from 0 to 4. 2c ) represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, where a hydrogen atom may be substituted, at least one of the ends may be interrupted, or the carbon-carbon bond may be interrupted, and q represents an integer of 0 or 1. ) This represents a group represented by ) or a phenyl ring or naphthyl ring residue.

[0028] [ka]

[0029] (In the formula, PhBzT 1d and PhBzT 2d Each of these may independently have substituents, with a thioaryl ring group (-SX) on the phenyl moiety of the benzotriazole skeleton. 1d -…or -SX 2d -...) is bonded, and A is attached to the phenyl skeleton at position 2 Ph. 1d It exhibits a 2-phenylbenzotriazole skeleton to which X is attached. 1d and X 2d Each independently represents a phenyl ring or naphthyl ring residue, and r R 1d and s R 2d Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxyl group, and r and s represent integers from 0 to 5. 1d This refers to a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may have a hydrogen atom substituted, at least one of its ends interrupted, or a carbon-carbon bond interrupted, and is a divalent hydrocarbon group having 1 to 20 carbon atoms. [III] The durable ultraviolet absorber of the present invention is the heat-resistant ultraviolet absorber described above, and is a highly light-resistant and heat-resistant durable ultraviolet absorber, When measured under the following conditions, it is characterized by at least one of the transmittance differences (ΔTuv) at wavelengths of 380, 390, and 400 nm being 6% or less: <Measurement conditions for the difference in transmittance> Samples of soda glass coated with acrylic resin and UV absorber in a mass ratio of 0.6-3.4:0.1 and with a film thickness of 2-50 μm were tested at a wavelength of 300-400 nm and an illuminance of 42 W / m². 2 The black panel is irradiated with ultraviolet light for 70 hours at a temperature of 63°C, and the transmittance of the ultraviolet-visible transmission spectrum before irradiation (T1uv) and after irradiation (T2uv) is calculated using the following formula.

[0030]

number

[0031] As an indicator of the light resistance of this durable UV absorber, the difference in transmittance (ΔTuv) at the above wavelengths of 380, 390, and 400 nm is preferably 6% or less, more preferably 4% or less, and even more preferably 2% or less.

[0032] The organic resin composition of the present invention comprises the above-mentioned highly light-resistant ultraviolet absorber, heat-resistant ultraviolet absorber, or durable ultraviolet absorber, and an organic resin.

[0033] [IV] The ultraviolet absorber of the present invention is an ultraviolet absorber used for an ultraviolet shielding film for glass or an ultraviolet shielding film forming composition, It is characterized by comprising a 2-phenylbenzotriazole derivative having a thioaryl ring group, a thiocyclohexyl ring group, a thioalkyl group, or a thioalkylene group, represented by any of the following formulas (1) to (6):

[0034] [ka]

[0035] (In the formula, PhBzT 1a The thioaryl ring group (-SX) may have substituents. 1a -…) shows a 2-phenylbenzotriazole skeleton to which X 1a X represents a residue of a phenyl ring or naphthyl ring, where X 1a l R 1a In addition, it may have substituents other than l R 1a Each of these independently represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may be a hydrocarbon group or alkoxy group having 1 to 18 carbon atoms, where a hydrogen atom in the carbon chain is substituted, the base end of the carbon chain is interrupted, or the carbon-carbon bond is interrupted, and l represents an integer from 0 to 5.

[0036] [ka]

[0037] (In the formula, PhBzT 1b represents a 2-phenylbenzotriazole skeleton to which a thiocyclohexyl ring group (-S-Cy-…) may have substituents, where Cy represents a cyclohexyl ring residue, and Cy has m R 1b In addition, it may have substituents other than m R 1b Each of these independently represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may be a hydrocarbon group or alkoxy group having 1 to 18 carbon atoms, where a hydrogen atom in the carbon chain is substituted, the base end of the carbon chain is interrupted, or the carbon-carbon bond is interrupted, and m represents an integer from 0 to 5.

[0038] [ka]

[0039] (In the formula, PhBzT 1c and PhBzT 2c Each of these may independently have a substituent, a thioaryl ring group or a thioalkylene group (-SA). 1c It exhibits a 2-phenylbenzotriazole skeleton to which -S-) is attached, A 1c The equation is as follows:

[0040] [ka]

[0041] (In the formula, X 1c and X 2c Each of these independently represents a residue of either a phenyl ring or a naphthyl ring, where X 1c and X 2c n R 1c and p R 2cIn addition, it may have substituents other than n R 1c and p R 2c Each of these independently represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may be a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxyl group, where a hydrogen atom in the carbon chain is substituted, the base end of the carbon chain is interrupted, or the carbon-carbon bond is interrupted, and n and p represent integers from 0 to 4, A 2c ) represents a group represented by ), or a phenyl ring residue, naphthyl ring residue, or a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, where a hydrogen atom may be substituted, at least one end may be interrupted, or the carbon-carbon bond may be interrupted, and q represents an integer of 0 or 1.

[0042] [ka]

[0043] (In the formula, PhBzT 1d and PhBzT 2d Each of these may independently have substituents, with a thioaryl ring group (-SX) on the phenyl moiety of the benzotriazole skeleton. 1d -…or -SX 2d -...) is bonded, and A is attached to the phenyl skeleton at position 2 Ph. 1d It exhibits a 2-phenylbenzotriazole skeleton to which X is attached. 1d and X 2d Each of these independently represents a residue of either a phenyl ring or a naphthyl ring, where X1d and X 2d are r R's 1d and s R's 2d may also have substituents other than these, and the r R's 1d and the s R's 2d are each independently a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, and may be a hydrocarbon group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group in which a hydrogen atom of a carbon chain is substituted, the terminal of the carbon chain is interrupted, or a carbon-carbon bond is interrupted, and r and s represent integers of 0 to 5. A 1d is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted, at least one of both ends is interrupted, or a carbon-carbon bond is interrupted.)

[0044]

Chemical formula

[0045] (In the formula, PhBzT 1e represents a 2-phenylbenzotriazole skeleton to which a thioalkyl group (-S-Y 1e ) is bonded, and Y 1e is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, and represents a linear or branched alkyl group having 1 to 22 carbon atoms in which a hydrogen atom is substituted, the terminal is interrupted, or a carbon-carbon bond is interrupted.)

[0046]

Chemical formula

[0047] (In the formula, PhBzT 1f and PhBzT 2fThe phenyl moiety of the benzotriazole skeleton, which may each independently have a substituent, has a thioalkyl group (-S-Y 1f or -S-Y 2f ) bonded thereto, and shows a 2-phenylbenzotriazole skeleton in which A 1f is bonded to the phenyl skeleton Ph at the 2-position. Y 1f and Y 2f each independently represent a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, and represent a linear or branched alkyl group having 1 to 22 carbon atoms, in which a hydrogen atom may be substituted, a group end may be interrupted, or a carbon-carbon bond may be interrupted.) A 1f represents a monovalent or divalent group selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, in which a hydrogen atom may be substituted, at least one of both ends may be interrupted, or a carbon-carbon bond may be interrupted.) [Effect of the Invention]

[0048] The ultraviolet absorber of the present invention efficiently absorbs harmful light in the wavelength range of 380 to 400 nm and suppresses the absorption of light with wavelengths above 400 nm, which is a cause of initial yellowing. This reduces the effects of harmful light, and allows for the creation of components with good affinity to organic materials and inorganic materials such as glass, resulting in a superior appearance. Furthermore, by introducing an aryl group via a thioether group to the 2-phenylbenzotriazole skeleton, the ultraviolet absorber of the present invention stabilizes the π-electron conjugated system or the intermolecular interactions of the hydrocarbon group introduced to the aryl group, resulting in excellent light resistance and heat resistance, and furthermore, excellent durability. An organic material composition containing the ultraviolet absorber does not allow the ultraviolet absorber to bleed out, has excellent affinity to the ultraviolet absorber, and maintains its appearance well. In particular, when the appearance is transparent, it can be a composition that suppresses yellowing and maintains its transparency well. Moreover, due to the above physical properties of the ultraviolet absorber and the prevention of degradation of organic materials, it exhibits excellent light resistance and heat resistance, i.e., durability, without discoloration, decrease in ultraviolet absorption capacity, or decrease in transparency over a long period of use. Furthermore, the ultraviolet absorber of the present invention can be in the form of such an organic material composition. [Brief explanation of the drawing]

[0049] [Figure 1] This shows the ultraviolet-visible absorption spectra (UV charts) of compounds 1-5 in the examples. [Figure 2] This shows the ultraviolet-visible absorption spectra (UV charts) of compounds 6-10 in the examples. [Figure 3] This shows the ultraviolet-visible absorption spectra (UV charts) of compounds 11-15 in the examples. [Figure 4] These are the ultraviolet-visible absorption spectra (UV charts) of compounds 16-18 in the examples, compounds 19 and 21 in the reference example, and compound 22 in the comparative example. [Modes for carrying out the invention]

[0050] The present invention will be described in detail below.

[0051] In this specification, when "the ultraviolet absorber of the present invention" is used, it means at least one of the following: [I] a highly light-resistant ultraviolet absorber, [II] a heat-resistant ultraviolet absorber, [III] a durable ultraviolet absorber, or [IV] an ultraviolet absorber used in an ultraviolet shielding film for glass or in a composition for forming an ultraviolet shielding film.

[0052] In this specification, "highly lightfast ultraviolet absorber" primarily refers to an absorber whose transmittance difference (ΔTuv) at wavelengths of 380, 390, and 400 nm falls within the range disclosed as preferred examples herein, although this is not an exhaustive definition.

[0053] In this specification, “heat-resistant ultraviolet absorber” means, but is not limited to, those within the range disclosed herein as preferred examples in terms of weight change rate and / or discoloration after heating. In this specification, "durable ultraviolet absorber" means, in addition to the heat resistance described above, but not limited to, a difference in transmittance (ΔTuv) at wavelengths of 380, 390, and 400 nm within the range disclosed as preferred examples herein.

[0054] In the following descriptions of specific embodiments and preferred examples of the 2-phenylbenzotriazole skeleton represented by formula (A) and the subsequent 2-phenylbenzotriazole derivatives of formulas (1) to (4), unless otherwise specified, the description applies to all ultraviolet absorbers of the present invention, mainly focusing on highly light-resistant ultraviolet absorbers. However, based on the results in the examples section described later, it also includes specific embodiments and preferred examples of ultraviolet absorbers used in heat-resistant ultraviolet absorbers or durable ultraviolet absorbers, organic resin compositions, ultraviolet shielding films for glass, or ultraviolet shielding film-forming compositions. The ultraviolet absorbers of the present invention, particularly highly light-resistant ultraviolet absorbers, heat-resistant ultraviolet absorbers, and durable ultraviolet absorbers, consist of 2-phenylbenzotriazole derivatives having a thioaryl ring group or a thiocyclohexyl ring group, and these 2-phenylbenzotriazole derivatives are represented by any of the above formulas (1) to (4). Furthermore, the ultraviolet absorbers used in ultraviolet shielding films for glass or compositions for forming ultraviolet shielding films consist of 2-phenylbenzotriazole derivatives having a thioaryl ring group, a thiocyclohexyl ring group, a thioalkyl group, or a thioalkylene group, and these 2-phenylbenzotriazole derivatives are represented by any of the above formulas (1) to (6).

[0055] (2-phenylbenzotriazole skeleton of 2-phenylbenzotriazole derivatives) PhBzT in equation (1) 1a PhBzT in equation (2) 1b PhBzT in equation (3) 1c and PhBzT 2c PhBzT in equation (4) 1d and PhBzT 2d PhBzT in equation (5) 1e PhBzT in equation (6) 1f and PhBzT 2f The 2-phenylbenzotriazole skeleton is represented by the following formula (A).

[0056] [ka]

[0057] In formula (A), R 1 ~R 9 Each of these independently represents at least one of a thioaryl ring group, a thiocyclohexyl ring group, a thioalkyl group, or a thioalkylene group, and the others represent a hydrogen atom or a substituent.

[0058] In formula (A), the substitution position of the thioaryl ring group, thiocyclohexyl ring group, thioalkyl group, or thioalkylene group is not particularly limited, and unless specified in formulas (1) to (6) above, R 1 ~R 9 Any of the following may be acceptable, 6 ~R 9 Preferably, R 7 , R 8 This is more preferable. The number of substitutions of thioaryl ring groups, thiocyclohexyl ring groups, thioalkyl groups, or thioalkylene groups is not particularly limited unless specified in formulas (1) to (6) above, but is for example 1 to 2, and 1 is preferred.

[0059] Examples of the above substituents include monovalent or divalent groups selected from the following hydrocarbon groups, aromatic groups, unsaturated groups, nitrogen-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms. When the above substituent is a divalent group, R 1 ~R 9 Any two of these (preferably two adjacent ones) come together to form a ring. These substituents are further monovalent or divalent groups selected from aromatic groups, unsaturated groups, nitrogen-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, as exemplified below, and may be substituted for hydrogen atoms, interrupted at least one of the ends, or have a carbon-carbon bond interrupted.

[0060] Examples of hydrocarbon groups include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, benzene rings, naphthalene rings, anthracene rings, etc., where hydrogen atoms may be substituted with alkyl groups, and the number of carbon atoms is preferably 1 to 18, more preferably 1 to 10. Specifically, there are no particular limitations on linear or branched alkyl groups, but examples include methyl group, benzyl group, α,α-dimethylbenzyl group, ethane-1-yl group, propane-1-yl group, 1-methylethane-1-yl group, butane-1-yl group, butane-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentane-1-yl group, pentane-2-yl group, hexane- Examples include 1-yl group, heptane-1-yl group, octan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, nonane-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, etc.Examples of linear or branched alkenyl groups include vinyl group, propa-1-en-1-yl group, allyl group, isopropenyl group, buta-1-en-1-yl group, buta-2-en-1-yl group, buta-3-en-1-yl group, 2-methylpropa-2-en-1-yl group, 1-methylpropa-2-en-1-yl group, penta-1-en-1-yl group, penta-2-en-1-yl group, penta-3-en-1-yl group, penta- Ta-4-en-1-yl group, 3-methylbuta-2-en-1-yl group, 3-methylbuta-3-en-1-yl group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, hexa-4-en-1-yl group, hexa-5-en-1-yl group, 4-methylpenta-3-en-1-yl group, hepta-1-en-1-yl group, hepta-6-en-1-yl group, octa-1-en-1 -yl group, octa-7-en-1-yl group, nona-1-en-1-yl group, nona-8-en-1-yl group, deca-1-en-1-yl group, deca-9-en-1-yl group, undeca-1-en-1-yl group, undeca-10-en-1-yl group, dodeca-1-en-1-yl group, dodeca-11-en-1-yl group, trideca-1-en-1-yl group, trideca-12-en-1-yl group, tetradeca-1-en-1- Examples include yl groups, tetradeca-13-en-1-yl groups, pentadeca-1-en-1-yl groups, pentadeca-14-en-1-yl groups, hexadeca-1-en-1-yl groups, hexadeca-15-en-1-yl groups, heptadeca-1-en-1-yl groups, heptadeca-16-en-1-yl groups, octadeca-1-en-1-yl groups, octadeca-9-en-1-yl groups, and octadeca-17-en-1-yl groups.Examples of linear or branched alkynyl groups include ethinyl, propa-1-in-1-yl, propa-2-in-1-yl, buta-1-in-1-yl, buta-3-in-1-yl, 1-methylpropa-2-in-1-yl, penta-1-in-1-yl, penta-4-in-1-yl, hexa-1-in-1-yl, hexa-5-in-1-yl, hepta-1-in-1-yl, hepta-6-in-1-yl, octa-1-in-1-yl, octa-7-in-1-yl, nona-1-in-1-yl, nona-8-in-1-yl, deca-1-in-1-yl, and deca-9-in-1-yl Examples include the groups, undeca-1-in-1-yl group, undeca-10-in-1-yl group, dodeca-1-in-1-yl group, dodeca-11-in-1-yl group, trideca-1-in-1-yl group, trideca-12-in-1-yl group, tetradeca-1-in-1-yl group, tetradeca-13-in-1-yl group, pentadeca-1-in-1-yl group, pentadeca-14-in-1-yl group, hexadeca-1-in-1-yl group, hexadeca-15-in-1-yl group, heptadeca-1-in-1-yl group, heptadeca-16-in-1-yl group, octadeca-1-in-1-yl group, octadeca-17-in-1-yl group, and so on. Among these, linear or branched alkyl groups having 1 to 18 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 10 carbon atoms are more preferred. Furthermore, the hydrogen atoms of these hydrocarbon groups may be substituted with halogen atoms such as fluorine, chlorine, bromine, or iodine. The aromatic group includes aromatic rings such as benzene rings, naphthalene rings, and anthracene rings, and preferably has 6 to 18 carbon atoms, more preferably 6 to 14. The monovalent aromatic group is not particularly limited, but examples include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, and 9-anthracenyl group. The divalent aromatic group is not particularly limited, but examples include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group, 2,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, 1,4-anthracenylene group, and 1,3-anthracenylene group.

[0061] 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, cyanato group, etc.), with a carbon number preferably of 1 to 10, more preferably of 1 to 8. 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, cyano group, cyanato group, isocyanate group, urethane group, etc.

[0062] The nitrogen-containing group includes a cyano group, a nitro group, or a primary to tertiary amino group, and preferably has 0 to 10 carbon atoms. The nitrogen-containing group is not particularly limited, but examples include cyano group, cyanato group, isocyanate group, nitro group, nitroalkyl group, carbamate group, urea group, amide group, imide group, carbamoyl group, urethane group, etc., imide group, amino group, primary amino group, secondary amino group, tertiary amino group, aminoalkyl group, 3,4,5,6-tetrahydrophthalimidylmethyl group, 2-[6-(2H-benzotriazole-2-yl-)-4-(1,1,3,3-tetramethylbutyl)phenol-yl]-methyl group, etc.

[0063] If the oxygen-containing group includes an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 12. If it does not include an aromatic ring group or an alicyclic group, the number of carbon atoms is preferably 0 to 18. The oxygen-containing group is not particularly limited, but examples include hydroxyl group, alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, t-butoxy group, sec-pentyloxy group, iso-pentyloxy group, t-pentyloxy group, 1-hexyloxy group, 2-hexyloxy group, 3-hexyloxy group, 1-heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, 4-heptyloxy group, 1-octyloxy group, 2-octyloxy group, 3-octyloxy group, 4-octyloxy group, 1-nonyloxy group, 2-nonyloxy group, 3-nonyloxy group, 4-nonyloxy group, 5-nonyloxy group, 1-decyloxy group Examples include oxy groups, 2-decyloxy groups, 3-decyloxy groups, 4-decyloxy groups, 5-decyloxy groups, 1-undecyloxy groups, 1-dodecyloxy groups, 1-tridecyloxy groups, 1-tetradecyloxy groups, 1-pentadecyloxy groups, 1-hexadecyloxy groups, 1-heptadecyloxy groups, 1-octadecyloxy groups, phenoxy groups, methylphenoxy groups, dimethylphenoxy groups, naphthoxy groups, phenylmethoxy groups, phenylethoxy groups, acetoxy groups, acetyl groups, aldehyde groups, carboxyl groups, urea groups, urethane groups, amide groups, imide groups, ether groups, carbonyl groups, ester groups, oxazole groups, morpholine groups, carbamate groups, carbamoyl groups, and polyoxyethylene groups. Among these, hydroxyl groups, alkoxy groups having 1 to 18 carbon atoms, ether groups having 1 to 18 carbon atoms, ester groups having 1 to 18 carbon atoms, and polyoxyethylene groups having 1 to 20 carbon atoms are preferred.

[0064] 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 18. The phosphorus-containing group is not particularly limited, but examples include trimethylphosphine group, triethylphosphine group, tripropylphosphine group, tributylphosphine group, tripentylphosphine group, trihexylphosphine group, tricyclohexylphosphine group, triphenylphosphine group, tritlylphosphine group, methylphosphite group, ethylphosphite group, phenylphosphite group, phosphonic acid group, phosphinic acid group, phosphoric acid group, phosphoric acid group, and phosphoric acid ester group.

[0065] The alicyclic group preferably has 3 to 10 carbon atoms, more preferably 3 to 8. The alicyclic group is not particularly limited, but examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

[0066] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0067] From the viewpoint of improving light resistance, the following combinations of substituents are preferred.

[0068] For items A to E below, in the combination of the ultraviolet absorber of the present invention and an organic material containing an organic resin, R in formula (A) 6 , R 7 , R 8 , R 9 The following are some preferred combinations. A-1 R in each equation (1), (3), and (4) 6 , R 7 , R 8 , R 9 At least one of them is a thioaryl ring group. Also, R in formula (2) 6 , R 7 , R 8 , R9 At least one of them is a thiocyclohexyl ring group. Also, in [IV] above, R of formula (3) 6 , R 7 , R 8 , R 9 At least one of these is a thioalkylene group. Also, R in formulas (5) and (6) 6 , R 7 , R 8 , R 9 At least one of them is a thioalkyl group. A-2 In A-1, the X of the thioaryl ring group 1a , X 1c , X 2c , X 1d , X 2d These are residues of a phenyl ring or naphthyl ring. A-3 In A-1 and A-2, PhBzT 1a PhBzT 1b PhBzT 1c PhBzT 2c PhBzT 1d PhBzT 2d A single thioaryl ring group or thiocyclohexyl ring group is attached to it. Also, in [IV] above, PhBzT 1c PhBzT 2c One thioalkylene group is bonded to it. PhBzT 1e PhBzT 1f PhBzT 2f A single thioalkyl group is attached to it. A-4 In any of A-1 to A-3, one thioaryl ring group or thiocyclohexyl ring group is R 7 or R 8 It is bonded to [IV] above. Also, one thioalkylene group and one thioalkyl group are R 7 or R 8 Combine. A-5 In any of A-1 to A-4, R other than a thioaryl ring group or a thiocyclohexyl ring group 6 ~R 9 All of them are hydrogen atoms. Also, in the above [IV], R other than thioalkylene groups and thioalkyl groups 6~R 9 They are all hydrogen atoms. A-6 In any of A-1 to A-5, the thioaryl ring group X 1a , X 1c , X 2c , X 1d , X 2d It is a residue of the phenyl ring. A-7 In any of A-1 to A-5, the thioaryl ring group X 1a , X 1c , X 2c , X 1d , X 2d This is a residue of the naphthyl ring.

[0069] R in equation (A) of equations (1) to (3) and (5) 1 , R 2 , R 3 , R 4 , R 5 A preferred example of the combination is as follows: PhBzT in equation (3) 1c and PhBzT 2c R 1 , R 2 , R 3 , R 4 , R 5 These can be independently different or identical. I-1 A hydrocarbon group having 1 to 18 carbon atoms (including a hydrocarbon group having 2 to 18 carbon atoms that includes an alkenyl group or an alkynyl group), a hydroxyl 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 and / or a polyoxyethylene group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms in which a hydrogen atom may be substituted by the substituent, the base end may be interrupted, or the carbon-carbon bond may be interrupted. I-2 In I-1, the substituent is at least one selected from hydrocarbon groups having 1 to 10 carbon atoms and hydroxyl groups. I-3 In I-2, the substituent is at least one selected from hydrocarbon groups having 1 to 8 carbon atoms and hydroxyl groups. I-4 In any of I-1 to I-3, the hydrocarbon group of the substituent is a linear or branched alkyl group. In I-5 and I-4, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxyl group. In I-6 and I-5, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxyl group, and there is one or fewer hydroxyl groups. I-7 In any of I-1 to I-6, the number of substituents is 1 to 4. I-8 In any of I-1 to I-7, R 1 ~R 4 It has a substituent at any of the other R positions. 1 ~R 5 It is a hydrogen atom. In any of I-9 I-1 to I-8, R 1 , R 2 , R 4 It has a substituent at any of the other R positions. 1 ~R 5 It is a hydrogen atom. In I-10 and I-9, R 1 R is a hydroxyl group, 2 is a t-butyl group, R 4 R is a methyl group, 3 , R 5 It is a hydrogen atom. I-11 In any of I-1 to I-9, R 1 , R 4 It has a substituent at any of the other R positions. 1 ~R 5 It is a hydrogen atom. In I-12 and I-11, R 1 R is a hydroxyl group, 4 R is a methyl group, 2 , R 3 , R 5 It is a hydrogen atom.

[0070] R in equation (A) of equations (4) and (6) 1 , R 2 , R 3 , R4 , R 5 A preferred example of the combination is as follows: PhBzT in equation (4) 1d and PhBzT 2d PhBzT in equation (6) 1f and PhBzT 2f R 1 , R 2 , R 3 , R 4 , R 5 These can be independently different or identical. I-13 PhBzT 1d and PhBzT 2d Each of the R 2 is, -A 1d -is the case. Also, PhBzT 1f and PhBzT 2f Each of the R 2 is, -A 1f - is In I-14 and I-13, -A 1d -, -A 1f - is a divalent hydrocarbon group having 1 to 8 carbon atoms. In I-15 and I-13, -A 1d -, -A 1f - is a divalent hydrocarbon group having 1 to 4 carbon atoms. In I-16 and I-13, -A 1d -, -A 1f - is a divalent hydrocarbon group with 1 to 2 carbon atoms. I-17 In any of I-14 to I-16, -A 1d -, -A 1f - represents a linear or branched alkyl group. In I-18 and I-17, -A 1d -, -A 1f - represents a methylene group or an ethylene group. I-19 In any of I-13 to I-18, -A 1d -, -A 1f - Other than R 1 , R 2 , R 3 , R 4 , R 5It contains one or more substituents selected from hydrocarbon groups having 1 to 18 carbon atoms (including hydrocarbon groups having 2 to 18 carbon atoms that include alkenyl groups and alkynyl groups), hydroxyl groups, aromatic groups having 6 to 18 carbon atoms, ether groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, ester groups having 1 to 18 carbon atoms, (meth)acryloyloxy groups and / or polyoxyethylene groups, or hydrocarbon groups having 1 to 18 carbon atoms in which hydrogen atoms may be substituted by their substituents, the base end may be interrupted, or the carbon-carbon bond may be interrupted. In I-20 and I-19, the substituent is at least one selected from hydrocarbon groups having 1 to 10 carbon atoms and hydroxyl groups. In I-21 and I-20, the substituent is at least one selected from hydrocarbon groups having 1 to 8 carbon atoms and hydroxyl groups. I-22 In any of I-19 to I-21, the hydrocarbon group of the substituent is a linear or branched alkyl group. In I-23 and I-22, the substituent is at least one selected from a methyl group, a t-butyl group, a 1,1,3,3-tetramethylbutyl group, and a hydroxyl group. In I-24 and I-23, the substituent is at least one selected from a methyl group, a t-butyl group, a 1,1,3,3-tetramethylbutyl group, and a hydroxyl group, and there is one or fewer hydroxyl groups. I-25 In any of I-19 to I-24, the number of substituents is 1 to 4. I-26 In any of I-19 to I-25, R 1 , R 3 , R 4 It has a substituent at any of the other R positions. 1 , R 3 , R 4 , R 5 It is a hydrogen atom. I-27 In any of I-19 to I-26, R 1 , R 4 It has a substituent at any of the other R positions. 3 , R 5 It is a hydrogen atom. In I-28 and I-27, R1 R is a hydroxyl group, 4 is 1,1,3,3-tetramethylbutyl, and R 3 , R 5 It is a hydrogen atom. (The thioaryl ring group represented by formulas (1) and (4), (-SX 1a -…, -SX 1d -…or -SX 2d (2-phenylbenzotriazole derivatives having -...) In equations (1) and (4), l Rs, respectively 1a and X 1a , r R 1d and X 1d s R 2d and X 2d The following are some preferred combinations. U-1 X 1a , X 1d , X 2d It is a residue of the phenyl ring. In U-2 U-1, l, r, s = 0, X 1a , X 1d , X 2d to substituent R 1a , R 1d , R 2d X 1a , X 1d , X 2d In R 1a , R 1d , R 2d All the parts that can be substituted are hydrogen atoms. In U-3 U-1, there are l, r, and s R 1a , R 1d , R 2d Each of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, with l, r, and s = 1 to 5. In U-4 and U-3, l, r, and s are 1 to 3. In U-5 and U-4, R 1a , R 1d , R 2d Each of these is independently a branched alkyl group having at least one carbon atom between 3 and 8. In U-6 and U-4, l, r, and s are 1, and R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In U-7 and U-6, l, r, and s = 1, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the alkyl group preferably has 1 to 8 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and especially preferably 4 carbon atoms. In any of the following cases, PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d For -S-, R 1a , R 1d , R 2d At least one of them is in the para position. In U-9 U-4, l, r, s = 2, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In U-10 and U-9, l, r, and s = 2, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the number of carbon atoms in each alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, and / or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2. U-11 In either U-9 or U-10, PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d For -S-, l, r, and s=2 are R 1a , R 1d , R 2dIt is located at the ortho, para, or ortho, meta positions. U-12 In any of U-3 to U-11, R 1a , R 1d , R 2d Each of these is a hydrocarbon group having a tertiary carbon and / or quaternary carbon independently, and is preferably an alkyl group. In U-13 U-1, there are l, r, and s R 1a , R 1d , R 2d Each of these is an alkoxy group having a linear or branched alkyl group with 1 to 18 carbon atoms, preferably an alkoxy group having a linear alkyl group with 1 to 8 carbon atoms, more preferably an alkoxy group having a linear alkyl group with 1 to 4 carbon atoms. Furthermore, l,r,s = 1 to 3, more preferably l,r,s = 1 to 2, and particularly preferably l,r,s = 1. In U-14 and U-13, l, r, and s are 1, and the alkoxy group is PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d It occupies a meta position relative to -S-. In U-15 U-1, there are l, r, and s R 1a , R 1d , R 2d is a hydroxyl group, preferably l,r,s=1-3, more preferably l,r,s=1-2, and especially preferably l,r,s=1. In U-16 and U-15, l, r, and s are 1, and the hydroxyl group is PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d It is in the para position relative to -S-. U-17 X 1a , X 1d , X 2d is a naphthyl ring residue, preferably l, r, s = 0.

[0071] The 2-phenylbenzotriazole derivative represented by formula (1) is not particularly limited, but examples include 5-phenylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-tert-butyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(2,4-dimethyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(3-methoxy-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, and 5-(4-(1,1-dimethyl-propyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-ben Zotriazole, 5-(4-isopropyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-(1,1,3,3-tetramethyl-butyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(2-methyl-5-tert-butyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-methyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(2,4-di(1,1-dimethylpropyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole Examples include 5-(4-hydroxyphenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-naphthylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, and 5-phenylthio-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.

[0072] (A 2-phenylbenzotriazole derivative having a thiocyclohexyl ring group (-S-Cy-…) represented by formula (2)) m R in equation (2) 1b The following are some preferred combinations. E-1 m=0, Cy has substituent R 1b There is no R in Cy 1b All the parts that can be substituted are hydrogen atoms. E-2 m pieces of R 1b Each of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, with m=1 to 5. In E-3 and E-2, m = 1 to 3. In E-4 and E-3, R 1b Each of these is independently a branched alkyl group having at least one carbon atom between 3 and 8. In E-5 and E-3, m=1, R 1b This is a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In E-6 and E-5, m=1, R 1b The alkyl group is a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group preferably has 1 to 8 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and especially preferably 4 carbon atoms. In any of E-7, E-2~6, PhBzT 1b -S- vs R 1b At least one of them is in the para position. In E-8 and E-3, m=2, R 1b Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In E-9 and E-8, m=2, R 1b Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the number of carbon atoms in each alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, and / or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2. In either E-10, E-8, or E-9, PhBzT 1b For -S-, R = m=2 1b It is located at the ortho, para, or ortho, meta positions. E-11 In any of E-2 to E-10, R 1b This is a hydrocarbon group having a tertiary carbon and / or quaternary carbon, preferably a branched alkyl group. In E-12 E-1, m R 1b Each of these is an alkoxy group having a linear or branched alkyl group with 1 to 18 carbon atoms, preferably an alkoxy group having a linear alkyl group with 1 to 8 carbon atoms, and more preferably an alkoxy group having a linear alkyl group with 1 to 4 carbon atoms. Furthermore, m=1 to 3 is preferred, more preferably m=1 to 2, and particularly preferably m=1. In E-13 and E-12, m=1, and the alkoxy group is PhBzT 1b -S- has a meta position In E-14 E-1, m R 1b m is a hydroxyl group, preferably m=1 to 3, more preferably m=1 to 2, and particularly preferably m=1. In E-15 and E-14, m=1 and the hydroxyl group is PhBzT 1b It is in the para position relative to -S-.

[0073] The 2-phenylbenzotriazole derivative represented by formula (2) is not particularly limited, but examples include 5-cyclohexylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-methyl-cyclohexyl)-thio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-methoxy-cyclohexyl)-thio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-isopropyl-cyclohexyl)-thio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, and the like.

[0074] (The thioaryl ring group represented by formula (3), (-SA) 1c (2-phenylbenzotriazole derivatives having -S-) In the above equation (3), A 2c This represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may be a divalent hydrocarbon group, a divalent aromatic group, or a sulfide group-S- having 1 to 20 carbon atoms, in which a hydrogen atom is substituted, at least one of the ends is interrupted, or the carbon-carbon bond is interrupted.

[0075] A 2c Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc. Among these, aliphatic hydrocarbon groups are preferred, and examples include linear or branched alkylene groups, linear or branched alkenylene groups, linear or branched alkynylene groups, etc. Specifically, although not particularly limited, examples include methylene group, 1,1-dimethylmethylene group, ethane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane- Examples include 1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, and eicosane-1,20-diyl group. Among these, linear or branched alkylene groups are preferred, and branched alkylene groups are more preferred.

[0076] When a divalent hydrocarbon group is replaced by a monovalent or divalent group, or at least one of its ends is interrupted, or the carbon-carbon bond is interrupted, the number of monovalent or divalent groups is not particularly limited, but examples include two or fewer, or one or fewer.

[0077] Specific examples of the monovalent or divalent aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom mentioned above include the R of the 2-phenylbenzotriazole skeleton represented by formula (A) above. 1 ~R 9 Examples of substituents similar to the monovalent or divalent groups described are included, and that description is referenced. A 2c The divalent aromatic group in this compound includes aromatic rings such as benzene rings, naphthalene rings, and anthracene rings, and preferably has 6 to 18 carbon atoms, more preferably 6 to 14. The divalent aromatic group is not particularly limited, but examples include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group, 2,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, 1,4-anthracenylene group, and 1,3-anthracenylene group.

[0078] In equation (3), each of the n R 1c and X 1c p R 2c and X 2c q A 2c The following are some preferred combinations. O-1 X 1c , X 2c It is a residue of the phenyl ring. In O-2 and O-1, n and p = 0, X 1c , X 2c to substituent R 1c , R 2c X 1c , X 2c In R1c , R 2c All the parts that can be substituted are hydrogen atoms. In O-3 and O-1, there are n and p R 1c , R 2c Each of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, with n and p = 1 to 5. In O-4 and O-3, n and p = 1 to 3. In O-5 and O-4, R 1c , R 2c Each of these is independently a branched alkyl group having at least one carbon atom between 3 and 8. In O-6 and O-4, n and p=1, R 1c , R 2c Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In O-7 and O-6, n and p=1, R 1c , R 2c Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the alkyl group preferably has 1 to 8 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and especially preferably 4 carbon atoms. In O-8 and O-4, n and p=2, R 1c , R 2c Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In O-9 and O-8, n and p=2, R 1c , R 2c Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the number of carbon atoms in each alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, and / or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2. In any of O-10, O-3 through O-9, R 1c , R 2cEach of these is a hydrocarbon group having a tertiary carbon and / or quaternary carbon independently, and is preferably an alkyl group. In O-11, there are n and p R 1c , R 2c Each of these is an alkoxy group having a linear or branched alkyl group with 1 to 18 carbon atoms, preferably an alkoxy group having a linear alkyl group with 1 to 8 carbon atoms, and more preferably an alkoxy group having a linear alkyl group with 1 to 4 carbon atoms. Furthermore, n,p=1 to 3 is preferred, more preferably n,p=1 to 2, and particularly preferred n,p=1. In O-12 O-1, n, p R 1c , R 2c is a hydroxyl group, preferably n,p=1-3, more preferably n,p=1-2, and particularly preferably n,p=1. O-13 X 1c , X 2c is a naphthyl ring residue, preferably n, p=0. O-14 In any of O-1 to O-13, q=1, A 2c The group is a sulfide group. Preferably, n, p=0, X 1c , X 2c to substituent R 1c , R 2c X 1c , X 2c In R 1c , R 2c All the parts that can be substituted are hydrogen atoms. O-15 In any of O-1 to O-13, q=1, A 2c The hydrocarbon group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) (preferably a linear or branched alkylene group). Preferably, n, p=0, X 1c , X 2c to substituent R 1c , R 2c X 1c , X 2c In R 1c , R 2c All the parts that can be substituted are hydrogen atoms. In O-16, q=0 in any of O-1 to O-13. Preferably, n, p=0, X 1c , X 2c to substituent R 1c , R 2c X 1c , X 2c In R 1c , R 2c All the parts that can be substituted are hydrogen atoms. O-17 In any of O-1 to O-16, -(A 1c ) q - is PhBzT 1c -S-, PhBzT 2c It is in a para position relative to -S-.

[0079] The 2-phenylbenzotriazole derivative represented by formula (3) is not particularly limited, but examples include 4,4'-thiobis[(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-yl-thiobenzene], 4,4'-propane-2,2-diylbis[(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-yl-thiobenzene], and 4,4'-biphenylbis[(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-yl-thio]. (Represented by formula (4), with a thioaryl ring group at position 5 (-SX 1d -…or -SX 2d (2-phenylbenzotriazole derivatives having -...) In the above formula (4), A 1d This represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may have a hydrogen atom substituted, at least one of its ends interrupted, or a carbon-carbon bond interrupted, and is a divalent hydrocarbon group having 1 to 20 carbon atoms.

[0080] A 1d As for the divalent hydrocarbon group having 1 to 20 carbon atoms in the above, A of formula (3) is 2cThis is similar to the divalent hydrocarbon groups with 1 to 20 carbon atoms in the above text, and the description is referenced. The description is also referenced for monovalent or divalent groups selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms.

[0081] A 1d The divalent aromatic group in is A in formula (3) above. 2c This is similar to the divalent aromatic group in [the relevant section], and its description is referenced.

[0082] Represented by formula (4), a thioaryl ring group (-SX) is located at the 5-position. 1d -…or -SX 2d The 2-phenylbenzotriazole derivatives having -...) are not particularly limited, but examples include 2,2'-methylenebis[6-(2H-benzotriazole-5-yl-(4-tert-butyl-thiophenyl))-4-(4-(1,1,3,3-tetramethyl-butyl)phenol] and 2,2'-methylenebis[6-(2H-benzotriazole-5-yl-(4-tert-butyl-thiophenyl))-4-(2-hydroxyethyl)phenol].

[0083] Examples of ultraviolet absorbers of the present invention have been described above, and preferred embodiments of highly light-resistant ultraviolet absorbers are further described below. • 2-phenylbenzotriazole derivatives are represented by any of the formulas (1), (3), or (4) in [I] above, where X 1a , X 1c , X 2c , X 1d , X 2d The '' represents a phenyl ring residue, where l, n, p, r, and s are 0. In particular, 2-phenylbenzotriazole derivatives are represented by either formula (1) or (3), where X is in formula (1) or (3). 1a , X 1c , X 2c The ∫ represents a phenyl ring residue, where l, n, and p are 0, and the R of the 2-phenylbenzotriazole skeleton.1 A hydroxyl group, R 4 It contains a methyl group. • 2-phenylbenzotriazole derivatives are represented by any of the formulas (1), (3), or (4) in [I] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of the following independently represents a hydrocarbon group with 1 to 18 carbon atoms, and l, n, p, r, and s represent integers from 1 to 5. In particular, in equations (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents at least one branched alkyl group with 3 to 8 carbon atoms, and l, n, p, r, and s represent integers from 1 to 3. Alternatively, in equations (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n, p, r, and s represent integers of 1. Alternatively, in equations (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements.1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n, p, r, and s represent integers of 2. Alternatively, in equations (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a hydrocarbon group having tertiary and / or quaternary carbon atoms with 1 to 18 carbon atoms, and l, n, p, r, and s represent integers from 1 to 5. • 2-phenylbenzotriazole derivatives are represented by any of the formulas (1), (3), or (4) in [I] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents an alkoxy group having a linear or branched alkyl group with 1 to 18 carbon atoms. • 2-phenylbenzotriazole derivatives are represented by any of the formulas (1), (3), or (4) in [I] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d This indicates a hydroxyl group. • 2-phenylbenzotriazole derivatives are represented by any of the formulas (1), (3), or (4) in [I] above, where X 1a , X 1c , X 2c , X 1d , X 2d This indicates a naphthyl ring residue. • The 2-phenylbenzotriazole derivative is represented by formula (2) in [I] above, where m is 0. • 2-phenylbenzotriazole derivatives are represented by formula (2) of [I] above, where R 1b Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms. • 2-phenylbenzotriazole derivatives are represented by formula (3) in [I] above, where X 1c and X 2c The phenyl ring shows a sustained ring, q is 1, and A 2c This indicates a sulfide group -S-. • 2-phenylbenzotriazole derivatives are represented by formula (3) in [I] above, where X 1c and X 2c The phenyl ring shows a sustained ring, q is 1, and A 2c This indicates a hydrocarbon group with 1 to 8 carbon atoms. • 2-phenylbenzotriazole derivatives are represented by formula (3) in [I] above, where X 1c and X 2c represents a phenyl ring residue, and q is 0.

[0084] Furthermore, preferred embodiments of the heat-resistant ultraviolet absorber are as follows: • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d This indicates a residue of the phenyl ring. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s represent integers from 0 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s represent integers from 1 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 2 to 8 carbon atoms, and l, n, p, r, and s represent integers from 1 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 4 to 8 carbon atoms, and l, n, p, r, and s represent integers from 1 to 3.

[0085] (UV absorber) The ultraviolet absorber of the present invention, which has a thioaryl ring group introduced to benzotriazole, is described in Patent Document 2 (International Publication No. 2016 / 021664). It exhibits excellent absorption of long-wavelength ultraviolet light and molar extinction coefficient, and materials using it can suppress discoloration to yellow. Furthermore, the ultraviolet absorber of the present invention has high light resistance, and the change in transmittance (difference in transmittance) due to the degradation (decomposition) of the ultraviolet absorber over a long period of time is small, making it possible to maintain the absorption effect of ultraviolet light up to the long-wavelength region. In a preferred embodiment of the highly light-resistant ultraviolet absorber of the present invention, after irradiating a material with ultraviolet light at a wavelength of 300-400 nm for 70 hours under the following measurement conditions, the difference in transmittance at any of the wavelengths of 380, 390, and 400 nm in the long-wavelength region is 6% or less. Among these, the more highly light-resistant ultraviolet absorber has a difference in transmittance of 6% or less at any of the wavelengths of 380, 390, and 400 nm, more preferably 4% or less for all of them, and even more preferably 2% or less for all of them. Furthermore, it has high heat resistance, and when adding the UV absorber to organic and inorganic materials, when heating and processing the added organic and inorganic materials, or when actually using these materials under high-temperature conditions, it is possible to suppress the reduction of the UV absorption effect due to thermal decomposition, discoloration, etc. In a preferred embodiment of the heat-resistant UV absorber of the present invention, it is preferable that it does not discolor when heated at 120°C for 48 hours, more preferably that it does not discolor when heated at 160°C for 6 hours, even more preferably that it does not discolor when heated at 160°C for 12 hours, and particularly preferably that it does not discolor when heated at 160°C for 24 hours. And / or, the weight change rate due to thermal decomposition of the ultraviolet absorber under a heating environment for a long period of time (constant temperature) is preferably less than 0.03% by weight after heating at 120°C for 48 hours, more preferably less than 0.20% by weight after heating at 160°C for 6 hours, even more preferably less than 0.08% by weight after heating at 160°C for 12 hours, and particularly preferably less than 0.04% by weight after heating at 160°C for 24 hours.

[0086] Furthermore, the ultraviolet absorber of the present invention possesses both heat resistance and the aforementioned light resistance, resulting in high durability from manufacturing to use, and excellent ultraviolet absorption and discoloration resistance. In a preferred embodiment of the durable ultraviolet absorber of the present invention, both the preferred embodiments of high light resistance and heat resistance are satisfied.

[0087] Furthermore, the UV absorber of the present invention is excellent in terms of heat resistance, light resistance, and affinity between the UV absorber and organic and inorganic materials when used incorporated into organic and inorganic materials, contributing to the preservation of the UV absorption capacity, discoloration resistance, and excellent appearance of organic and inorganic materials. In particular, when resin is used as the organic material, the UV absorber is excellent in that it suppresses the degradation of the resin without bleeding out, and when glass is used as the inorganic material, the UV absorber is excellent in that it preserves the UV absorption capacity of the glass. <Measurement conditions for the difference in transmittance (ΔTuv)> Samples of soda glass coated with acrylic resin and UV absorber in a mass ratio of 0.6-3.4:0.1 and with a film thickness of 2-50 μm were tested at a wavelength of 300-400 nm and an illuminance of 42 W / m². 2 Under conditions of a black panel temperature of 63°C, ultraviolet light is irradiated for 70 and 140 hours, and the transmittance of the ultraviolet-visible transmission spectrum before irradiation (T1uv) and after irradiation (T2uv) is calculated using the following formula.

[0088]

number

[0089] The light resistance of the UV absorber of the present invention is given by X of formula (1). 1a , Cy in equation (2), X in equation (3) 1c and X 2c X in equation (4) 1d and X 2d Influenced by, and furthermore, each X 1a , Cy, X 1c , X 2c , X 1d , X 2d The presence or absence of substituents or appropriate substituent R 1a , R 1b , R 1c and R 2c , R 1d and R 2d Lightfastness is improved by selecting X in equations (1), (3), and (4). 1a , X 1c , X 2c , X 1d , X 2dA phenyl ring residue is preferred over a naphthyl ring residue, R 1a , R 1c , R 2c , R 1d , R 2d Hydrocarbon groups and alkoxy groups are preferred over hydroxyl groups, and among hydrocarbon groups, linear or branched alkyl groups are preferred, exhibiting high light resistance. Furthermore, in equation (1), X 1a These are residues of the phenyl ring, with l=1~3, R 1a However, at least one of the atoms is preferably a branched alkyl group having 3 to 8 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths of 380, 390, and 400 nm is 6.0 or less.

[0090] X 1a This is a phenyl ring residue, l=1, R 1a If it is a linear or branched alkyl group, The alkyl group preferably has 1 to 18 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group preferably has 1 to 10 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group preferably has 1 to 8 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group with 2 to 8 carbon atoms is more preferable, and the difference in transmittance at any of the 380, 390, and 400 nm wavelengths after 70 hours of irradiation is 4.0 or less, and the difference in transmittance at two of the 380, 390, and 400 nm wavelengths after 140 hours of irradiation is 6.0 or less. The alkyl group has 3 to 8 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the 380, 390, and 400 nm wavelengths is 4.0 or less, and after 140 hours of irradiation, the difference in transmittance at two of the 380, 390, and 400 nm wavelengths is 6.0 or less. A alkyl group with 3 to 5 carbon atoms is more preferable, and the difference in transmittance at any of the wavelengths 380, 390, and 400 nm after 70 hours of irradiation is 4.0 or less, and the difference in transmittance at any of the wavelengths 380, 390, and 400 nm after 140 hours of irradiation is 6.0 or less. • The alkyl group has 4 to 5 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the 380, 390, and 400 nm wavelengths is 4.0 or less. After 140 hours of irradiation, one of the 380, 390, and 400 nm wavelengths has a transmittance of 6.0 or less, and the difference in transmittance between the other two wavelengths is 4.0 or less. A C4 alkyl group is particularly preferred, and the difference in transmittance at any of the wavelengths 380, 390, and 400 nm after 70 hours of irradiation is 2.0 or less, and the difference in transmittance at any of the wavelengths 380, 390, and 400 nm after 140 hours of irradiation is 4.0 or less. ·R 1a Preferably, the alkyl group has a tertiary carbon and / or quaternary carbon, and the difference in transmittance at any of the wavelengths of 380, 390, and 400 nm after 70 hours of irradiation is 4.0 or less.

[0091] X 1a This is a phenyl ring residue, l=2, R 1a When the alkyl group is linear or branched, the number of carbon atoms in each alkyl group is preferably 1 to 18, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths of 380, 390, and 400 nm is 6.0 or less. The alkyl group preferably has 1 to 10 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group preferably has 1 to 5 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group with 1 to 4 carbon atoms is more preferable, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 4.0 or less. • A more preferable configuration is one carbon atom in each alkyl group, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 2.0 or less. The alkyl group preferably has a total of 2 to 12 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group has a total of 2 to 10 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 6.0 or less. The alkyl group has a total of 2 to 5 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 4.0 or less. A total of 2 carbon atoms in the alkyl group is more preferable, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 2.0 or less.

[0092] Also, l=0, that is, X 1a It is preferable that all substituents are hydrogen atoms, and that the difference in transmittance at any of the wavelengths 380, 390, and 400 nm after irradiation times of 70 and 140 hours is 2.0 or less.

[0093] On the other hand, in equation (3), ·q=1, A 2c It is more preferable that the group is a sulfide group, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths of 380, 390, and 400 nm is 2.0 or less. ·q=1, A 2c The carbon atom preferably has 1 to 8 carbon atoms, and after 70 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 2.0 or less, and after 140 hours of irradiation, the difference in transmittance at any of the wavelengths 380, 390, and 400 nm is 4.0 or less. It is preferable that q=0, and after 70 hours of irradiation, the difference in transmittance for all wavelengths of 380, 390, and 400 nm is 6.0 or less.

[0094] Generally, when UV absorbers are added to resins as components, low-melting-point compounds bleed out quickly over time. On the other hand, during processing and molding of inorganic materials such as thermoplastic resins and glass by heating, they bleed out or decompose, preventing them from fully exhibiting their UV absorption effect, or causing blocking. Furthermore, when UV absorbers are crushed (micronized) and dispersed for use, low-melting-point UV absorbers agglomerate due to the heat generated in the process, making them difficult to use. Higher melting points are preferable, and combining them with light resistance allows for the maintenance of light absorption characteristics. From these viewpoints, the melting point of the highly light-resistant UV absorber of the present invention is preferably 100°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, particularly preferably 145°C or higher, and especially preferably 150°C or higher. In terms of melting point, X in formula (1) 1a A naphthyl ring is preferred. 1a If R is a phenyl ring residue, 1a A hydroxyl group is preferred, R 1a When l=1 is a linear or branched alkyl group, l=1 is preferred over l=0. When l=1, the alkyl group preferably has 2 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 4 carbon atoms. In formula (3), when q=1, A 2c A hydrocarbon group (preferably a linear or branched alkylene group) is preferred. Furthermore, q=0 is preferred.

[0095] As described above, when UV absorbers are added to organic or inorganic materials, when these materials are heated and processed, or when they are used under high-temperature conditions, the UV absorbers decompose. This not only prevents them from fully absorbing UV rays, but also causes discoloration of the materials containing the UV absorbers due to the thermal decomposition of the UV absorbers. Therefore, UV absorbers must be heat-resistant, and it is desirable that they exhibit minimal discoloration and weight loss due to thermal decomposition when heated. Under prolonged heating (at a constant temperature for a certain period of time) conditions (manufacturing, use), the thermal decomposition of UV absorbers results in weight loss and discoloration, and the less discoloration there is, the smaller the weight change.

[0096] From the standpoint of discoloration, it is desirable that the degree of discoloration is small when exposed to higher temperatures and longer periods of heating. For example, yellow is preferred over black, pale yellow is more preferred, and no discoloration at all is even more preferable.

[0097] As described above, the UV absorber of the present invention has excellent light resistance, heat resistance, and durability. When used in a resin as an organic material, it can prevent the deterioration of the resin composition and maintain the UV absorption capacity and appearance of the resin composition for a long period of time.

[0098] For example, as an indicator of discoloration of an ultraviolet absorber left in a constant temperature environment for a certain period of time in a constant temperature oven, it is preferable that there is no discoloration after 48 hours at 120°C, more preferably after 6 hours at 160°C, even more preferably after 12 hours at 160°C, and especially preferably after 24 hours at 160°C.

[0099] From the standpoint of weight loss rate, it is desirable that the weight loss rate be small when subjected to heating at higher temperatures for longer periods. For example, a weight loss rate of less than 0.20% by weight is preferred, less than 0.08% by weight is more preferred, less than 0.04% by weight is even more preferred, and less than 0.03% by weight is particularly preferred.

[0100] For example, as an indicator of the weight change rate due to thermal decomposition of an ultraviolet absorber left standing in a constant temperature environment for a certain period of time in a constant temperature oven, it is preferable that the weight change rate is less than 0.03% by weight after heating at 120°C for 48 hours, more preferably less than 0.20% by weight after heating at 160°C for 6 hours, even more preferably less than 0.08% by weight after heating at 160°C for 12 hours, and particularly preferably less than 0.04% by weight after heating at 160°C for 24 hours.

[0101] In terms of heat resistance under prolonged heating conditions (constant temperature for a constant period), UV absorbers that meet the above-mentioned indicators of discoloration or weight change rate are desirable, and those that meet a combination of both indicators are even more desirable.

[0102] From the viewpoint of heat resistance, the structure of the ultraviolet absorber of the present invention is X of formulas (1), (3), and (4). 1a , X 1c, X 2c , X 1d , X 2d The compound is preferably a residue of a phenyl ring, and X is of formulas (1), (3), and (4). 1a , X 1c , X 2c , X 1d , X 2d R is a phenyl ring residue, with l, n, p, r, and s R groups. 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s are integers from 0 to 3, are more preferably the l, n, p, r, and s of formulas (1), (3), and (4). 1a , R 1c , R 2c , R 1d , R 2d A compound in which each is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s are integers from 1 to 3, is more preferable, and l, n, p, r, and s are R 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each is independently a linear or branched alkyl group having 2 to 8 carbon atoms, and l, n, p, r, and s are integers from 1 to 3, are particularly preferred, with l, n, p, r, and s being the R 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each of the elements is independently a linear or branched alkyl group having 4 to 8 carbon atoms, and l, n, p, r, and s are integers from 1 to 3, are particularly preferred.

[0103] The ultraviolet absorber of the present invention is preferably one that combines the desirable levels of discoloration and weight loss in terms of heat resistance mentioned above with light resistance such that the difference in transmittance is 6% or less at least one of 380, 390, and 400 nm, more preferably 6% or less at all wavelengths, even more preferably 4% or less at all wavelengths, and even more preferably 2% or less at all wavelengths. An ultraviolet absorber in one embodiment of the present invention, which includes such examples, has excellent light resistance, does not deteriorate even when exposed to ultraviolet light during long-term use, exhibits ultraviolet absorption ability over a long period of time, and further suppresses the deterioration of organic resins. It also has excellent heat resistance, and when organic materials, inorganic materials, etc. to which the highly light-resistant ultraviolet absorber of the present invention is added are manufactured, processed, pulverized (micronized), dispersed, and further when used in actual use after processing, they are exposed to high-temperature environments for a long time (at a constant temperature for a certain period of time), and discoloration and weight loss rates are minimal. Thus, in one aspect of the present invention, a UV absorber is provided that does not bleed out from manufacturing to use, maintains its UV absorption ability, has excellent light resistance, heat resistance, and durability, and furthermore, has good affinity (adhesion) with organic and inorganic materials, and can produce components, organic and inorganic materials with excellent appearance.

[0104] (composition) In this specification, the term "composition" includes compositions containing the ultraviolet absorber of the present invention, regardless of their properties, such as solid, fluid, gel, or sol, and also includes not only components but also raw materials for manufacturing those components.

[0105] In this specification, the term "component" is not particularly limited, but includes, for example, any shaped object. Examples of uses for compositions such as components containing the ultraviolet absorber of the present invention include those described below.

[0106] Examples of materials for the composition containing the ultraviolet absorber of the present invention include organic materials and inorganic materials. The ultraviolet absorber of the present invention has high affinity, compatibility, and adhesion with various organic and inorganic materials. When the ultraviolet 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.

[0107] The compositions containing the ultraviolet absorber of the present invention include organic material compositions and inorganic material compositions. The shape of these organic material compositions and inorganic material compositions is not particularly limited and includes, for example, coating films, coated films, laminated films, films, sheets, plates, powders, granules, pellets, tablets, molded articles, etc.

[0108] In organic and inorganic material compositions containing the ultraviolet absorber of the present invention, the ultraviolet absorber of the present invention can be used to obtain organic and inorganic material compositions that exhibit not only excellent light resistance but also heat resistance, such as not experiencing discoloration, a decrease in ultraviolet absorption capacity, or a decrease in transparency over a long period of use without bleeding out, thereby suppressing degradation. Furthermore, it has good affinity with organic materials, inorganic materials, and especially organic materials.

[0109] Based on the characteristics of the UV absorber of the present invention described above, organic and inorganic material compositions containing it can efficiently absorb harmful light in the wavelength range of 380-400 nm while suppressing yellowing, resulting in organic and inorganic material compositions with excellent appearance, no bleed-out of the UV absorber, and no discoloration, decrease in UV absorption capacity, or decrease in transparency over long periods of use, thus exhibiting not only excellent light resistance but also excellent heat resistance.

[0110] 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 ultraviolet absorber of the present invention. The inorganic material composition contains 50% by mass or more of the inorganic material relative to the total amount of all materials excluding water, solvent, and the ultraviolet absorber of the present invention.

[0111] The composition containing the ultraviolet absorber 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. The composition containing the ultraviolet 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 ultraviolet 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 ultraviolet absorber of the present invention in a liquid such as water or an organic solvent.

[0112] The organic material is not particularly limited, but examples include organic resins, materials derived from plants and animals, materials derived from crude oil, and organic compounds. In the present invention, the organic resin composition is an organic composition containing the ultraviolet absorber of the present invention and an organic resin, and is included in the organic material composition.

[0113] 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.

[0114] 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 such resins as 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.

[0115] 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.

[0116] The polymer of the thermoplastic resin is not particularly limited, but examples include the following:

[0117] 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.

[0118] 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.

[0119] The styrene-based resin is not particularly limited, but examples include polystyrene.

[0120] 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.

[0121] 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.

[0122] The vinyl chloride resin is not particularly limited, but examples include polyvinyl chloride, polyvinylidene chloride, and the like.

[0123] Fluorine-based resins are not particularly limited, but examples include polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride.

[0124] The vinyl resin is not particularly limited, but examples include polyvinyl acetate, polyvinyl alcohol, polyvinyl sulfonic acid, and its salts.

[0125] The polycarbonate resin is not particularly limited, but examples include polycarbonate.

[0126] The polyamide resin is not particularly limited, but examples include polyamide, nylon 6, nylon 66, nylon 11, nylon 12, etc.

[0127] The polyimide resin is not particularly limited, but examples include polyimide.

[0128] The polyamide-imide resin is not particularly limited, but examples include polyamide-imide.

[0129] The polymaleimide resin is not particularly limited, but examples include polymaleimide and poly-N-phenylmaleimide.

[0130] The polyvinylpyrrolidone-based resin is not particularly limited, but examples include polyvinylpyrrolidone.

[0131] The polyurethane resin is not particularly limited, but examples include polyurethane.

[0132] Polysulfone-based resins are not particularly limited, but examples include polysulfone.

[0133] 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:

[0134] The butadiene-styrene copolymer is not particularly limited, but examples include butadiene-styrene copolymers.

[0135] The acrylonitrile-styrene copolymer is not particularly limited, but examples include acrylonitrile-styrene copolymers.

[0136] The acrylonitrile-butadiene-styrene copolymer is not particularly limited, but examples include acrylonitrile-butadiene-styrene copolymers.

[0137] The styrene-isoprene copolymer is not particularly limited, but examples include styrene-isoprene copolymers.

[0138] The styrene-acrylic acid copolymer is not particularly limited, but examples include styrene-acrylic acid copolymers.

[0139] The vinyl chloride-vinylidene chloride-acrylonitrile copolymer is not particularly limited, but examples include vinyl chloride-vinylidene chloride-acrylonitrile copolymer.

[0140] 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.

[0141] The polymer of the thermosetting resin is not particularly limited, but examples include the following:

[0142] Phenolic resins are not particularly limited, but examples include phenolic resins.

[0143] The urea-based resin is not particularly limited, but examples include urea resin.

[0144] The melamine resin is not particularly limited, but examples include melamine resin.

[0145] The unsaturated polyester resin is not particularly limited, but examples include unsaturated polyester resins.

[0146] Alkyd resins are not particularly limited, but examples include alkyd resins.

[0147] The epoxy resin is not particularly limited, but examples include epoxy resins.

[0148] The episulfide resin is not particularly limited, but examples include episulfide resins.

[0149] The copolymer of the thermosetting resin is not particularly limited, but examples include the following:

[0150] The acrylic melamine resin is not particularly limited, but examples include acrylic melamine resin.

[0151] The acrylic urethane resin is not particularly limited, but examples include acrylic urethane resin.

[0152] From the viewpoint of compatibility between the UV absorber of the present invention and the organic resin, and the transparency of the organic resin composition containing the UV absorber, it is preferable to use thermoplastic resins (polymers and copolymers) and thermosetting resins (polymers and copolymers). Among the polymers of thermoplastic resins, (meth)acrylic resins (polymethyl methacrylate resins), ester resins (polyethylene terephthalate), polycarbonate resins (polycarbonate), and styrene resins (polystyrene) are preferred, and among the copolymers of thermoplastic resins, acrylonitrile-butadiene-styrene copolymers are preferred. Among the polymers of thermosetting resins, urea resins (urea resins) and melamine resins (melamine resins) are preferred. Among the copolymers of thermosetting resins, acrylic melamine resins (acrylic melamine resins) are preferred.

[0153] From the viewpoint of dispersion of the compound of the present invention, heat processing, and suppression of elution from the resin by bleed-out, thermoplastic resins (polymers, copolymers) and thermosetting resins (polymers, copolymers) can be preferably used, and more preferably, polymers and copolymers of thermoplastic resins and polymers of thermosetting resins can be used. Among the polymers of thermoplastic resins, (meth)acrylic resins (polymethyl methacrylate resins), ester resins (polyethylene terephthalate), polycarbonate resins (polycarbonate), and styrene resins (polystyrene) are preferred, and (meth)acrylic resins, ester resins, and polycarbonate resins are more preferred. Among the copolymers of thermoplastic resins, acrylonitrile-butadiene-styrene copolymers are preferred. Among the polymers of thermosetting resins, urea resins (urea resins) and melamine resins (melamine resins) are preferred, and urea resins are more preferred.

[0154] From the viewpoint of the heat resistance of the organic resin composition containing the ultraviolet absorber of the present invention, that is, the reduction in transmittance when heated for a long time (at a constant temperature for a certain period of time), thermoplastic resins (polymers, copolymers) and thermosetting resins (polymers, copolymers) are preferred as the organic resin. Although not particularly limited, for example, among the polymers of thermoplastic resins, (meth)acrylic resins (polymethyl methacrylate resins), ester resins (polyethylene terephthalate), polycarbonate resins (polycarbonate), and styrene resins (polystyrene) are preferred, and among the copolymers of thermoplastic resins, acrylonitrile-butadiene-styrene copolymers are preferred. Among the polymers of thermosetting resins, urea resins (urea resins) and melamine resins (melamine resins) are preferred. Among the copolymers of thermosetting resins, acrylic melamine resins (acrylic melamine resins) are also mentioned. More preferably, a copolymer of a polymer of a thermoplastic resin and a thermosetting resin can be used. Thermoplastic resins are particularly preferred, and for example, polycarbonate resins (polycarbonate) and (meth)acrylic resins (polymethyl methacrylate resin) can be used.

[0155] Among the ultraviolet absorbers of the present invention, from the viewpoint of obtaining an organic resin composition with excellent heat resistance, an ultraviolet absorber that satisfies the above heat resistance index can be used, and X of formulas (1), (3), and (4) 1a , X 1c , X 2c , X 1d , X 2d The compound is preferably a residue of a phenyl ring, and X is of formulas (1), (3), and (4). 1a , X 1c , X 2c , X 1d , X 2d R is a phenyl ring residue, with l, n, p, r, and s R groups. 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s are integers from 0 to 3, are more preferably the l, n, p, r, and s of formulas (1), (3), and (4). 1a , R 1c , R 2c , R 1d , R 2d A compound in which each is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s are integers from 1 to 3, is more preferable, and l, n, p, r, and s are R 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each is independently a linear or branched alkyl group having 2 to 8 carbon atoms, and l, n, p, r, and s are integers from 1 to 3, are particularly preferred, with l, n, p, r, and s being the R 1a , R 1c , R 2c , R 1d , R 2d Compounds in which each of the elements is independently a linear or branched alkyl group having 4 to 8 carbon atoms, and l, n, p, r, and s are integers from 1 to 3, are particularly preferred.

[0156] 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 ultraviolet absorber of the present invention. The organic resin composition is, for example, obtained by mixing, dispersing, or dissolving the ultraviolet absorber of the present invention and the organic resin, or by mixing, dispersing, or dissolving the ultraviolet absorber in the organic resin. Inorganic compounds used as fillers, silane coupling agents, primers, etc., may be added to the organic resin composition.

[0157] 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 dioxide, alkali-free glass, and soda-lime glass. Examples of water glass include aqueous solutions of water-soluble alkali metal salts, such as sodium silicate and potassium silicate. Examples of low-melting-point glass include lead oxide (PbO) and boric anhydride (B2O3) as the main components. Examples of silicone resin include methyl silicone resin, methylphenyl silicone resin, and organic resin-modified silicone 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. Silane coupling agents are not particularly limited, but examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane N-2-(aminoethyl)-3-aminopropyl Examples include methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatetopropylethoxysilane. 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, P, and Sb.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.

[0158] Shape of the component The shape of the component is not particularly limited and may be any shape, and examples include coatings, adhesives, tacks, flexible or pliable films or rigid plate-shaped components, powder, granular, pellet-shaped, tablet-shaped components, masterbatches, molded articles, etc. [1] Coating Specific application examples include coating the surfaces of materials such as resin and glass. The coating method is not particularly limited, but examples include applying, spraying, forming a film, or creating a coating containing the UV absorber of the present invention to the surface of a component using a resin, paint, silica material, glass, solvent dispersion, etc., which are mixed, dissolved, or dispersed with the UV absorber of the present invention. [2] Adhesives Specific application examples, though not limited to them, include adhesives obtained by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in organic adhesives (organic resins, synthetic rubber, starch, glue, etc.) or inorganic adhesives (silica, ceramics, cement, solder, water glass, etc.) applied to various materials and components. [3] Adhesive Specific application examples are not limited to those mentioned above, but include adhesives obtained by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in adhesives applied to various materials and components (such as organic resins, organic oligomers, rubber-based adhesives, starch, glue, silicone-based adhesives, and silane coupling agent-based adhesives). [4] film Specific application examples, though not limited to them, include components obtained by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in a flexible or pliable film-like resin, glass, or silicon oxide precursor. The film may be a single-layer film, a multilayer film or film-attached substrate in which one or more layers are provided on a base film or substrate according to various applications, and in the case of a multilayer film, the ultraviolet absorber of the present invention is contained in at least one layer. The ultraviolet absorber of the present invention can also be used in film-like resins or glass, or as an interlayer in glass made of glass, containing the ultraviolet absorber of the present invention. [5] Board Specific application examples are not limited to those mentioned above, but include, for example, members obtained by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in a plate-shaped resin or glass. [6] Powder, granules, pellets, tablets Specific application examples are not limited to those mentioned above, but include, for example, components obtained by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in powder, granular, pelletized, or tablet-shaped resins or glass. [7] Masterbatch Specific application examples are not limited to granular or pelletized resin compositions obtained by mixing, dissolving, or dispersing the UV absorber, pigment, or other coloring agent of the present invention with a resin as needed. These compositions are used for coloring or preparing colored resins by melt-mixing them with other resins. [8] Molded products Specific application examples are not limited to those mentioned above, but include articles formed by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention in resin or glass.

[0159] additives The compositions and components containing the ultraviolet 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.

[0160] The ultraviolet absorber of the present invention is used in fields where high light resistance, high heat resistance, and high durability are required, and the type, shape, and application of the composition and components are not limited.

[0161] Compositions and components containing the UV absorber of the present invention can be made into UV absorber-containing compositions that have excellent not only light resistance but also heat resistance, such as not experiencing discoloration, a decrease in UV absorption capacity, or a decrease in transparency over a long period of use. For example, coating films and films for transparent resins and transparent glass containing the UV absorber of the present invention can be made into coating films and films that do not yellow, discolor, experience a decrease in UV absorption capacity, or experience a decrease in transparency over a long period from manufacture to use. The uses of the UV absorber of the present invention are not particularly limited, but it is particularly suitable for use in applications where there is a possibility of exposure to light with wavelengths of 380-400 nm, and even 380-420 nm, including sunlight or ultraviolet light.

[0162] 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 other optical products and their preservation. It can also be used in protective 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.

[0163] The ultraviolet absorbers of the present invention are preferable for use in the manufacture and processing of organic and inorganic materials containing ultraviolet absorbers because they exhibit little discoloration and weight loss even when exposed to a heated environment for a long period of time (at a constant temperature). Among the ultraviolet absorbers of the present invention, in terms of exhibiting little discoloration due to heating when used in combination with organic resins to manufacture and process organic resin compositions, it is preferable that they do not discolor when heated at 120°C for 48 hours, more preferably at 160°C for 6 hours, even more preferably at 160°C for 12 hours, and particularly preferably at 160°C for 24 hours or more. And / or, in terms of the weight loss rate due to thermal decomposition of the ultraviolet absorber, it is preferable that the weight loss is less than 0.03% by weight after heating at 120°C for 48 hours, more preferably less than 0.20% by weight after heating at 160°C for 6 hours, even more preferably less than 0.08% by weight after heating at 160°C for 12 hours, and particularly preferably less than 0.04% by weight after heating at 160°C for 24 hours. UV absorbers that exhibit little discoloration or weight loss in a heated environment are preferred, and UV absorbers that exhibit little discoloration and weight loss are more preferred. The organic resin to be combined with the UV absorber of the present invention is not particularly limited, but examples include the above-mentioned thermoplastic resins (polymers and copolymers) and thermosetting resins (polymers and copolymers). Among organic resins, combination with thermoplastic resins is preferred because they are widely subjected to heat molding and processing. As thermoplastic resins, for example, among the polymers of thermoplastic resins, (meth)acrylic resins (polymethyl methacrylate resin), ester resins (polyethylene terephthalate), polycarbonate resins (polycarbonate), and styrene resins (polystyrene) can be preferably used, and among the copolymers of thermoplastic resins, acrylonitrile-butadiene-styrene copolymers can be preferably used.

[0164] By combining with the UV absorber of the present invention, an organic resin composition is obtained that efficiently absorbs light with wavelengths from 380 to 400 nm, suppressing yellowing. Furthermore, due to the light resistance, heat resistance, durability, compatibility, and affinity of the UV absorber of the present invention with organic resins, the organic resin composition containing the UV absorber of the present invention has an excellent appearance and does not discolor, maintains transparency, suppresses yellowing, or cause bleed-out of the UV absorber when used in environments with heating during manufacturing and processing, high temperatures, and / or UV exposure.

[0165] (Absorption of harmful light from 250 to 420 nm and suppression of early yellowing) Due to its optical properties, the UV absorber of the present invention can sufficiently absorb light in the wavelength range of 250 to 400 nm, and depending on the amount added, it can also absorb wavelengths of 400 to 420 nm. Moreover, it has a high UV absorption effect (molar extinction coefficient), and even with a small amount added, it can sufficiently absorb light in the wavelength range of 250 to 400 nm. Furthermore, because the slope of the absorption peak is greater than that of conventional UV absorbers, it can suppress the yellowing of resin components.

[0166] Furthermore, in order to obtain a resin component with excellent appearance that suppresses yellowing by absorbing harmful light in the wavelength range up to ~400 (420) nm, which may trigger adverse effects on the human body, such as damage to eye tissue, and suppressing the absorption of light with wavelengths above 400 (420) nm, which is a cause of yellowing of the component, it is preferable that the light absorption peak in a 50~100 μM chloroform solution is at 350~390 nm, more preferably at 360~380 nm, and particularly preferably at 360~375 nm. Also, the absorption peak in these wavelength ranges is the maximum absorption wavelength (λ maxIt is preferable that the wavelength peak is sharp (the absolute value of the slope is large) on the longer wavelength side in order to suppress the absorption of light with wavelengths longer than 400 nm and suppress yellowing. It is preferable that the slope on the longer wavelength side of the absorption peak (the absolute value of the slope of the line connecting the absorption peak and the peak end of the absorption spectrum on the longer wavelength side) in a 100 μM chloroform solution for compounds of formulas (1) and (2), and in a 50 μM chloroform solution for compounds of formulas (3) and (4) is 0.025 or higher, more preferably 0.030 or higher, even more preferably 0.040 or higher, and even more preferably 0.042 or higher. In addition, in order to absorb efficiently with a small amount, the molar extinction coefficient (maximum molar extinction coefficient: ελ) of the absorption peak in the 350-390 nm range is preferable. max The concentration is preferably 17,000 L / (mol·cm) or more, more preferably 18,000 L / (mol·cm) or more, even more preferably 20,000 L / (mol·cm) or more, and even more preferably 40,000 L / (mol·cm) or more.

[0167] By using these UV absorbers, yellowing is suppressed in organic material compositions (organic resin compositions) and inorganic material compositions, resulting in a good transparent appearance.

[0168] (UV absorbers used in UV-shielding films or UV-shielding film-forming compositions for glass) The UV absorbers mentioned in [IV] above will be explained below. The ultraviolet absorber described in [IV] above is an ultraviolet absorber used in ultraviolet shielding films for glass or compositions for forming ultraviolet shielding films, and consists of a 2-phenylbenzotriazole derivative having a thioaryl ring group, a thiocyclohexyl ring group, a thioalkyl group, or a thioalkylene group, represented by any of the above formulas (1) to (6).

[0169] In the above [IV], X in equations (1), (2), (3), and (4) 1a , Cy, X 1c , X 2c , X 1d , X 2d R may be present in 1a , R 1b, R 1c , R 2c , R 1d , R 2d Other substituents include R in formula (A) above. 1 ~R 9 Examples of substituents listed include those described above.

[0170] The UV absorber described in [IV] above efficiently absorbs harmful light in the wavelength range of 380 to 400 nm and suppresses the absorption of light with wavelengths above 400 nm, which is a cause of initial yellowing, thereby enabling the production of a component with less influence from harmful light and superior appearance. Furthermore, it exhibits excellent light resistance or heat resistance, or excellent light resistance and heat resistance, i.e., durability. In particular, it is possible to provide glass with a UV shielding film that is suitable for reducing the transmittance of light near 400 nm over a long period of time while suppressing significant yellowing, as well as a UV shielding film suitable for glass with high visible light transmittance, and a composition and dispersion for UV absorber shielding films. Furthermore, the UV absorber described in [IV] above exhibits excellent heat resistance, making it possible to prevent a decrease in the UV shielding effect due to thermal decomposition under heating processes such as during the formation of the UV shielding film on glass and during subsequent secondary processing, as well as under usage conditions. From the viewpoint of heat resistance, preferred structures of the UV absorber of the present invention are given by formulas (1), (3), and (4). • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d This indicates a residue of the phenyl ring. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s represent integers from 0 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms), and l, n, p, r, and s represent integers from 1 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these independently represents a linear or branched alkyl group having 2 to 8 carbon atoms, and l, n, p, r, and s represent integers from 1 to 3. • 2-phenylbenzotriazole derivatives are represented by formulas (1), (3), and (4) in [II] above, where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2dEach of these independently represents a linear or branched alkyl group having 4 to 8 carbon atoms, and l, n, p, r, and s represent integers from 1 to 3.

[0171] The ultraviolet absorber of the present invention is suitable for ultraviolet shielding films. As described above, it efficiently absorbs harmful light in the wavelength range of 380 to 400 nm and has optical properties that suppress the absorption of light with wavelengths above 400 nm, which is a cause of initial yellowing. Due to its good affinity for glass, an ultraviolet shielding film containing the ultraviolet absorber of the present invention adheres well to glass, resulting in highly transparent glass, suppressed yellowing, and the ability to maintain its ultraviolet shielding effect for a long period of time.

[0172] For example, the ultraviolet absorber of the present invention can be used in the following glass compositions and applications.

[0173] The hydroxyl groups present on the glass surface and the thioether groups of the UV absorber of the present invention have affinity via hydrogen bonding, and the UV absorber [IV] above has excellent affinity with glass. As a result, the UV shielding film has excellent adhesion to the glass, and glass containing a UV shielding film with excellent transparency can be obtained.

[0174] When glass is used in applications requiring a high refractive index, the UV absorber of the present invention has a high refractive index due to its structural characteristics, and glass containing a UV shielding film using the UV absorber can also maintain its refractive index.

[0175] The ultraviolet shielding film is not particularly limited and may be a part of the laminated film of one side surface of glass, both surfaces of glass, an interlayer of laminated glass, a glass surface, or an interlayer of laminated glass. The materials used in a composition suitable for forming an ultraviolet shielding film are not particularly limited but include organic materials, inorganic materials, and organic-inorganic materials. The shape of the ultraviolet shielding film is not particularly limited and may include coating films, coated films, laminated films, films, sheets, plates, molded products, etc. (preferably coating films and films), and these may have an adhesive layer or bonding layer, and may have adhesive properties. The material of the ultraviolet shielding film is not particularly limited and may include resins, paper, fibers, glass, metals, minerals, etc. In the case of resins and glass, they may be crystalline, amorphous, or liquid crystal, and are suitable for ultraviolet shielding films on glass. The ultraviolet absorbers described in [IV] above include the following ultraviolet absorbers a and b.

[0176] <UV absorber a> One of the following UV absorbers: (1) or (2): (1) An ultraviolet absorber used in an ultraviolet shielding film for an inorganic material composition including glass, wherein the raw material of the ultraviolet shielding film is not particularly limited, but includes, for example, silicate materials produced by the sol-gel method that are raw materials for glass containing silicon dioxide, glass, water glass, low-melting-point glass, quartz, silicon resin, alkoxysilane, silane coupling agent, etc., and the ultraviolet absorber of the ultraviolet shielding film described above in [IV] An example of the aforementioned ultraviolet shielding film is a coating film formed on the surface of glass, wherein the coating film contains silicon dioxide as the main component and the ultraviolet absorber described in [IV] above, and the coating film is made of glass. (2) An ultraviolet absorber used in a composition for forming an ultraviolet shielding film for glass, wherein the ultraviolet shielding film forming composition comprises raw materials used for the material of the ultraviolet shielding film, not limited to but including, for example, a silicon dioxide precursor that is a raw material for glass containing silicon dioxide, an alkoxysilane, a silane coupling agent, etc., and the ultraviolet absorber of [IV] above. The form of the ultraviolet absorber used in the ultraviolet shielding film-forming composition is not particularly limited and can be used by dissolving it in a solvent and adding it, or by dispersing the ultraviolet absorber in powder, granular, or fine particle form.

[0177] When a coating film or film is made of glass with silicon dioxide as the main component and an ultraviolet absorber is dispersed in it, the average particle size of the ultraviolet absorber fine particles is preferably 150 nm or less, more preferably 10 to 150 nm, even more preferably 50 to 140 nm, and particularly preferably 70 to 140 nm, from the viewpoint of transparency and ultraviolet shielding effect. If the average particle size of the fine particles is too large, it may reduce the transparency of the film, and if it is too small, it may degrade the ultraviolet absorption capacity or reduce its durability.

[0178] An example of the ultraviolet shielding film forming composition is one which comprises a silicon dioxide precursor and the ultraviolet absorber described in [IV] above, wherein the ultraviolet absorber described in [IV] above has the form of fine particles with an average particle size of 150 nm or less.

[0179] <UV absorber b> (1) A UV absorber used in a UV shielding film for glass, which is used in the UV shielding film formed from an organic material composition containing the UV absorber of [IV] above. (2) An ultraviolet absorber used in a composition for forming an ultraviolet shielding film for glass, which is used in an organic material composition containing the ultraviolet absorber of [IV] above.

[0180] The ultraviolet absorber and organic material composition of the present invention have high heat resistance and can be preferably used in resins having a thermoforming temperature of 80°C or higher, more preferably 120°C or higher, and especially 160°C or higher, or in manufacturing and using resins at those temperatures.

[0181] In the (2) composition of the above-mentioned ultraviolet absorbers a and b, optional components may include additives such as 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, and solvents such as water and organic solvents.

[0182] Here, the organic material composition is the composition described above. The organic material composition is preferably an organic resin composition containing the ultraviolet absorber and organic resin described in [IV] above.

[0183] Of the ultraviolet absorbers in [IV] above, formulas (1), (3), and (4) refer to the descriptions in [I] to [III] above. For formula (2), refer to the description in [I] above.

[0184] In formula (3), if a thioalkylene group is present, A 1cThis represents a linear or branched alkylene group having 1 to 22 carbon atoms, which is a monovalent or divalent group selected from phenyl ring residues, naphthyl ring residues, or aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, and in which hydrogen atoms may be substituted, at least one of the ends may be interrupted, or the carbon-carbon bond may be interrupted. The alkylene group is not particularly limited, but examples include methylene group, 1,1-dimethylmethylene group, ethane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9 Examples include diyl groups, decane-1,10-diyl groups, undecane-1,11-diyl groups, dodecane-1,12-diyl groups, tridecane-1,13-diyl groups, tetradecane-1,14-diyl groups, pentadecane-1,15-diyl groups, hexadecane-1,16-diyl groups, heptadecane-1,17-diyl groups, octadecane-1,18-diyl groups, nonadecane-1,19-diyl groups, eicosane-1,20-diyl groups, heneicosane-1,21-diyl groups, and docosane-1,22-diyl groups. Among these, linear or branched alkylene groups are preferred, and linear alkylene groups are more preferred.

[0185] When the alkylene group is a monovalent or divalent group in which a hydrogen atom is substituted, at least one of its ends is interrupted, or a carbon-carbon bond is interrupted, the number of monovalent or divalent groups is not particularly limited, but examples include two or fewer, or one or fewer.

[0186] Specific examples of the monovalent or divalent aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom mentioned above include the R of the 2-phenylbenzotriazole skeleton represented by formula (A) above. 1 ~R 9Examples of substituents similar to the monovalent or divalent groups described are included, and that description is referenced.

[0187] In formula (5), thioalkyl group (-SY 1e Y in ) 1e This represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may have a hydrogen atom substituted, a broken base end, or a broken carbon-carbon bond, and is a linear or branched alkyl group having 1 to 22 carbon atoms. These alkyl groups are not particularly limited, but examples include 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, hexane-1-yl group, heptane-1-yl group, octan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, Examples include nonan-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, nonadecane-1,19-diyl group, eicosane-1,20-diyl group, heneicosane-1,21-diyl group, docosane-1,22-diyl group, and benzyl group. Among these, linear or branched alkyl groups having 1 to 18 carbon atoms and benzyl groups are preferred, and linear or branched alkyl groups having 1 to 10 carbon atoms and benzyl groups are more preferred.

[0188] Furthermore, in formula (6), the thioalkyl group (-SY 1f ,-SY 2f Y in ) 1f and Y 2fEach of these independently represents a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms, which may be a linear or branched alkyl group having 1 to 22 carbon atoms, with hydrogen atoms substituted, the base end interrupted, or the carbon-carbon bond interrupted. These alkyl groups are not particularly limited, but examples include 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, hexane-1-yl group, heptane-1-yl group, octan-1-yl group, and 1,1,3,3-tetramethylbutane-1-yl group. Examples include the yl group, nonane-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, nonadecane-1,19-diyl group, eicosane-1,20-diyl group, heneicosane-1,21-diyl group, docosane-1,22-diyl group, etc. Among these, linear or branched alkylene groups are preferred, and linear alkylene groups are more preferred. Among these, groups with 1 to 18 carbon atoms are preferred, and groups with 1 to 10 carbon atoms are more preferred.

[0189] When an alkyl group is a monovalent or divalent group in which a hydrogen atom is substituted, the base end is interrupted, or the carbon-carbon bond is interrupted, the number of monovalent or divalent groups is not particularly limited, but examples include two or fewer, or one or fewer.

[0190] Specific examples of the monovalent or divalent aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom mentioned above include the R of the 2-phenylbenzotriazole skeleton represented by formula (A) above. 1 ~R 9 Examples of substituents similar to the monovalent or divalent groups described are included, and that description is referenced.

[0191] In the above [IV], R in equations h(1) to (6) 6 , R 7 , R 8 , R 9 The combinations are R in the above A-1 to A-7 and equations (1) to (6). 1 , R 2 , R 3 , R 4 , R 5 The combinations are m R from I-1 to I-28 above and equation (2). 1b The combinations are E-1 to E-15 above, and in equation (3), each with n R 1c and X 1c p R 2c and X 2c q A 2c The combinations above, O-1 to O-17, are preferred references.

[0192] Furthermore, in equations (1) and (4) in [IV] above, l R 1a and X 1a , r R 1d and X 1d s R 2d and X 2d The following are some preferred combinations. U'-1 X 1a , X 1d , X 2d It is a residue of the phenyl ring. In U'-2 U'-1, l, r, s = 0, X 1a , X 1d , X 2d to substituent R 1a , R 1d , R 2d X 1a , X 1d , X 2d In R 1a , R 1d , R 2d All the parts that can be substituted are hydrogen atoms. In U'-3 U'-1, there are l, r, and s R 1a , R 1d , R 2dEach of these is independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, with l, r, and s = 1 to 5. In U'-4 and U'-3, l, r, and s are 1 to 3. In U'-5 U'-4, R 1a , R 1d , R 2d Each of these is independently a branched alkyl group having at least one carbon atom between 3 and 8. In U'-6 U'-4, l, r, s = 1, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In U'-7 and U'-6, l, r, and s = 1, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the alkyl group preferably has 1 to 8 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 3 to 8 carbon atoms. In any of the following cases, PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d For -S-, R 1a , R 1d , R 2d At least one of them is in the para position. In U'-9 U'-4, l, r, s = 2, R 1a , R 1d , R 2d Each of these is independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). In U'-10 U'-9, l, r, s = 2, R 1a , R 1d , R 2dEach of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, wherein the number of carbon atoms in each alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, and / or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2. In either U'-11 U'-9 or 10, PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d For -S-, l, r, and s=2 are R 1a , R 1d , R 2d It is located at the ortho, para, or ortho, meta positions. In any of the following cases from U'-3 to U'-11, R 1a , R 1d , R 2d Each of these is a hydrocarbon group having a tertiary carbon and / or quaternary carbon independently, and is preferably an alkyl group. In U'-13 U'-1, there are l, r, and s R 1a , R 1d , R 2d Each of these is an alkoxy group having a linear or branched alkyl group with 1 to 18 carbon atoms, preferably an alkoxy group having a linear alkyl group with 1 to 8 carbon atoms, more preferably an alkoxy group having a linear alkyl group with 1 to 4 carbon atoms. Furthermore, l,r,s = 1 to 3, more preferably l,r,s = 1 to 2, and particularly preferably l,r,s = 1. In U'-14 and U'-13, l, r, and s are 1, and the alkoxy group is PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d It occupies a meta position relative to -S-. In U'-15 U'-1, there are l, r, and s R 1a , R 1d , R 2d is a hydroxyl group, preferably l,r,s=1-3, more preferably l,r,s=1-2, and especially preferably l,r,s=1. In U'-16 and U'-15, l, r, and s are 1, and the hydroxyl group is PhBzT 1a -S-, PhBzT 1d -S-, PhBzT 2d It is in the para position relative to -S-. U'-17 X 1a , X 1d , X 2d is a naphthyl ring residue, preferably l, r, s = 0.

[0193] Preferred embodiments of the ultraviolet absorber described in [IV] above are further described below. K-1 UV absorber as described in [IV] above In Car-2, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (2), (3), and (4), where X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, m, n, p, r, and s R elements. 1a , R 1b , R 1c , R 2c , R 1d , R 2d Each of these is an independent linear or branched alkyl group having 1 to 18 carbon atoms, and l, m, n, p, r, and s represent integers from 0 to 5. In Ka-3, Ka-1 and Ka-2, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (2), (3), and (4), and in the above formulas (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The '' indicates a phenyl ring residue, and the thioaryl ring group or thiocyclohexyl ring group is attached to the phenyl portion of the benzotriazole skeleton. In Ka-4, Ka-2 and Ka-3, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (3), and (4), and in the above formulas (1), (3), and (4), X 1a , X1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these is independently at least one linear or branched alkyl group having 3 to 8 carbon atoms, and l, n, p, r, and s represent integers of 1 or 2. In Ka-5, Ka-2 to Ka-4, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (3), and (4), and in the above formulas (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each independently represents an alkyl group having at least one tertiary carbon and / or quaternary carbon, and l, n, p, r, and s represent integers of 1 or 2. In Ka-6 and Ka-1, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (3), and (4), and in formulas (1), (3), and (4), X 1a , X 1c , X 2c , X 1d , X 2d The 'R' symbol indicates a phenyl ring residue, with l, n, p, r, and s R elements. 1a , R 1c , R 2c , R 1d , R 2d Each of these is an alkoxy group, hydroxyl group, or halogen atom having a linear or branched alkyl group with 1 to 18 carbon atoms, and l, n, p, r, and s represent integers of 1 or 2. In Ka-7 and Ka-2 to Ka-6, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (3), and (4), and in formulas (1), (3), and (4), the 2-phenylbenzotriazole skeleton has a hydroxyl group and a methyl group. In Ka-8 and Ka-7, the 2-phenylbenzotriazole derivative is represented by any of the above formulas (1), (3), and (4), wherein in formulas (1), (3), and (4), the 2-phenylbenzotriazole skeleton has a thioaryl ring group at the phenyl portion of the benzotriazole skeleton, and the phenyl skeleton at position 2 has a hydroxyl group, a t-butyl group, and a methyl group. In Ka-9 and Ka-1, the 2-phenylbenzotriazole derivative is represented by formula (6), and in formula (6), Y 1f and Y 2f Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a linear or branched alkyl group having 1 to 22 carbon atoms that may be substituted with a hydroxyl group.

[0194] <UV absorber a> Below, we will explain the ultraviolet absorber a from the ultraviolet absorbers described in [IV] above, using an example of its use in glass for transport equipment (including vehicles) with a glassy coating film.

[0195] The glass in which this UV absorber a is used comprises glass and a UV shielding film formed on its surface. The UV shielding film contains silicon dioxide and UV absorber a. Preferably, the UV shielding film has silicon dioxide as its main component.

[0196] Furthermore, while the film quality of the UV-shielding film is arbitrary, it is preferably glassy. In this specification, a film being glassy means that the matrix component of the film is glassy, ​​and even if the film contains crystalline components such as organic compound A, organic compound B (described later), and ITO fine particles, the film is considered glassy. In this specification, "main component" is a term that means a component that accounts for 50% or more, preferably 60% or more, by mass. Silicon oxide is a component that imparts durability and the hardness necessary for practical use to the film. UV absorber a functions as a UV-shielding component.

[0197] The UV-shielding film may contain components other than silicon dioxide and UV absorber a. The optional components of the film are not particularly limited, but examples include organic compound B, described later, which is a UV-shielding component not corresponding to UV absorber a, and organic compound C, which is a hydrophilic organic compound. Organic compound C may be a polymer. The UV-shielding film may further contain other components, such as structural units derived from a silane coupling agent. These structural units are silane coupling agent derivatives produced by the reaction of the silane coupling agent with other organic and / or inorganic substances.

[0198] The size and form of the UV absorber a are not limited, but to enhance the light transmittance of the glass containing the UV shielding film, it is added as fine particles. Adding it as fine particles improves the persistence of the UV shielding effect compared to adding it as a solute. To suppress the haze rate of the film, the average particle size of the fine particles is adjusted to 150 μm or less. Suitable UV absorber a is an organic compound that is solid at room temperature. In this specification, "room temperature" means 25°C.

[0199] Furthermore, polymers obtained by polymerizing UV absorbers are also known as UV-blocking components that are solid at room temperature. However, since such UV-blocking components are manufactured by polymerizing UV absorbers into which polymerizable functional groups such as (meth)acrylic groups have been introduced, their UV-blocking effect per unit mass is inferior to that of low-molecular-weight UV absorbers.

[0200] The molecular weight of organic compound A is preferably 5000 or less, more preferably 3000 or less, even more preferably 2000 or less, particularly preferably 1500 or less, and in some cases may be 1300 or less, even more preferably 1200 or less, particularly 900 or less, and especially 800 or less. The molecular weight of organic compound A is preferably 200 or more, and more preferably 300 or more. Organic compound A preferably does not contain polymerizable carbon-carbon double bonds in its molecule. Examples of polymerizable carbon-carbon double bonds include double bonds contained in polymerizable functional groups such as vinyl groups, vinylene groups, and vinylidene groups.

[0201] In the above example, it is preferable that the ultraviolet absorber a maintains a crystalline state in the ultraviolet shielding film-forming composition and the ultraviolet shielding film. The crystalline state of ultraviolet absorber a can be confirmed by X-ray diffraction. The ultraviolet absorber a may be crushed using a known dry or wet grinding device to obtain a predetermined average particle size before being incorporated into the ultraviolet shielding film-forming composition. The time it takes for the ultraviolet absorber a to be crushed to obtain a predetermined average particle size depends on the type of grinding device, the amount of material added, and the grinding conditions such as the rotation speed. For this reason, in mass production, it is advisable to determine in advance the time required to obtain a predetermined average particle size by repeatedly interrupting the grinding process using the grinding device as needed and checking the average particle size of the sampled crushed material. When grinding, surfactants, water-soluble resins, etc., may be added to the ultraviolet absorber a to be crushed as appropriate. The ultraviolet absorber a may be dispersed in the film as fine particles with an average particle size of 150 nm or less, preferably 10 to 150 nm, more preferably 50 to 140 nm, and particularly preferably 70 to 140 nm. If the average particle size of the microparticles is too large, it will reduce the transparency of the film, but if it is too small, it may degrade the UV absorption capacity or reduce its durability. The "average particle size" mentioned above, including the measurements in the examples section described later, is a value based on measurements using the dynamic light scattering method, a type of photon correlation method. Specifically, it is the particle size at which the cumulative frequency is 50% in the volume-based distribution of the equivalent spherical diameter. The "average particle size" can be measured, for example, using the Nikkiso Microtrack Ultrafine Particle Size Distribution Analyzer 9340-UPA150. The presence of microparticles of the UV absorber a dispersed in the film can be confirmed by observation using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The average value A of the top 10% of the maximum lengths of each microparticle present in the film cross-section observed using SEM or TEM will not be less than the "average particle size" value defined above. Therefore, if the above average value A is 150 nm or less, the "average particle size" can be considered to be 150 nm or less. Furthermore, the average value B of the bottom 10% of lengths in the direction perpendicular to the direction that defines the maximum length of each fine particle present in the above-mentioned film cross-section will not exceed the value of "average particle size" as defined above.Therefore, for example, if the above average value B is 50 nm or more, the "average particle size" may be considered to be 50 nm or more. The ultraviolet absorber a can also be introduced into the film as a solute dissolved in an organic solvent capable of dissolving it. Introduction as a solute is a more easily implemented method and is also desirable for achieving a more uniform distribution of ultraviolet absorber a in the ultraviolet shielding film. However, introducing ultraviolet absorber a into the film as fine particles improves the persistence of the film's ultraviolet shielding ability. Furthermore, adding ultraviolet absorber a as fine particles yields more favorable spectral absorption characteristics than addition as a solute. Addition as fine particles can cause the absorption peak due to organic compound A in the spectral absorbance curve to shift to longer wavelengths than when added as a solute. This shift makes it possible to more effectively shield light near 400 nm wavelength. However, on the other hand, the shift of the absorption peak to the longer wavelength side makes the yellowish tint of the UV-shielding film stronger. Taking these factors into consideration, organic compound A is suitable for sufficiently reducing the transmittance of light near 400 nm while suppressing the strong yellowish tint of the UV-shielding film. The UV-shielding film-forming composition may be a film-forming solution containing a silicon dioxide precursor and UV absorber a. The solvent constituting the film-forming solution is not particularly limited, but examples include water and organic solvents. However, in terms of dispersing the UV absorber as fine particles as in the above example, water and lower alcohols are suitable, with water being the most suitable. As lower alcohols, alcohols with 1 to 3 carbon atoms such as methanol, ethanol, and isopropanol are preferred. The UV-shielding film-forming composition may also contain components that may be incorporated into the UV-shielding film, such as organic compound B and silane coupling agents. The composition for forming the ultraviolet shielding film may contain additives such as antioxidants, heat stabilizers, weather stabilizers, light stabilizers, pigments, dyes, fillers, plasticizers, antistatic agents, nucleating agents, wetting agents, preservatives, fungicides, defoamers, and stabilizers, as needed. The silicon dioxide precursor is not limited in type as long as it can supply silicon dioxide to the ultraviolet shielding film. When forming the ultraviolet shielding film by the sol-gel method described later, the preferred silicon dioxide precursor is a silicon compound having a hydrolyzable functional group, typically a silicon tetraalkoxide.Furthermore, silicon dioxide is also supplied from silicon atoms contained in the silane coupling agent. Therefore, the silane coupling agent also functions as a silicon dioxide precursor. The silicon dioxide in the ultraviolet shielding film may account for 40% or more by mass, 50% or more by mass (in which case silicon dioxide becomes the main component of the film), and in some cases, 70% or more by mass of the entire film. Preferably, the ultraviolet shielding film has a form in which silicon dioxide is the main component and fine particles of organic compound A and other components are dispersed in a network of Si-O bonds. A film having such a form is suitable for outdoor use as window glass, etc. Preferably, the ultraviolet shielding film forming composition contains a silicon dioxide precursor such that the silicon dioxide content of the ultraviolet shielding film formed from the composition is approximately as described above. Preferably, the ultraviolet absorber a is contained in the ultraviolet shielding film in an amount of 0.01 to 90%, more specifically 0.1 to 80%, 1 to 80%, particularly 5 to 60%, even more specifically 5 to 50%, and especially 7 to 30%, expressed by mass%, relative to the silicon dioxide in the ultraviolet shielding film. Considering this, the amount of UV absorber a is expressed in mass%, and is not particularly limited, but is preferably added in an amount of, for example, 0.5 to 25%, more preferably 0.5 to 15% relative to the volume of the film-forming solution. Organic compound B is a UV shielding component that does not correspond to UV absorber a. Organic compound B is not particularly limited, but is, for example, a UV absorber containing a benzotriazole, triazine, benzophenone, or benzoate skeleton. Not particularly limited, but is, for example, an organic compound having a molecular structure that contains a 2-phenyl-benzotriazole skeleton and to which a sulfur atom-containing group is not attached, or a benzophenone compound. Similar to UV absorber a, it is preferable that organic compound B maintains a crystalline state in the UV shielding film-forming composition and the UV shielding film. Organic compound B may be crushed using a known dry or wet grinding device to a predetermined average particle size before being incorporated into the UV shielding film-forming composition. The preferred average particle size of organic compound B is as described above for UV absorber a. It is preferable that the total amount of organic compound B and ultraviolet absorber a be blended in such a ratio that the ratio of ultraviolet absorber a to silicon dioxide in the ultraviolet shielding film is as described above.Organic compound B should be added in such a way that its mass is less than that of UV absorber a, preferably less than 50% of that of UV absorber a.

[0202] Organic compound B may have two or more 2-phenylbenzotriazole skeletons. Preferably, the two or more 2-phenylbenzotriazole skeletons are connected by alkylene groups. A preferred example of organic compound B having two 2-phenylbenzotriazole skeletons is the R of each skeleton in formula (A) above. 2 It has a form in which it is bonded to each other by methylene groups attached to it. In this form, the R of each skeleton 1 is a hydroxyl group, R 4 is a tert-butyl group, R 3 and R 5 It may also be a hydrogen atom. For example, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] is one such example.

[0203] Another example of organic compound B is benzophenone compounds. Examples include 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone).

[0204] Organic compound C is a hydrophilic organic compound and may be a polymer. Organic compound C contributes to improving the dispersibility of UV absorber a and the benzotriazole-based UV shielding component of organic compound B in the UV shielding film, thereby enhancing the light shielding ability of the benzotriazole-based UV shielding component and further suppressing its degradation. When forming a relatively thick UV shielding film (for example, thicker than 300 nm, or even thicker than 500 nm) by liquid-phase film formation such as the sol-gel method, cracks may occur due to the evaporation of the liquid component contained in the film-forming solution. Organic compound C is also a component that enables the formation of a thick film while suppressing the occurrence of cracks. Organic compound C is preferably at least one selected from polyether compounds, polyol compounds, polyvinylpyrrolidones, and polyvinylcaprolactams. Polyether compounds are compounds containing two or more ether bonds. Polyol compounds are compounds containing two or more hydroxyl groups. Polyvinylpyrrolidones are polymers containing vinylpyrrolidone and its derivatives as monomers. Polyvinylcaprolactams are polymers containing vinylcaprolactam and its derivatives as monomers. Examples of organic compound C include polyether-type surfactants and polyol compounds produced by the reaction of epoxy groups of polyepoxy compounds. Organic compound C may also be a polymer. Examples of organic compound C include polycaprolactone polyol, bisphenol A polyol, polyethylene glycol, and polypropylene glycol. Organic compound C is preferably added to the film in a mass percentage of silicon dioxide in the film, such that it is 0-75%, more specifically 0.05-50%, particularly 0.1-40%, especially 1-30%, possibly 10% or less, and preferably 7% or less. The type of silane coupling agent is not particularly limited, but organic compounds represented by LSiM3 are preferred. Here, L is at least one selected from vinyl groups, glycidoxy groups, methacrylic groups, amino groups, and mercapto groups, and M is a halogen element or an alkoxy group. In silane coupling agents, the L group reacts with organic matter in the UV-shielding film, and the X group hydrolyzes and reacts with inorganic matter in the film.Through this reaction, the silane coupling agent contributes to improving the dispersibility of the UV-shielding component, which is organic compound A or organic compounds A and B, in the film, thereby enabling the formation of a thick film while suppressing the occurrence of cracks. It is preferable to add the silane coupling agent to the film such that the silicon dioxide supplied from the silane coupling agent is 0-30%, preferably 0.1-20%, and more preferably 1-10%, of the total silicon dioxide in the UV-shielding film, expressed in mole percent. The amount of silicon dioxide supplied from the silane coupling agent is calculated according to the number of oxygen atoms bonded to the silicon atoms of the structural units derived from the silane coupling agent in the UV-shielding film. For example, the silicon dioxide supplied from the silane coupling agent represented by LSiM3 above has three oxygen atoms bonded to the silicon atoms, so SiO₂. 1.5This is how it is displayed. Other components that the UV-shielding film may contain include indium tin oxide (ITO) fine particles. ITO fine particles are a preferred component for absorbing near-infrared light. The ITO fine particles are preferably dispersed in the film as fine particles with an average particle size of 200 nm or less, preferably 5 to 150 nm. Similar to the fine particles of UV absorber a, if the particle size is too large, it will reduce the transparency of the film, and if it is too small, the effect of the addition will not be sufficiently obtained. It is also preferable to prepare a dispersion of ITO fine particles in advance and add it to the film-forming solution. The UV-shielding film may contain inorganic components other than silicon dioxide and ITO fine particles. Examples of such inorganic components include components derived from the acid catalyst used in the sol-gel method. The silicon dioxide in the UV-shielding film should account for 30% by mass or more of the total film, preferably 40% by mass or more, more preferably 50% by mass or more (in this case, silicon dioxide becomes the main component of the film), and possibly 70% by mass or more. The ultraviolet shielding film preferably has silicon dioxide as its main component, with fine particles of ultraviolet absorber a and other components dispersed in a network of Si-O bonds. Glass containing a film having such a form is not particularly limited, and examples include glass used in buildings and transportation equipment, specifically vehicles such as automobiles and railway cars, ships, aircraft, daylighting glass, fluorescent lamps, mercury lamps, halogen bulbs, and LED lights, and is particularly suitable for outdoor use as window glass.

[0205] The following describes a preferred method for forming the ultraviolet shielding film shown in the above example using the sol-gel method. The organic solvent used in the sol-gel method is preferably one that is highly compatible with silicon alkoxides and water, and a lower alcohol having 1 to 3 carbon atoms is suitable. Examples of silicon alkoxides used as silicon oxide precursors include silicon tetraalkoxides such as silicon tetramethoxide, silicon tetraethoxide (TEOS), and silicon tetraisopropoxide. Hydrolyzed silicon alkoxides may also be used as silicon oxide precursors. The concentration of silicon alkoxide in the solution formed by the sol-gel method is preferably 3 to 15% by mass, particularly 3 to 13% by mass, expressed as the silicon oxide concentration when the silicon alkoxide is converted to silicon oxide. If this concentration is too high, cracks may occur in the film. The amount of water relative to the silicon alkoxide is preferably 4 times or more, specifically 4 to 40 times, preferably 4 to 35 times, expressed as a molar ratio. As the hydrolysis catalyst, it is preferable to use an acid catalyst, particularly a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, or p-toluenesulfonic acid. Since organic matter derived from the acid catalyst may reduce film hardness, inorganic acids are preferred as the acid catalyst. Hydrochloric acid is the most preferred acid catalyst because it is highly volatile and does not easily remain on the film. The concentration of the acid catalyst is preferably in the range of 0.001 to 2 mol / kg, expressed as the molal concentration of protons assuming complete dissociation of protons from the acid. By adding an excess of water to the extent described above and adding the acid catalyst to achieve the concentration described above, a relatively thick film can be easily formed by the sol-gel method at a temperature range that prevents the decomposition of organic matter. A film-forming solution for an ultraviolet shielding film can be prepared by mixing a solution to which the sol-gel method can be applied, containing the components listed above, with a dispersion of fine particles such as ultraviolet absorber a, and further adding organic compound C, etc., as needed. However, the method of preparing the film-forming solution is not limited to this, and the components necessary for film formation by the sol-gel method may be added sequentially to the dispersion of fine particles. The film-forming solution may be prepared to include, along with fine particles such as ultraviolet absorber a, components necessary for forming a film by a method other than the sol-gel method, such as polysilazane.In the coating process of the film-forming solution, it is preferable to maintain the relative humidity of the atmosphere at less than 40%, and more preferably at 30% or less. Maintaining low relative humidity prevents the film from excessively absorbing moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, the remaining water that penetrates into the film matrix may reduce the strength of the film. The drying process of the film-forming solution is preferably carried out to include an air-drying process under the coating environment and a heat-drying process involving heating. The air-drying process is preferably carried out by exposing the coated film of the film-forming solution to an atmosphere where the relative humidity is maintained at less than 40%, and more preferably at 30% or less. In the heat-drying process, the condensation polymerization reaction of silanol groups generated by hydrolysis proceeds, and the removal of liquid components remaining in the film, especially water, proceeds, and the silicon dioxide matrix (a network of Si-O bonds) develops. The heat-drying process is preferably carried out by exposing the coated film to an atmosphere at 300°C or less, for example, 100-200°C. The heating and drying process is preferably carried out by exposing the coated film to an atmosphere of 300°C or lower, for example, 100-200°C, and possibly 50-100°C. The heating temperature in the heating and drying process is preferably below the melting point of the ultraviolet absorber a and organic compound B added as fine particles, particularly the ultraviolet absorber a added as fine particles. The heating temperature for heating the film in the heating and drying process is preferably selected from a range lower than the melting point of the ultraviolet absorber a added as fine particles. When organic compound B is added as fine particles, the heating temperature is preferably selected from a range lower than the melting point of both the ultraviolet absorber a and the organic compound B. In this case, the melting points of the ultraviolet absorber a and the organic compound B are preferably 65°C or higher, particularly 100°C or higher, for example, 120-240°C, and may also be 140-240°C.

[0206] Glass can be obtained by liquid-phase film formation by sequentially carrying out the series of steps described above, namely a) a step of preparing a film-forming solution for an ultraviolet shielding film containing fine particles of ultraviolet absorber a and other components, b) a step of applying the film-forming solution onto glass, and c) a step of drying the film-forming solution. This manufacturing method is a method for producing a glass article having an ultraviolet shielding film, comprising the steps of: preparing a film-forming solution for an ultraviolet shielding film containing an organic compound A as a solute, which is solid at room temperature and has an average molecular weight of 5000 or less, as fine particles with an average particle size of 150 nm or less; applying this film-forming solution onto glass; and drying the film-forming solution on the glass to form an ultraviolet shielding film. This manufacturing method constitutes another aspect of the present invention. The film thickness of the ultraviolet shielding film is preferably greater than 300 nm and 15 μm or less, more preferably 500 nm or more and 10 μm or less, and particularly preferably 1000 nm or more and 5000 nm or less. If the film is too thin, sufficient UV protection may not be achieved, and if the film is too thick, the transmittance of the film will decrease, impairing the transparency of the glass.

[0207] The glass is not particularly limited, and soda lime silicate glass can be used. A typical composition example of this glass is shown below. In the following, all "%" indicating the content of each component in the glass are in mass percent. Alkali metal oxide (R2O) specifically refers to the total amount of Na2O and K2O. T-Fe2O3 is the total iron oxide converted to Fe2O3. In addition, each composition example may contain trace components that are not indicated. For example, general clear glass can be used. An example of its glass composition is shown below. (Clear glass) SiO2: 70~73% by mass Al2O3: 0.6~2.4% CaO: 7-12% MgO: 1.0~4.5% R2O: 13-15% (R is an alkali metal) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0.08~0.2%.

[0208] Furthermore, it is preferable to use soda lime silicate glass having a composition in which the concentration of iron oxide is increased and, if necessary, other ultraviolet absorbing components such as titanium dioxide and cerium oxide are added. As soda lime silicate glass, glass having a glass composition containing more than 0.2%, preferably 0.4% or more, more preferably 0.5% or more, for example 0.5 to 1.3% iron oxide, and having a light transmittance of 70% or less, preferably 50% or less, at a wavelength of 380 nm, and a light transmittance of 75% or more at a wavelength of 550 nm may be used. For example, green glass, heat-absorbing glass, and ultraviolet-cut green glass can be used. Some examples of such glass compositions are shown below. (Green glass) SiO2: 70~73% by mass Al2O3: 0.6~2.4% CaO: 7-12% MgO: 1.0~4.5% R2O: 13-15% (R is an alkali metal) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0.4-0.6% (Heat-absorbing glass) SiO2: 70~73% by mass Al2O3: 0.6~2.4% CaO: 7-12% MgO: 1.0~4.5% R2O: 13-15% (R is an alkali metal) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0.5~1.1% (UV-cut green glass) SiO2: 70~73% by mass Al2O3: 0.6~2.4% CaO: 7-12% MgO: 1.0~4.5% R2O: 13-15% (R is an alkali metal) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0.7-1.3% CeO2: 0-2% TiO2: 0-0.5%. However, high-transmittance glass with an iron oxide content of 0.1% by mass or less, preferably 0.01% to 0.06%, can also be used. An example is shown below. (High-transmittance glass) SiO2: 70~73% by mass Al2O3: 0.6~2.4% CaO: 7-12% MgO: 1.0~4.5% R2O: 13-15% (R is an alkali metal) Total iron oxide (T-Fe2O3) converted to Fe2O3: 0.01~0.06%. In the above, the iron oxide concentration is a value calculated by converting the total iron oxide contained in the glass to Fe2O3.

[0209] However, the glass is not limited to those described above; it may also be glass with low light transmittance in the visible range. Examples of such glass include glass manufactured for vehicle windows with a light transmittance of 20-60% at a wavelength of 550 nm. Since it is difficult to adequately shield the ultraviolet range, especially in the long-wavelength region, using only the components that make up the glass is difficult, the application of the ultraviolet shielding film described above is also useful for glass with low visible light transmittance.

[0210] The glass having the above-mentioned ultraviolet shielding film has an ultraviolet transmittance T based on ISO9050 (1990 edition). UV 380 may be 2% or less, preferably 1% or less, and more preferably 0.5% or less. Furthermore, the glass having the above ultraviolet shielding film has an ultraviolet transmittance T calculated according to ISO 13837 (convention A). UV 400 may be 2% or less, preferably 1.5% or less, and particularly preferably 1% or less. The glass having the above ultraviolet shielding film may have a visible light transmittance YA of 70% or more, measured using a CIE standard A light source. The glass having the above ultraviolet shielding film may have T UV 400 may be less than 2%, and YA may be 70% or more.

[0211] The glass having the above-mentioned ultraviolet shielding film allows transmitted light from a CIE standard C light source to be L* a * b * Displayed according to the color system, a values ​​between -15 and 0. * and b less than or equal to 12 * It may have a * b is -12 or greater and -7 or less, for example, -9 or greater and -8 or less, * The yellowness index (YI) of the transmitted light for a C-light source of the CIE standard may be 10 or less, for example, 5 to 10. Furthermore, the glass having the above ultraviolet shielding film may have a yellowness index (YI) of 14 or less for transmitted light for a C-light source of the CIE standard, as defined in Japanese Industrial Standard (JIS) K7373:2006. The yellowness index (YI) may be 10 or less, and even 8 or less. Furthermore, the dominant wavelength of transmitted light for a C-light source of the CIE standard may be 560 nm or less for the glass having the above ultraviolet shielding film. The dominant wavelength may be 555 nm or less, for example, in the range of 550 to 555 nm. The blue light cut rate of the glass having the above ultraviolet shielding film may be 41% or less, preferably 37% or less, and particularly preferably 36% or less, based on the blue light hindrance function of JIS T7330. Here, the blue light cut rate can be defined as the ratio of the effective radiant intensity related to retinal damage caused by blue light from sunlight (hereinafter, effective radiant intensity of sunlight) to the effective radiant intensity reduced by transmitting light through the glass, expressed as a percentage. Specifically, it can be determined by the following method: The effective radiant intensity of sunlight is calculated by summing the weighting function for the blue light hindrance function described in Annex A of JIS T7330:2000 up to the wavelength range of 380 to 550 nm. Next, the effective radiant intensity of the light transmitted through the glass (hereinafter referred to as the effective radiant intensity of transmitted light) is calculated by taking the sum of the products of the spectral transmittance of the glass and the weighting function at each wavelength in the above wavelength range. The ratio of the effective radiant intensity of transmitted light to the effective radiant intensity of sunlight can be taken and this value can be converted to a percentage by subtracting it from 1.

[0212] The glass having the above-mentioned UV-shielding film is suitable for wavelengths of 295-450 nm and illuminances of 76 mW / cm². 2 UV transmittance T after 100 hours of irradiation with UV light UV UV transmittance T before irradiation with the above UV light from 400 UV The difference ΔT after subtracting 400 UVThe percentage of 400 can be 2% or less, even 1% or less, and especially 0.5% or less. The glass having the above-mentioned ultraviolet shielding film is suitable for wavelengths of 295-450 nm and illuminances of 76 mW / cm². 2 The difference ΔYA, obtained by subtracting the visible light transmittance YA before irradiation with the ultraviolet light from the visible light transmittance YA after 100 hours of irradiation with the ultraviolet light, may be -0.5% or more, particularly -0.2% or more. ΔYA may be between -0.5% and 1%, or even between -0.2% and 0.5%. [Examples]

[0213] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. <Synthesis Example 1> Synthesis of Compound 1

[0214] [ka]

[0215] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), benzenethiol (17.4 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 1 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1445, 1390cm -1 Triazole ring stretching vibration 665cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.37 (s, 3H, -Ph-OH-C H3-C(CH3)3), 7.16 (s, 1H), 7.38 (d, 4H), 7.48 (s, 2H), 7.68 (s, 1H), 7.83 (d, 1H), 8.03 (d, 1H), (insg.10arom. C H ), 11.55 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 116.8, 118.0, 119.3, 128.3, 128.8, 129.6, 132.7 (CH arom ), 125.5, 141.2, 143.2 (C arom ), 129.8 ( C arom -CH3), 139.2 ( C arom -S), 139.2 (S- C arom ), 139.2 ( C arom -C(CH3)3), 146.7 ( C arom -OH)

[0216] <Synthesis Example 2> Synthesis of Compound 2

[0217]

change

[0218] 2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-tert-butylbenzenethiol (26.3 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125 °C for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and water washing, and then recrystallization and column purification to obtain Compound 2. FT-IR (KBr): 3000 cm -1 : O-H stretching vibration 1444, 1390 cm -1 : Triazole ring stretching vibration 668 cm -1 : C-S stretching vibration 1 1H-NMR (CDCl3 400 MHz): δ1.36 (s, 9H, -S-Ph-C(C H 3)3), 1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.37 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 7.16 (s, 1H), 7.35 (d, 1H), 7.44 (s, 4H), 7.59 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 13C-NMR (CDCl3 100 MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 31.3 (-S-Ph-C( C H3)3), 34.8 (-S-Ph- C (CH3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 115.4, 117.8, 119.3, 126.8, 128.8, 129.2, 133.2 (CH arom), 125.4, 141.5, 143.3 (C arom ), 128.3 ( C arom -CH3), 138.5 ( C arom -S), 138.5 (S - C arom ), 139.1, 152.0 ( C arom -C(CH3)3), 146.7 ( C arom -OH)

[0219] <Synthesis Example 3> Synthesis of Compound 3

[0220] [ka]

[0221] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 2,4-dimethylbenzenethiol (21.9 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 3 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1447, 1385cm -1 Triazole ring stretching vibration 665cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.47 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.38 (s, 9H, -Ph-OH-C H 3-C(CH3)3, -Ph-C H 3-C H3), 7.08 (d, 1H), 7.15 (d, 2H), 7.30 (m, 2H), 7.43 (d, 1H), 7.77 (d, 1H), 8.01 (d, 1H), (insg.8arom. C H ), 11.57 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.6 (-Ph- C H3-CH3), 20.9 (-Ph-OH- C H3-C(CH3)3), 20.6 (-Ph-CH3- C H3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 113.3, 117.7, 119.2, 128.0, 128.3, 128.6, 135.8 (CH arom ), 125.4, 141.3, 143.4, 152.0 (C arom ), 128.2, 132.0, 141.9 ( C arom -CH3), 138.8 ( C arom -C(CH3)3), 139.1 ( C arom -S), 139.9 (S - C arom ), 146.6 ( C arom -OH)

[0222] <Synthesis Example 4> Synthesis of Compound 4

[0223]

change

[0224] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 3-methoxybenzenethiol (22.2 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 4 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1380cm -1 Triazole ring stretching vibration 660cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.38 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 3.79 (s, 3H, C H 3O-Ph-S-), 6.90 (d, 1H), 7.00 (s, 1H), 7.06 (d, 1H), 7.17 (s, 1H), 7.30 (s, 1H), 7.40 (d, 1H), 7.74 (s, 1H), 7.84 (s, 1H), 8.04 (s, 1H), (insg.9arom. C H ), 11.56 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 55.4 (-S-Ph-O- C H3), 114.1, 117.3, 117.5, 118.0, 119.3, 124.6, 128.9, 130.0, 130.4 (CH arom), 125.4, 141.5, 143.3 (C arom ), 128.3 ( C arom -CH3), 138.5 ( C arom -S), 138.5 (S - C arom ), 139.1 ( C arom -C(CH3)3), 146.7 ( C arom -OH), 159.9 ( C arom -OCH3)

[0225] <Synthesis Example 5> Synthesis of Compound 5

[0226] [ka]

[0227] 4-tert-amylphenol (25.0 g, 152.2 mmol), dimethylcarbamoyl chloride (28.2 g, 228.3 mmol), and sodium hydride (7.3 g, 167.4 mmol) were reacted in 50 g of THF at 60°C for 4 hours. After the reaction was complete, toluene and water were added, followed by acid treatment with hydrochloric acid. The organic layer, washed with water, was removed by vacuum distillation. The resulting liquid was purified by column chromatography to obtain solid intermediate 5-1. Intermediate 5-1 was reacted in 50 g of sulfolane at 240°C for 4 hours. After the reaction was complete, toluene and water were added, followed by washing with water and vacuum distillation to obtain liquid intermediate 5-2. Intermediate 5-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours. After cooling, hydrochloric acid was added and stirred, followed by washing with water, recrystallization, and column chromatography to obtain 4-tert-amylthiophenol.

[0228] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (3.8 g, 12.0 mmol), 4-tert-amylthiophenol (2.8 g, 15.5 mmol), potassium carbonate (3.6 g, 26.4 mmol), and potassium iodide (0.1 g, 0.8 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 5 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1380cm -1 Triazole ring stretching vibration 660cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ0.72 (t, 3H, -S-Ph-CCH2C H 3), 1.31 (s, 6H, -S-Ph-C(C H 3)2), 1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 1.66 (q, 2H, -S-Ph-CC H 2CH3), 2.37 (s, 3H, -Ph-OH-C H C H ), 11.58 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ9.18 (-S-Ph-CCH2 C H3), 20.9 (-Ph-OH- C H3-C(CH3)3), 28.3 (-S-Ph-C( C H3)2), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C(CH3)3), 36.8 (-S-Ph- C (CH3)2), 38.1 (-S-Ph-C C H2CH3), 115.5, 117.8, 119.3, 127.4, 128.8, 129.3, 133.0 (CH arom ), 125.4, 141.5, 143.3 (C arom ), 128.3 ( C arom -CH3), 138.4 ( C arom -S), 138.4 (S - C arom ), 139.1 ( C arom -C(CH3)3), 146.7 ( C arom -OH), 150.4 ( C arom -C(CH3)2)

[0229] <Synthesis Example 6> Synthesis of Compound 6

[0230] [ka]

[0231] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-isopropylbenzenethiol (24.1 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 6 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1446, 1389cm -1 Triazole ring stretching vibration 666cm -1 :CS stretching vibration 1H-NMR (CDCl3400MHz): δ1.30 (d, 6H, (C H 3)2CH-Ph-S-), 1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.37 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 2.95 (m, 1H, (CH3)2C H -Ph-S-), 7.16 (s, 1H), 7.28 (s, 2H), 7.36 (d, 1H), 7.45 (s, 2H), 7.57 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 23.9 (( C H3)2CH-Ph-S-), 29.5 (-Ph-OH-CH3-C( C H3)3), 33.9 ((CH3)2 C H-Ph-S-), 35.4 (-Ph-OH-CH3- C (CH3)3), 115.3, 117.8, 119.3, 127.9, 128.7, 129.2, 129.6, 133.6 (CH arom ), 125.4, 141.4, 143.3 (C arom ), 128.3 ( C arom -CH3), 138.5 ( C arom -S), 138.5 (S - C arom ), 139.1 ( C arom -C(CH3)3), 146.7 ( C arom -OH), 149.7 (C arom - C H)

[0232] <Synthesis Example 7> Synthesis of Compound 7

[0233] [Chemical formula]

[0234] 4-(1,1,3,3-Tetramethylbutyl)phenol (25.0 g, 121.2 mmol), dimethylcarbamoyl chloride (22.5 g, 181.7 mmol), and sodium hydride (5.8 g, 133.3 mmol) were reacted in 50 g of THF at 60 °C for 4 hours. After completion of the reaction, toluene and water were added, followed by addition of hydrochloric acid for acid treatment, and the washed organic layer was distilled off under reduced pressure. The obtained liquid was purified by column chromatography to obtain solid intermediate 7-1. The obtained intermediate 7-1 was reacted in 50 g of sulfolane at 240 °C for 4 hours. After completion of the reaction, toluene and water were added for washing with water, and after distillation under reduced pressure, liquid intermediate 7-2 was obtained. The obtained intermediate 7-2 and potassium hydroxide were stirred in ethanol at 60 °C for 3 hours, cooled, hydrochloric acid was added and stirred, followed by washing with water, recrystallization, and column purification to obtain 4-(1,1,3,3-tetramethylbutyl)thiophenol.

[0235] 2-(2-Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (5.5 g, 17.3 mmol), 4-(1,1,3,3-tetramethylbutyl)thiophenol (5.0 g, 22.5 mmol), potassium carbonate (5.3 g, 38.1 mmol), and potassium iodide (0.2 g, 1.2 mmol) were reacted in 60 g of DMF at 125 °C for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 7. FT-IR (KBr): 3000 cm -1 : O-H stretching vibration 1450, 1380 cm -1 : Triazole ring stretching vibration 660 cm -1 : C-S stretching vibration 1 H-NMR (CDCl3 400 MHz): δ0.76 (s, 9H, -S-Ph-CCH2C(CH 3)3), 1.40 (s, 6H, -S-Ph-C(C H 3)2), 1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 1.77 (s, 2H, -S-Ph-CC H 2), 2.37 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 7.16 (d, 1H), 7.34 (m, 1H), 7.42 (s, 4H), 7.59 (s, 1H), 7.80 (d, 1H), 8.02 (s, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 31.8 (-S-Ph-CCH2C( C H3)3), 31.4 (-S-Ph-C( C H3)2), 32.5 (-S-Ph- C ), 35.4 (-Ph-OH-CH3- C (CH3)3), 38.6 (-S-Ph-CCH2 C (CH3)3), 57.0 (-S-Ph-C C H2), 115.4, 117.8, 119.3, 127.6, 128.7, 129.2, 133.0 (CH arom ), 125.4, 141.5, 143.3 (C arom ), 128.3 ( C arom -CH3), 138.5 ( C arom -S), 138.5 (S - C arom ), 139.1 ( C arom -C(CH3)3), 146.7 ( C arom -OH), 151.2 (C arom -C(CH2)2)

[0236] <Synthesis Example 8> Synthesis of Compound 8

[0237] [ka]

[0238] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 5-tert-butyl-2-methylbenzenethiol (28.5 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 8 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1385cm -1 Triazole ring stretching vibration 665cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.31 (s, 9H, -S-Ph-C(C H 3)3), 1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.36 (s, 6H, -Ph-OH-C H 3-C(CH3)3, -S-Ph-C H 3), 7.15 (d, 1H), 7.34 (m, 4H), 7.56 (d, 1H), 7.80 (d, 1H), 8.01 (d, 1H), (insg.8arom. C H ), 11.57 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.1 (-Ph- CH3), 20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 31.3 (-Ph-CH3-C( C H3)3), 34.5 (-Ph-CH3- C (CH3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 113.6, 117.7, 119.2, 126.7, 128.7, 130.4, 130.8, 132.5 (CH arom ), 125.4, 141.3, 143.4, 152.0 (C arom ), 128.3, 128.4 ( C arom -CH3), 138.5 ( C arom -S), 139.1 (S - C arom ), 138.8, 150.4 ( C arom -C(CH3)3), 146.6 ( C arom -OH)

[0239] <Synthesis Example 9> Synthesis of Compound 9

[0240] [ka]

[0241] Compound 9 was obtained by reacting 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), p-toluenethiol (19.7 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing, and then recrystallization and column purification. FT-IR(KBr): 3000cm -1:OH stretching vibration 1444, 1389cm -1 :Torion ring telescopic vibration 667cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.37 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 2.40 (s, 3H, C) H 3-Ph-S-), 7.16 (s, 1H), 7.23 (s, 2H), 7.32 (d, 1H), 7.43 (s, 2H), 7.56 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom. C H ), 11.56 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 21.2 ( C H3-Ph-S-), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3) , 115.3, 117.8, 119.3, 128.7, 129.3 130.5, 133.7(CH arom ), 125.4, 141.2, 143.4 (C arom ), 128.3 ( C arom -CH3), 138.9( C arom -S), 138.7(S - C arom ), 139.1( C arom -C(CH3)3), 146.7( C arom -OH)

[0242] <Synthesis Example 10> Synthesis of Compound 10

[0243] [ka]

[0244] 2,4-di-tert-amylphenol (25.0 g, 106.7 mmol), dimethylcarbamoyl chloride (19.8 g, 160.0 mmol), and sodium hydride (5.1 g, 117.4 mmol) were reacted in 50 g of THF at 60°C for 4 hours. After the reaction was complete, toluene and water were added, followed by acid treatment with hydrochloric acid. The organic layer, washed with water, was removed by vacuum distillation. The resulting liquid was purified by column chromatography to obtain solid intermediate 10-1. Intermediate 10-1 was reacted in 50 g of sulfolane at 240°C for 4 hours. After the reaction was complete, toluene and water were added, followed by washing with water and vacuum distillation to obtain liquid intermediate 10-2. Intermediate 10-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours. After cooling, hydrochloric acid was added and stirred, followed by washing with water, recrystallization, and column chromatography to obtain 2,4-di-tert-amylthiophenol.

[0245] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (2.9 g, 9.2 mmol), 2,4-di-tert-amylthiophenol (3.0 g, 12.0 mmol), potassium carbonate (2.8 g, 20.3 mmol), and potassium iodide (0.1 g, 0.6 mmol) were reacted in 60 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 10 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1380cm -1 Triazole ring stretching vibration 660cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ0.60 (m, 6H, -S-Ph-(CCH2C H 3)2), 1.23 (s, 6H, -S-Ph-C(C H3)2), 1.39 (m, 15H, -S-Ph-C(C H 3)2,-Ph-OH-CH3-C(C H 3)3), 1.58 (q, 2H, -S-Ph-CC H 2CH3), 1.96 (q, 2H, -S-Ph-CC H 2CH3), 2.26 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 7.05 (m, 2H), 7.20 (d, 1H), 7.27 (s, 1H), 7.30 (s, 1H), 7.35 (s, 1H), 7.68 (d, 1H), 7.92 (d, 1H), (insg.8arom. C H ), 11.50 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ9.22 (-S-Ph-CCH2 C H3), 9.54 (-S-Ph-CCH2 C H3), 20.9 (-Ph-OH- C H3-C(CH3)3), 28.3 (-S-Ph-C( C H3)2), 28.8 (-S-Ph-C( C H3)2), 29.6 (-Ph-OH-CH3-C( C H3)3), 34.4 (-S-Ph- C ), 35.4 (-Ph-OH-CH3- C (CH3)3), 37.0 (-S-Ph- C ), 36.8 (-S-Ph-C C H2), 40.5 (-S-Ph-C C H2), 114.0, 117.6, 119.3, 125.0, 126.6, 127.3, 128.6, 128.7, 140.9 (CH arom ), 125.4, 141.2, 143.4 (C arom ), 128.3 ( C arom -CH3), 138.3 ( C arom-S), 138.3 (S - C arom ), 139.1 ( C arom -C(CH3)3), 146.6 ( C arom -OH), 150.1 ( C arom -C), 150.2 ( C arom -C)

[0246] <Synthesis Example 11> Synthesis of Compound 11

[0247] [ka]

[0248] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-hydroxybenzenethiol (20.0 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 11 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1445, 1390cm -1 Triazole ring stretching vibration 667cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.36 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 5.02 (s, 1H, -Ph-O H), 6.90 (d, 2H), 7.15 (s, 1H), 7.29 (d, 1H), 7.46 (m, 3H), 7.80 (d, 1H), 8.01 (d, 1H), (insg.9arom. C H ), 11.57 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 114.0, 116.9, 117.7, 119.3, 128.3, 136.5 (CH arom ), 125.4, 141.3, 143.3 (C arom ), 128.7 ( C arom -CH3), 139.1 ( C arom -C(CH3)3), 139.8 ( C arom -S), 139.8 (S - C arom ), 146.7, 156.6 ( C arom -OH)

[0249] <Synthesis Example 12> Synthesis of Compound 12

[0250]

change

[0251] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 2-naphthalenchiol (25.4 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 12 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1444, 1389cm -1 Triazole ring stretching vibration 667cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.36 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 7.16 (s, 1H), 7.39 (d, 1H), 7.51 (m, 3H), 7.72-7.86 (m, 5H), 8.02 (d, 1H), (insg.12arom.C H ), 11.56 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 117.0, 118.0, 119.3, 126.8, 127.6, 127.8, 128.9, 129.4, 131.0, 131.9, 132.8, 133.9 (CH arom ), 125.4, 131.0, 133.9, 141.7, 143.2 (C arom ), 128.3 ( C arom-CH3), 137.2 ( C arom -S), 137.2 (S - C arom ), 139.2 ( C arom -C(CH3)3), 146.7 ( C arom -OH)

[0252] <Synthesis Example 13> Synthesis of Compound 13

[0253] [ka]

[0254] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4,4'-thiobisbenzenethiol (9.0 g, 36.0 mmol), potassium carbonate (10.9 g, 79.2 mmol), and potassium iodide (0.4 g, 2.5 mmol) were reacted in 62.5 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 13 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1444, 1389cm -1 Triazole ring stretching vibration 667cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 18H, -Ph-OH-CH3-C(C H 3)3), 2.37 (s, 6H, -Ph-OH-C H 3-C(CH3)3), 7.17 (s, 2H), 7.32-7.39 (m, 10H), 7.77 (s, 2H), 7.83 (d, 2H), 8.03 (d, 2H), (insg.18arom.C H ), 11.53 (s, 2H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 118.0, 118.2, 119.4, 129.0, 130.2, 131.9, 132.6, 133.6 (CH arom ), 125.3, 141.8, 143.2 (C arom ), 128.4 ( C arom -CH3), 135.3 ( C arom -S), 136.0 (S - C arom ), 139.2 ( C arom -C(CH3)3), 146.8 ( C arom -OH)

[0255] <Synthesis Example 14> Synthesis of Compound 14

[0256]

change

[0257] 2,2-Bis(4-hydroxyphenyl)propane (24.6 g, 107.8 mmol), dimethylcarbamoyl chloride (40.0 g, 323.6 mmol), and sodium hydride (10.4 g, 238.4 mmol) were reacted in 100 g of THF at 60°C for 4 hours. After the reaction was complete, toluene and water were added, followed by acid treatment with hydrochloric acid. The organic layer, washed with water, was removed by distillation under reduced pressure. The resulting liquid was purified by column chromatography to obtain solid intermediate 14-1. Intermediate 14-1 was reacted in 50 g of sulfolane at 240°C for 4 hours. After the reaction was complete, toluene and water were added, followed by washing with water and distillation under reduced pressure to obtain solid intermediate 14-2. The obtained intermediate 14-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours, cooled, and then hydrochloric acid was added and stirred. After washing with water, recrystallization and column purification were performed to obtain 2,2-bis(4-mercaptophenyl)propane.

[0258] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (8.0 g, 25.3 mmol), 2,2-bis(4-mercaptophenyl)propane (3.0 g, 11.5 mmol), potassium carbonate (7.0 g, 50.6 mmol), and potassium iodide (0.3 g, 1.8 mmol) were reacted in 60 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 14 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1380cm -1 Triazole ring stretching vibration 660cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.49 (s, 18H, -Ph-OH-CH3-C(C H 3)3), 1.73 (s, 6H, -S-Ph-C(C H 3)2), 2.37 (s, 6H, -Ph-OH-C H3-C(CH3)3), 7.16 (d, 2H), 7.29 (m, 4H), 7.37 (m, 2H), 7.41 (m, 4H), 7.67 (s, 2H), 7.81 (d, 2H), 8.02 (s, 2H), (insg.18arom. C H ), 11.58 (s, 2H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 30.6 (-S-Ph-C( C H3)2-Ph-S), 5,4 (-Ph-OH-CH3- C (CH3)3), 43.0 (-S-Ph- C (CH3)2-Ph-S), 116.3, 117.9, 119.3, 128.1, 128.8, 129.6, 132.7 (CH arom ), 125.4, 141.5, 143.3 (C arom ), 128.3 ( C arom -CH3), 137.6 ( C arom -S), 137.6 (S - C arom ), 139.2 ( C arom -C(CH3)2), 146.7 ( C arom -OH)

[0259] <Synthesis Example 15> Synthesis of Compound 15

[0260]

change

[0261] Biphenyl-4,4'-diol (20.0 g, 107.4 mmol), dimethylcarbamoyl chloride (39.8 g, 322.0 mmol), and sodium hydride (10.3 g, 236.1 mmol) were reacted in 100 g of THF at 60°C for 4 hours. After the reaction was complete, toluene and water were added, followed by acid treatment with hydrochloric acid. The organic layer, washed with water, was removed by vacuum distillation. The resulting liquid was purified by column chromatography to obtain solid intermediate 15-1. Intermediate 15-1 was reacted in 50 g of sulfolane at 240°C for 4 hours. After the reaction was complete, toluene and water were added, followed by washing with water and vacuum distillation to obtain solid intermediate 15-2. Intermediate 15-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours. After cooling, hydrochloric acid was added and stirred, followed by washing with water, recrystallization, and column chromatography to obtain biphenyl-4,4'-dithiol.

[0262] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (4.6 g, 14.6 mmol), biphenyl-4,4'-dithiol (1.5 g, 6.9 mmol), potassium carbonate (4.0 g, 28.9 mmol), and potassium iodide (0.2 g, 1.2 mmol) were reacted in 60 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 15 was obtained by recrystallization and column purification. FT-IR(KBr): 3000cm -1 :OH stretching vibration 1450, 1380cm -1 Triazole ring stretching vibration 660cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.48 (s, 18H, -Ph-OH-CH3-C(C H 3)3), 2.38 (s, 6H, -Ph-OH-C H CH ), 11.56 (s, 2H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 118.1, 119.3, 128.1, 128.4, 128.9, 130.0, 132.8 (CH arom ), 125.4, 141.7 143.2 (C arom ), 128.4 ( C arom -CH3), 136.9 ( C arom -S), 136.9 (S - C arom ), 139.2 ( C arom -C(CH3)3), 146.8 ( C arom -OH)

[0263] <Synthesis Example 16> Synthesis of Compound 16

[0264] [ka]

[0265] Compound 16 was obtained by adjusting the pH, then filtering, washing with MeOH, washing with water, recrystallization, and column purification. FT-IR(KBr): 2930cm -1:OH stretching vibration 1450, 1391cm -1 :Torion ring telescopic vibration 667cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ 1.40 (m, 4H, CH2(C H 2)2(CH2)2CH-S), 1.49 (S, 9H, -Ph-OH-CH3-C(C H 3)3), 1.54 (m, 2H, C H 2(CH2)2(CH2)2CH-S), 1.83 (m, 2H, CH2(CH2)2CH2C H 2CH-S), 2.06 (m, 2H, CH2(CH2)2C H 2CH2CH-S), 2.38 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 3.29 (m, 1H, CH2CH2CH2C H -S), 7.17 (s, 1H), 7.43 (d, 1H), 7.80 (s, 1H), 7.84 (d, 1H), 8.06 (d, 1H), (insg.5arom. C H ), 11.62 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ 20.9 (-Ph-OH- C H3-C(CH3)3), 25.7 (CH2( C H2)2(CH2)2CH-S), 26.0 ( C H2(CH2)2(CH2)2CH-S), 29.5 (-Ph-OH-CH3-C( C H3)3), 33.1 (CH2(CH2)2( C H2)2CH-S), 35.4 (-Ph-OH-CH3- C (CH3)3), 46.3 (CH2(CH2)2(CH2)2 C HS), 117.2, 117.5, 119.3, 128.3, 128.8 ( C H arom ), 141.5, 143.2 (C arom ), 125.4 ( C arom -N), 131.2 ( C arom -CH3), 136.1 ( C arom -S), 139.1 ( C arom -C(CH3)3), 146.7 ( C arom -OH)

[0266] <Synthesis Example 17> Synthesis of Compound 17

[0267] [ka]

[0268] 500 mL of toluene was mixed with 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (59.2 g, 0.187 mol) and heated to 80°C. Next, aluminum trichloride (50.0 g, 0.375 mol) was added, and the mixture was stirred for 30 minutes. After cooling to room temperature, 500 mL of ice-cold deionized water was slowly added. The aqueous layer was then removed, the organic layer was washed with water, and after being removed by reduced-pressure distillation, recrystallization was performed to obtain intermediate 17-1. The obtained intermediate 17-1 (20.0 g, 0.077 mol), benzenethiol (11.0 g, 0.100 mol), potassium carbonate (23.4 g, 0.169 mol), and potassium iodide (0.9 g, 0.005 mol) were reacted in 80 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing, and then recrystallization and column purification to obtain compound 17. FT-IR(KBr): 2950cm -1 :OH stretching vibration 1459, 1388cm -1 Triazole ring stretching vibration 670cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ2.38 (s, 3H, -Ph-OH-C HC H ), 10.94 (s, 1H, -Ph-O H -CH3) 13 C-NMR (CDCl3100MHz): δ20.5 (-Ph-OH- C H3), 116.8, 118.1, 118.8, 121.0, 128.3, 129.6, 131.3, 132.8 (CH arom ), 124.8, 141.8, 143.4 (C arom ), 129.9 ( C arom -CH3), 137.6 ( C arom -S), 139.2 (S- C arom ), 147.5 ( C arom -OH)

[0269] <Synthesis Example 18> Synthesis of Compound 18

[0270] [ka]

[0271] 5-chloro-2-nitroaniline (150.0 g, 0.869 mol) was added to 42% tetrafluoroboric acid (381.6 g, 1.825 mol) and cooled to 5-10°C. 50% sodium nitrite aqueous solution (119.7 g, 0.869 mol) was added dropwise over 2 hours at 5-10°C. After addition, the mixture was stirred for 1 hour, diethyl ether was added, the crystals were filtered, and then washed to obtain intermediate 18-1.

[0272] 4-tert-octylphenol (130.0 g, 0.630 mol), sodium hydroxide (26.5 g, 0.663 mol), and sodium carbonate (35.4 g, 0.334 mol) were added to 850 mL of methanol and 450 mL of deionized water and mixed. Intermediate 18-1 (171.0 g, 0.630 mol), dissolved in 3240 mL of deionized water, was added dropwise over 4 hours at 5-10°C. After addition, the mixture was stirred for 1 hour, and after acid treatment, the precipitated crystals were filtered and washed to obtain intermediate 18-2.

[0273] Intermediate 18-2 (75.0 g, 0.192 mol), 2M NaOH aqueous solution (288.5 g), and zinc powder (150.99 g) were added to 400 mL of toluene and stirred at 85°C for 2 hours. After the reaction was complete, the mixture was filtered, washed, and recrystallized to obtain intermediate 18-3.

[0274] Intermediate 18-3 (5.0 g, 0.014 mol), 4-tert-butylbenzenethiol (3.5 g, 0.021 mol), potassium carbonate (4.3 g, 0.031 mol), and potassium iodide (0.2 g, 0.001 mol) were reacted in 50 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Intermediate 18-4 was obtained by recrystallization and column purification.

[0275] Intermediate 18-4 (0.20 g, 0.410 mmol), aqueous formalin solution (0.05 g, 0.615 mmol), and diethylamine (0.05 g, 0.697 mmol) were added to 25 mL of 1-butanol and reacted at 150°C for 17 hours. After the reaction was complete, intermediate 18-5 was obtained by column purification.

[0276] Intermediate 18-4 (1.00 g, 2.052 mmol), intermediate 18-5 (1.34 g, 2.341 mmol), and 28% sodium methylate MeOH solution (1.33 g) were added to 25 mL of xylene and reacted in an autoclave at 175°C for 15 hours. After the reaction was complete, compound 18 was obtained by column purification. FT-IR(KBr): 2953cm-1 :OH stretching vibration 1460, 1389cm -1 :Torion Ring Telescopic Vibration 670cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ0.68 (s, 18H, -Ph-OH-CCH2C(C H 3)3), 1.35 (s, 18H, -S-Ph-C(C H 3)3), 1.36 (s, 12H, -Ph-OH-C(C H 3)2CH2C(CH3)3), 1.70 (s, 4H, -Ph-CC H 2C), 4.26 (s, 2H, -Ph-OH-C H 2-OH-Ph-), 7.34 (m, 2H), 7.37 (m, 2H), 7.43 (d, 8H), 7.63 (s, 2H), 7.80 (d, 2H), 8.02 (d, 2H), (insg.18arom. C H ), 11.36 (s, 2H, -Ph-O H ) 13 C-NMR (CDCl3100MHz): δ30.9 (-Ph-OH- C H2-OH-Ph-), 31.3 (-S-Ph-C( C H3)3), 31.7 (-Ph-OH-C( C H3)2CH2C(CH3)3), 31.8 (-Ph-OH-C(CH3)2CH2C( C H3)3), 32.3 (-Ph-OH-C(CH3)2CH2 C (CH3)3), 34.7 (-S-Ph- C (CH3)3), 38.2 (-Ph-OH- C (CH3)2CH2C(CH3)3), 56.6 (-Ph-OH-C(CH3)2 C H2C(CH3)3), 115.9, 116.5, 117.9, 126.7, 129.4, 129.6, 133.0 (CH arom ), 124.4, 141.6, 143.4 (C arom ), 129.3 (C arom -CH2), 129.9 ( C arom -S), 138.1 (S - C arom ), 141.4 ( C arom -C(CH3)3), 145.6 ( C arom -OH), 151.8 ( C arom -C(CH3)2)

[0277] <Synthesis Example 19> Synthesis of Compound 19

[0278] [ka]

[0279] Compound 19 was obtained by reacting 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.0 g, 0.158 mol), octanthiol (46.3 g, 0.316 mol), potassium carbonate (48.1 g, 0.348 mol), and potassium iodide (1.8 g, 0.011 mol) in 125 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing, and then recrystallization. FT-IR(KBr): 2956cm -1 :OH stretching vibration 1445, 1392cm -1 Triazole ring stretching vibration 662cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ 0.89 (t, 3H, C H 3(CH2)7-S) , 1.33 (m, 8H, CH3(C H 2)4(CH2)3-S), 1.49 (m, 11H, -Ph-OH-CH3-C(C H 3)3, CH3(CH2)4C H 2(CH2)2-S), 1.73 (quin, 2H, CH3(CH2)5CH 2CH2-S), 2.38 (s, 3H, -Ph-OH-C H 3-C(CH3)3), 3.02 (t, 2H, CH3(CH2)5CH2C H 2-S), 7.16 (s, 1H), 7.36 (d, 1H), 7.69 (s, 1H), 7.78 (d, 1H), 8.04 (s, 1H), (insg.5arom. C H ), 11.62 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3 100MHz): δ 14.0 ( C H3(CH2)7-S), 20.9 (-Ph-OH- C H3-C(CH3)3), 22.6 (CH3 C H2(CH2)5CH2-S), 28.7 (CH3CH2( C H2)4CH2CH2-S), 29.5 (-Ph-OH-CH3-C( C H3)3), 31.8 (-Ph-OH-CH3- C (CH3)3), 33.8 (CH3(CH2)5 C H2CH2-S), 35.4 (CH3(CH2)5CH2 C H2-S), 113.6, 117.5, 119.3, 128.7, 129.2 ( C H arom ), 125.4, 141.2, 143.4 ( C arom ), 128.3 ( C arom -CH3), 138.0( C arom -S), 139.1( C arom -C(CH3)3), 146.7( C arom -OH)

[0280] <Synthesis Example 20> Synthesis of Compound 20

[0281]

Chemical Structure

[0282] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (20.0 g, 63.3 mmol), benzyl mercaptan (15.7 g, 126.6 mmol), potassium carbonate (19.3 g, 139.4 mmol), and potassium iodide (0.74 g, 4.5 mmol) were reacted in 50.0 g of DMF at 125°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing, and then recrystallization to obtain compound 20. FT-IR(KBr): 2960cm -1 :OH stretching vibration 1441, 1392cm -1 Triazole ring stretching vibration 664cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.49 (s, 9H, -Ph-OH-CH3-C(C H 3)3), 2.38 (s, 3H, -Ph-OH-C H 3-C(CH3)3) , 4.24 (s, 2H, Ph-C H 2-S-) , 7.16 (s, 1H), 7.26~7.38 (m, 6H), 7.72 (s, 1H), 7.80 (d, 1H), 8.04 (d, 1H), (insg.10arom. CH), 11.58 (s, 1H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 29.5 (-Ph-OH-CH3-C( C H3)3), 35.4 (-Ph-OH-CH3- C (CH3)3), 38.6 (Ph- C H2-S-), 115.4, 117.6, 119.3, 128.7, 128.8, 128.8, 129.7, 137.0( C Harom ), 125.4, 141.4, 143.4 ( C arom ), 128.3 ( C arom -CH3), 136.5( C arom CH2-S-), 138.7(S- C arom ), 139.1( C arom -C(CH3)3), 146.7( C arom -OH)

[0283] <Synthesis Example 21> Synthesis of Compound 21

[0284] [ka]

[0285] 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (10.0 g, 31.7 mmol), hexanedithiol (4.76 g, 31.7 mmol), potassium carbonate (8.75 g, 63.3 mmol), and potassium iodide (0.37 g, 2.2 mmol) were reacted in 50 g of DMF at 130°C for 12 hours. After the reaction was complete, the pH was adjusted, followed by filtration, MeOH washing, and water washing. Compound 21 was obtained by recrystallization and column purification. FT-IR(KBr): 3009cm -1 :OH stretching vibration 1431, 1391cm -1 Triazole ring stretching vibration 656cm -1 :CS stretching vibration 1 H-NMR (CDCl3400MHz): δ1.49 (s, 18H, -Ph-OH-CH3-C(C H 3)3), 1.55 (m, 4H, -S-CH2CH2C H 2C H 2CH2CH2-S-), 1.77 (m, 4H, -S-CH2C H 2CH2CH2CH 2CH2-S-), 2.38(s, 6H, (-Ph-OH-C H 3-C(CH3)3), 3.04 (t, 4H, -SC H 2CH2CH2CH2CH2C H 2-S-), 7.16 (s, 2H), 7.37 (d, 2H), 7.70 (s, 2H), 7.81 (d, 2H), 8.05 (s, 2H) (insg.10arom. CH), 11.60 (s, 2H, -Ph-O H -CH3-C(CH3)3) 13 C-NMR (CDCl3 100MHz): δ20.9 (-Ph-OH- C H3-C(CH3)3), 28.4 (-Ph-OH-CH3- C (CH3)3), 28.6 (-S-CH2CH2 C H2 C H2CH2CH2-S-), 29.5 (-Ph-OH-CH3-C( C H3)3), 33.1 (-S-CH2 C H2CH2CH2 C H2CH2-S-), 35.4 (-S- C H2CH2CH2CH2CH2 C H2-S-), 113.7, 117.6, 119.3, 128.3, 129.3 ( C H arom ), 141.2, 143.4 ( C arom ), 125.4( C arom -N), 128.3 ( C arom -CH3), 137.7( C arom -S), 139.1( C arom -C(CH3)3), 146.7( C arom -OH)

[0286] 1. Evaluation of the optical properties of UV absorbers and the lightfastness of organic resin compositions containing UV absorbers. <1> Optical properties of UV absorbers The ultraviolet absorber compounds 1-12, 16, 17, and 19 were dissolved in chloroform at a concentration of 100 μM, and compounds 13-15, 18, 21, and 22 were dissolved at a concentration of 50 μM. These solutions were then placed in a 10 mm quartz cell, and their absorption spectra were measured using a UV-Vis spectrophotometer (JASCO V-550) (Figures 1-4).

[0287] The absolute value of the slope on the longer wavelength side of the absorption peak in the 350-390 nm wavelength range was determined by using the following formula (Table 3), with the peak end defined as the intersection point of the long-wavelength absorption spectrum of the absorption peak of each compound and the baseline (the line where the slope of the absorption spectrum in the 400-500 nm range is 0) (e.g., Figure 1). |The slope on the longer wavelength side of the absorption peak in the 350-390nm wavelength range| = |(Absorbance at the peak end - Absorbance of the absorption peak in the 350-390nm wavelength range) / (Absorbance wavelength at the peak end - Wavelength of the absorption peak in the 350-390nm wavelength range)|

[0288] Furthermore, the molar extinction coefficient is the absorption peak in the wavelength region of 350-390 nm (maximum absorption wavelength: λ max The absorbance of ) was read and calculated using the following formula (Table 4). Molar extinction coefficient: ε max (L / (mol·cm)=A: absorbance / [c: molar concentration (mol / L) × l: optical path length of cell (cm)]

[0289] Because all of compounds 1 to 18 have either a thioaryl ring group or a thiocyclohexyl ring group, compared to the common long-wavelength absorbing type UV absorber 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole (absorption peak: 353.5 nm, slope: 0.0219) and Comparative Example 1 (compound 22, TINUVIN360, manufactured by Ciba Specialty Chemicals Co., Ltd.), they exhibit superior UV absorption ability in the long-wavelength region, with absorption peaks at the maximum absorption wavelength between 360 and 375 nm. The absolute value of the slope on the long-wavelength side of the absorption peak is 0.030 or higher, and in particular, the slopes of compounds 1, 2, 3, 6, 8, 10, 11, 12, and 13 are 0.040 or higher, and furthermore, the slopes of compounds 2, 3, 6, 8, and 12 are 0.042 or higher, suggesting a high yellow suppression effect on films and transparent materials.

[0290] Regarding the molar extinction coefficient, compounds 1-12, 16, and 17 of formulas (1) and (2) had a coefficient of 20,000 L / (mol·cm) or higher, confirming that they can efficiently absorb long-wavelength ultraviolet light in small amounts compared to 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole (15,300 L / (mol·cm)). In particular, compounds 13-15 and 18 of formulas (3) and (4), which have two 2-phenylbenzotriazole skeletons, had a coefficient of 40,000 L / (mol·cm) or higher, demonstrating superior effectiveness compared to comparative example 22 (33,700 L / (mol·cm)) which does not have a thioaryl ring group.

[0291] Furthermore, the absorption spectra in Figures 1-4 suggest that, compared to the reference example compounds 19 and 21, the UV absorbers compounds 1-15, 17, and 18 of formulas (1), (3), and (4) exhibit a larger overall absorption peak in the 250-330 nm region (higher absorbance) due to the introduction of phenyl ring residues and naphthyl ring residues to the thioaryl ring group. This allows them to absorb UV light over a wide range from low to long wavelengths, suggesting high effectiveness in suppressing quality degradation of materials and UV absorbers, and preventing health hazards. <2> Preparation of lightfastness evaluation samples for UV absorbers (organic resin compositions containing UV absorbers) Compounds 1-16 and 19-21 were dissolved in a 20 wt% acrylic resin (paraloid B72) toluene solution in the following mass ratios, taking into account the solubility of the compounds. The mixture was then coated onto soda glass and dried at 80°C for 10 minutes to obtain evaluation samples. ·Compounds 1~6,8~11,16,19,20 Mixing ratio (mass ratio) 20 wt% acrylic resin toluene solution:compound = 3.0:0.1 (Acrylic resin:compound = 0.6:0.1) Dry film thickness: 2-3 μm ·Compound 7,12 Mixing ratio 20 wt% acrylic resin toluene solution:compound = 6.0:0.1 (Acrylic resin:compound = 1.2:0.1) Dry film thickness: 4-6 μm ·Compound 13 Mixing ratio (mass ratio) 20 wt% acrylic resin toluene solution:compound = 12.0:0.1 (Acrylic resin:compound = 2.4:0.1) Dry film thickness: 7-9 μm ·Compounds 14,15,21 Mixing ratio (mass ratio) 20 wt% acrylic resin toluene solution:compound = 17.0:0.1 (Acrylic resin:compound = 3.4:0.1) Dry film thickness: 50 μm <3> Evaluation of lightfastness of UV absorbers (organic resin compositions containing UV absorbers) For the obtained evaluation samples, the ultraviolet-visible transmission spectrum was measured using a UV-Vis spectrophotometer (Hitachi U-3310), and the initial (pre-irradiation) ultraviolet transmittance (T1uv:%) at 380, 390, and 400 nm was read. Then, using an ultraviolet irradiation device (Suga Xenon Weather Meter X25FL-Z), the wavelength was 300-400 nm and the irradiance was 42 W / m². 2Under conditions of a black panel temperature of 63°C, ultraviolet light was irradiated, and the ultraviolet-visible transmission spectra were measured after 70 and 140 hours of irradiation. The transmittance (T2uv:%) at 380, 390, and 400 nm derived from the ultraviolet absorber was read, and the difference in transmittance ΔTuv(%) was calculated using the following formula to evaluate the light resistance of the ultraviolet absorber (Tables 1A and 1B).

[0292]

number

[0293] When UV absorbers do not degrade in UV absorption capacity (there is no decrease in UV absorption capacity) and have excellent light resistance, ΔTuv becomes smaller. The ΔTuv values ​​for irradiation times of 70 and 140 hours in Tables 1A and 1B were evaluated using the following criteria, from ◎ to × (Tables 2A and 2B). ◎ : ΔTuv=0~2.0 ○ : ΔTuv=2.1~4.0 △ : ΔTuv=4.1~6.0 × : ΔTuv=6.1~

[0294] Furthermore, the scores from ◎ to × were assigned to a scale of 0 to 3, and the scores for each compound's irradiation time (70 and 140 hours) were added together (S(70h), S(140h)). ◎ : 3 ○ : 2 △ : 1 × : 0

[0295] Compounds 1-12 of formula (1) (Examples 1-12) had S(70h) values ​​of 1-9, while compound 19 (Reference Example 1) where the X of the thioalkoxy group (-SX) is an alkyl group rather than an aryl ring residue, and compound 20 (Reference Example 2) where the phenyl ring residue is not directly bonded to a sulfur atom, had an S(70h) value of 0. Similarly, compounds 13-15 of formula (3) (Examples 13-15) had S(70h) values ​​of 4-9, while compound 21 of Reference Example 3 had an S(70h) value of 3, where the X of the aryl ring residue (X) 1a , X 1c , X 2cThe ultraviolet absorber of the present invention, in which the ) is directly bonded to the sulfur atom, was suggested to exhibit excellent lightfastness. The ultraviolet absorbers of formulas (1), (3), and (4) are thought to have exhibited high lightfastness due to the π-electron interaction between the phenyl and naphthyl ring residues of the aromatic aryl ring directly bonded to the sulfur atom and the 2-phenylbenzotriazole skeleton. Furthermore, compound 16 (S(70h):6) of formula (2) also showed good lightfastness compared to the reference example compounds 19-21 (S(70h):0-3).

[0296] Also, X 1a Compound 1, which has a phenyl ring residue, had S(70h)=9, while compound 12, which has a naphthyl ring, had S(70h)=2, indicating that compounds with a phenyl ring residue showed a favorable trend.

[0297] R 1a When comparing R 1a Compounds having alkoxy groups (compound 4: S(70h)=8, S(140h)=6) and hydrocarbon groups (compounds 2, 3, 5~10: S(70h)=4~9, S(140h)=0~6) rather than hydroxyl groups (compound 11: S(70h)=1, S(140h)=0) exhibited superior lightfastness. In particular, at l=0, X 1a Compound 1 (S(70h)=9, S(140h)=9), in which all substituents are hydrogen atoms, exhibited high lightfastness.

[0298] Also, in equation (1), X 1a When the residue was a phenyl ring, the following trend was observed. · l=1~3, R 1a However, compounds 2, 5, 6, 7, 8, and 10, which have at least one branched alkyl group with 3 to 8 carbon atoms, showed a difference in transmittance of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher photoresistance than compounds 19 and 20 (reference examples 1 and 2) with similar structures.

[0299] l=1, R 1a is a linear or branched alkyl group, Compounds 2, 5, 6, 7, and 9, with alkyl groups having 1 to 18 carbon atoms, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 2, 5, 6, 7, and 9, which have alkyl groups with 1 to 10 carbon atoms, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 2, 5, 6, 7, and 9, which have 1 to 8 carbon atoms in the alkyl group, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 2, 5, 6, and 7, with alkyl groups having 2 to 8 carbon atoms, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a transmittance difference of 6.0 or less at two wavelengths of 380, 390, and 400 nm after 140 hours of irradiation, demonstrating higher light resistance than compound 9 and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compounds 2, 5, 6, and 7, which have 3 to 8 carbon atoms in the alkyl group, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a transmittance difference of 6.0 or less at two wavelengths of 380, 390, and 400 nm after 140 hours of irradiation. They exhibited higher light resistance than compound 9 and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compounds 2, 5, and 6, which have 3 to 5 carbon atoms in the alkyl group, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 140 hours of irradiation, demonstrating higher light resistance than compounds 7 and 9, and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compounds 2 and 5, with alkyl groups having 4 to 5 carbon atoms, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a transmittance of 6.0 or less at one wavelength of 380, 390, and 400 nm, and a transmittance difference of 4.0 or less at two wavelengths after 140 hours of irradiation. These compounds exhibited higher light resistance than compounds 6, 7, and 9, and compounds 19 and 20 with similar structures (Reference Examples 1 and 2). Compound 2, with four carbon atoms in the alkyl group, showed a transmittance difference of 2.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 140 hours of irradiation, demonstrating higher light resistance than compounds 5, 6, 7, and 9, and compounds 19 and 20 with similar structures (Reference Examples 1 and 2).

[0300] Also, l=1, R 1a Compounds 2, 5, 6, and 7, which are alkyl groups having tertiary and / or quaternary carbon atoms, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compound 9 and compounds 19 and 20 (Reference Examples 1 and 2) with similar structures.

[0301] l=2, R 1a is a linear or branched alkyl group, Compounds 3, 8, and 10, each with 1 to 18 carbon atoms in the alkyl group, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 3, 8, and 10, each with 1 to 10 carbon atoms in the alkyl group, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 3, 8, and 10, each with 1 to 5 carbon atoms in the alkyl group, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2) with similar structures. Compounds 3 and 8, each with 1 to 4 carbon atoms in the alkyl group, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compound 10 and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compound 3, with each alkyl group having one carbon atom, showed a transmittance difference of 2.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 8 and 10, and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compounds 3, 8, and 10, with alkyl groups having a total of 2 to 12 carbon atoms, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 3, 8, and 10, with a total of 2 to 10 C1 / C1 alkyl groups, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 19 and 20 (Reference Examples 1 and 2), which have similar structures. Compounds 3 and 8, with a total of 2 to 5 C1 / C1 alkyl groups, showed a transmittance difference of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compound 10 and compounds 19 and 20 (reference examples 1 and 2) with similar structures. Compound 3, which has a total of 2 carbon atoms in the alkyl group, showed a transmittance difference of 2.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 8 and 10, and compounds 19 and 20 with similar structures (Reference Examples 1 and 2).

[0302] The compound of formula (3) showed the following trend. ·q=1, A 2c Compound 13, in which the group is a sulfide group, showed a transmittance difference of 2.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher light resistance than compounds 15 and 21 (Reference Example 3), which have similar structures. ·q=1, A 2cCompound 14, whose carbon atom is a hydrocarbon group having 1 to 8 carbon atoms, showed a difference in transmittance of 2.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, and a difference in transmittance of 4.0 or less at all wavelengths of 380, 390, and 400 nm after 140 hours of irradiation, demonstrating higher light resistance than compounds 13, 15, and compound 21 (Reference Example 3), which have similar structures. Compound 15, with q=0, showed a transmittance difference of 6.0 or less at all wavelengths of 380, 390, and 400 nm after 70 hours of irradiation, demonstrating higher photoresistance than compound 21 (Reference Example 3), which has a similar structure.

[0303] The UV absorber of the present invention suppresses the degradation of organic resins from ultraviolet light. However, due to the excellent light resistance of the UV absorber, it has been suggested that organic resin compositions containing this UV absorber can absorb long wavelengths while suppressing yellowing and degradation for a long period of time from the initial stage.

[0304] 2. Evaluation of the melting point of UV absorbers The melting points of compounds 1-21 were measured using a differential scanning calorimeter (DSC6220, SII Corporation), and the DSC peak top temperature was defined as the melting point (Tables 1A and 1B). The melting point of compound 17 was 114°C, and the melting point of compound 18 was 176°C.

[0305] Compounds 1 to 18 of the present invention all have a melting point of 100°C or higher. Compounds 1 to 3, 5 to 12, 14 to 16, and 18 have a melting point of 130°C or higher, compounds 2, 5 to 9, 11, 12, 14 to 16, and 18 have a melting point of 140°C or higher, and compounds 2, 6 to 8, 11, 12, 14, 15, and 18 have a melting point of 145°C or higher. In particular, compounds 2, 11, 12, 14, 15, and 18 have a melting point of 150°C or higher, and were confirmed to have excellent properties in suppressing bleed-out and blocking, dispersion, and heat processability.

[0306] In equation (1), l=1, and R is at the para position relative to the -S- bond of the thioalkoxy group. 1a Compounds 2, 5, 6, 7, 9 (melting point 140~155°C) having a hydrocarbon group (alkyl group) are R 1a Compound 1 (melting point 136°C) consists entirely of hydrogen atoms, and R1a Compound 4 (melting point 115°C) has a higher melting point than compound 4 (melting point 115°C), and among these, compounds 2, 5, 6, and 7 (melting points 141-155°C) with 3-8 C1 alkyl groups have a higher melting point than compound 9 (melting point 140°C) with 1 C1. Furthermore, compounds 2 and 6 (melting points 148-155°C) with 3-4 C1 alkyl groups have a higher melting point than compounds 5, 7, and 9 (melting points 141, 146, 140°C) with 1, 5, and 8 C1 groups. Compound 2 (with 4 C1) in particular showed a tendency to have a high melting point.

[0307] Compounds 1-12, which have a thioaryl ring group introduced into formula (1), are different from compound 19, which has a thioalkyl group, in terms of formula (3) A 1c Introducing A for q=0 and q=1 2c Compounds 14 and 15, which have a hydrocarbon group, are A 1c Compound 21, which contains an alkylene group, tended to have a higher melting point.

[0308] Also, R is available when l=1 or 2. 1a Compounds with hydrocarbon groups 2,3,5~10 (melting point 131~155℃), R 1a All of them are hydrogen atoms in compound 1 (melting point 136°C) and R 1a Compared to compound 4 with an alkoxy group (melting point 115°C), R 1a Compounds 11 (melting point 208°C), 14 (melting point 196°C), 15 (melting point 236°C), and X are hydroxyl group compounds. 1a Compounds 12 (melting point 161°C) and 18 (melting point 176°C), which contain naphthyl groups, have high melting points and are particularly useful in terms of bleed-out and processability. Furthermore, as described in Patent Document 2 (International Publication No. 2016 / 021664), compound 11 is R 1a If the polymer raw material has a hydroxyl group, which is a reactive functional group, and the polymer has a functional group that reacts with that hydroxyl group, the hydroxyl group will react with the polymer, become immobilized in the resin, and suppress bleed-out over time.

[0309] [Table 1A]

[0310] [Table 1B]

[0311] [Table 2A]

[0312] [Table 2B]

[0313] [Table 3]

[0314] [Table 4]

[0315] 3. Evaluation of the transparency (compatibility between UV absorber and organic resin) of organic resin compositions containing UV absorbers. The transparency of the organic resin composition due to the compatibility of the compound of the present invention with organic resins was confirmed (Table 5).

[0316] Various materials were used to create polymers of thermoplastic resins to which the product of the present invention was added. These included polymethyl methacrylate resin film (acrylic) as a (meth)acrylic resin, polyethylene terephthalate film (PET) as an ester resin, polycarbonate film (PC) as a polycarbonate resin, and polystyrene film (PS) as a styrene resin. The polymers of thermoplastic resins included acrylonitrile-butadiene-styrene copolymer film (ABS resin) as an acrylonitrile-butadiene-styrene copolymer. The polymers of thermosetting resins included urea resin film as a urea resin polymer, melamine resin film as a melamine resin polymer, and acrylic melamine resin film as an acrylic melamine polymer.

[0317] (Preparation of polymethyl methacrylate resin film) Polymethyl methacrylate resin films with a thickness of 100-150 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, respectively, using the following procedure.

[0318] 0.0062 g each of compounds 1, 2, 6, 9, and 17 were dissolved in 1.00 g of a toluene solution of 20 wt% polymethyl methacrylate resin. 0.2 mL of each solution was then spread onto a 1.5 × 1.5 cm glass slide, and dried at 80°C for 10 minutes to obtain a polymethyl methacrylate resin film.

[0319] Furthermore, a comparative blank film was prepared using 1.00 g of a toluene solution of 20 wt% polymethyl methacrylate resin, without any additives, by the same procedure as described above.

[0320] (Polyethylene terephthalate film: PET production) Polyethylene terephthalate films with a thickness of 40-100 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0321] A polyethylene terephthalate film was obtained by kneading 0.2 g of polyethylene terephthalate chips with 0.0062 g each of compounds 1, 2, 6, 9, and 17 at 280°C, coating this mixture onto a glass slide substrate, quickly stretching it, and then air-cooling it.

[0322] Furthermore, a comparison blank film was prepared using the same procedure as described above, without adding any additives.

[0323] (Polycarbonate film: PC manufacturing) Polycarbonate films with a thickness of 100-200 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0324] A polycarbonate film was obtained by kneading 0.2 g of polycarbonate chips with 0.0062 g each of compounds 1, 2, 6, 9, and 17 at 280°C, coating this mixture onto a glass slide substrate, quickly stretching it, and then air-cooling it.

[0325] Furthermore, a comparison blank film was prepared using the same procedure as described above, without adding any additives.

[0326] (Production of polystyrene film: PS) Polystyrene films with a thickness of 100-200 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0327] 0.0062 g each of compounds 1, 2, 6, 9, and 17 were dissolved in 1.00 g of a toluene solution of 20 wt% polystyrene resin. 0.2 mL of each solution was then spread onto a 1.5 × 1.5 cm glass slide, and dried at 80°C for 10 minutes to obtain a polystyrene film.

[0328] Furthermore, a comparative blank film was prepared using 1.00 g of a toluene solution of 20 wt% polystyrene resin, without any additives, by the same procedure as described above.

[0329] (Acrylonitrile-butadiene-styrene copolymer film: Preparation of ABS resin) Acrylonitrile-butadiene-styrene copolymer films with a thickness of 100-200 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0330] 0.0062 g each of compounds 1, 2, 6, 9, and 17 were dissolved in 1.00 g of a 20 wt% ABS resin THF solution. 0.2 mL of each solution was then spread onto a 1.5 × 1.5 cm glass slide, and dried at 80°C for 10 minutes to obtain an acrylonitrile-butadiene-styrene copolymer film.

[0331] Furthermore, a comparative blank film was prepared using 1.00 g of a 20 wt% ABS resin THF solution, without any additives, by the same procedure as described above.

[0332] (Preparation of urea resin film) Urea resin films with a thickness of 50-100 μm were prepared by adding 0.1 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0333] A monomer solution was prepared by dissolving 1 mL of 37 wt% formaldehyde solution, 0.25 g of urea, and 0.16 g of ammonium acetate. Next, 0.0007 g of compounds 1, 2, 6, 9, and 17 were dissolved in 2 mL of THF, respectively, and then homogeneously mixed with 1 mL of the monomer solution. 0.2 mL of this mixture was then spread onto a 1.5 × 1.5 cm glass slide. The glass slide was then placed in an oven and heated from room temperature to 150°C over 30 minutes, followed by a reaction at 150°C for 5 hours.

[0334] Furthermore, a comparative blank film was prepared by uniformly mixing 0.1 mL of monomer solution and 0.2 mL of THF without adding any additives, and performing the same procedure as described above. (Preparation of melamine resin film) Melamine resin films with a thickness of 10 to 50 μm were prepared by adding 0.1 wt% of each of compounds 1 and 2 from Examples 19 to 23, respectively, using the following procedure.

[0335] A hexamethylolmelamine solution was prepared by adding 1 g of melamine and 24.60 g of water to 5.15 g of formaldehyde solution, which had been adjusted to pH 7.5 with sodium hydroxide, and heating the mixture. Next, 0.0019 g each of compounds 1, 2, 6, 9, and 17 were dissolved in 1 mL of THF, and these were uniformly mixed with 2 mL of the hexamethylolmelamine solution. 0.2 mL of this mixture was then spread onto a 1.5 × 1.5 cm glass slide. The glass slide was then placed in an oven and heated from room temperature to 150°C over 30 minutes, followed by a reaction at 150°C for 5 hours.

[0336] Furthermore, a comparative blank film was prepared by uniformly mixing 0.2 mL of monomer solution and 0.1 mL of THF without adding any additives, and performing the same procedure as described above. (Preparation of acrylic melamine resin film) Acrylic melamine resin films with a thickness of 100-150 μm were prepared by adding 3.0 wt% of each of compounds 1, 2, 6, 9, and 17 from Examples 19-23, according to the following procedure.

[0337] 0.0020 g of each compound from Examples 1, 2, 6, 9, and 17 was dissolved in 0.1 mL of THF, and then uniformly mixed with 0.1 g (65% effective content) of bake-dry topcoat paint (Baked-dry topcoat (acrylic melamine monomer): Acrysite UB-63 Clear, manufactured by Saito Paint Co., Ltd.). 0.2 mL of this mixture was then applied to a 1.5 × 1.5 cm glass slide. The glass slide was then placed in an oven and heated from room temperature to 150°C over 30 minutes, after which it was reacted at 150°C for 2 hours to prepare the sample.

[0338] Furthermore, a comparative blank film was prepared by uniformly mixing 0.1 g of acrylic melamine monomer and 0.1 mL of THF without adding any additives, and performing the same procedure as described above.

[0339] (exterior) The film's appearance was visually inspected and evaluated according to the following criteria. Evaluation criteria (polymethyl methacrylate resin film, PS film, ABS resin film) ○: Transparent, similar to the comparison blank. ×: Shows cloudiness compared to the comparison blank. Evaluation criteria (PET film, PC film) ○: Transparent, similar to the comparison blank. ×: Cloudy compared to the comparison blank. Evaluation criteria (urea resin film, melamine resin film, acrylic melamine resin film) ○: Transparent, similar to the comparison blank. ×: Crystal precipitation observed compared to the comparison blank.

[0340] Table 5 confirms that the compounds of the present invention exhibit good compatibility with any resin, resulting in the production of transparent organic resin compositions.

[0341] [Table 5]

[0342] 4. Evaluation of the elution (bleed-out) of UV absorbers from organic resin compositions. In the compounds of the present invention and the organic resin compositions described in section 3 above, the elution properties of the compounds (ultraviolet absorbers) from the resin were evaluated using compounds 1, 2, 6, 9, and 17 by the following procedure (Table 6).

[0343] A resin solution prepared using the same procedure as in 3. above was spread at a rate of 0.8 mL onto a 1.5 × 6.0 cm glass slide. Each prepared film / slide (using the same procedure as in 3. above) was immersed in 80 mL of heptane and left to stand in a 60°C constant temperature bath for 6 hours. The films / slides were then removed, the heptane was removed by reduced pressure distillation, and the resulting eluate was dissolved in THF and quantified by HPLC (High-Performance Liquid Chromatography, Thermo Fisher Scientific UltiMate3000).

[0344] The appearance of the film after testing was observed visually and evaluated according to the following criteria. Evaluation Criteria ○: Has the same level of transparency as before the test. △: Slightly cloudier compared to before the exam. ×: It's much cloudier compared to before the exam.

[0345] Table 6 shows that the elution amounts for the thermoplastic resins / polymers containing compounds 1, 2, 6, 9, and 17 of the present invention—polymethyl methacrylate resin film (meth)acrylic resin, polyethylene terephthalate film (ester resin), polycarbonate film (polycarbonate resin), polystyrene film (styrene resin), ABS resin film (acrylonitrile-butadiene-styrene copolymer), urea resin film (urea resin), and melamine resin film (melamine resin)—were 10.0 wt% or less, and the results were good with no significant deterioration in appearance after testing. Furthermore, among the thermoplastic resins / polymers, polymethyl methacrylate resin film, polyethylene terephthalate film, and polycarbonate, and among the thermosetting resins / polymers, urea resin film, showed particularly good results with elution amounts of less than 1.0 wt%. On the other hand, the acrylic melamine resin film (thermosetting resin / polymer) showed cloudiness after testing, with an elution amount of over 95% confirmed.

[0346] The results above suggest that, in particular, organic resin compositions such as thermoplastic resins / polymers, thermoplastic resins / copolymers, and thermosetting resins / polymers containing the compound of the present invention have excellent appearance, suppress elution due to bleed-out, etc., during dispersion, heat processing, and long-term use, and can maintain ultraviolet absorption capacity for a long period of time.

[0347] These thermoplastic resins / polymers can be classified into crystalline resins (e.g., polyethylene terephthalate) and amorphous resins (polymethyl methacrylate resin, polycarbonate, polystyrene). Among both crystalline and amorphous resins, we confirmed that resins with high molecular orientation (polymethyl methacrylate resin, polycarbonate) have aromatic rings in their side chains and exhibit a higher elution suppression effect than resins with low molecular orientation (polystyrene).

[0348] [Table 6]

[0349] 5. Evaluation of the heat resistance of UV absorbers The heat resistance of the UV absorbers was evaluated by the weight change rate due to thermal decomposition. 5g each of compounds 2, 6, 9, 1, and 19, dried in a vacuum dryer at 50°C for 12 hours, were weighed into 30mL screw-cap tubes, and their weights were measured. The screw-cap tubes containing the compounds were placed in a constant-temperature oven set at 120°C, and changes in appearance and weight change rates were checked after 24, 48, 72, 100, and 300 hours. Changes in appearance were evaluated according to the following criteria. The weight change rate was calculated using the formula [((weight before heating - weight after heating) / weight before heating) × 100], after measuring the weight before and after heating using an electronic balance.

[0350] Next, heat resistance evaluations were performed under conditions of 80°C and 160°C. Similar to the above, 5g each of compounds 2, 6, 9, and 1, dried in a vacuum dryer at 50°C for 12 hours, were weighed into 30mL screw-cap tubes, their weights were measured, and the screw-cap tubes were placed in a constant-temperature oven set to 80°C. The changes in appearance and weight after 300 hours were observed. Furthermore, the same procedure was followed, placing the tubes in a constant-temperature oven set to 160°C, and the changes in appearance and weight after 6, 12, and 24 hours were observed. The changes in appearance were evaluated according to the following criteria. Evaluation Criteria 120°C heat resistance evaluation ○; Appearance change: No change △; Appearance change: Pale yellow ×; Appearance change: yellow 160℃ heat resistance evaluation ◎; Appearance change: No change ○; Appearance change: pale yellow △; Appearance change: Yellow ×; Appearance change: Black

[0351] In a heat resistance test at 80°C for 300 hours, compounds 2, 6, 9, and 1 showed no discoloration. No weight change was observed either. As shown in Table 7, after heating at 120°C for 48 hours, compound 19 of the reference example turned pale yellow, but compounds 2, 6, 9, and 1 of the present invention's examples did not discolor. This confirms that the heat resistance of the compounds of the present invention, which have a thioaryl ring group, is superior to that of compound 19 of the reference example.

[0352] Next, the effect of substituents on the thioaryl ring group was evaluated under 160°C conditions, as shown in Table 8. Compounds 2, 6, and 9 (6h: no change to yellow), which have alkyl groups on the thioaryl ring group, showed less change in appearance over a longer period of time and had superior heat resistance compared to compound 1 (6h: black), which does not have an alkyl group on the thioaryl ring group. Furthermore, compounds 2 and 6 (6h: no change, 12h: no change to pale yellow), which have three and four C1 alkyl groups, showed higher heat resistance than compound 9 (6h: yellow, 12h: yellow), which has one C1 alkyl group. In particular, compound 2 (12h: no change), which has four C1 alkyl groups, showed superior heat resistance compared to compound 6 (12h: pale yellow), which has three C1 alkyl groups.

[0353] Furthermore, regarding weight change under heating conditions, Table 7 shows that while compound 19 in the reference example showed a weight change of 0.03% by weight after heating at 120°C for 48 hours, compounds 2, 6, 9, and 1 in the examples all showed a weight change of 0.01% by weight, confirming the superiority of the aryl ring group.

[0354] Next, as shown in Table 8, when compound 1 was heated at 160°C for 6 hours, the weight change rate was 0.20% by weight, while compounds 2, 6, and 9 all had weight change rates of 0.1% by weight or less, indicating that compounds with alkyl groups on the phenyl ring group exhibited superior heat resistance. Furthermore, when heated at 160°C for 12 hours, compound 6 had a weight change rate of 0.03% by weight, while compound 2 had a weight change rate of 0.01% by weight, indicating that compounds with C3 and C4 alkyl groups on the phenyl ring group exhibited superior heat resistance, and after 24 hours of heating, compound 2 (weight change rate: 0.01) with C4 had superior heat resistance compared to compound 6 (weight change rate: 0.04) with C3.

[0355] Furthermore, when the 5% weight loss temperature of compounds 1 and 19 during heating was measured using a TG / DTA (manufactured by SII) under a nitrogen atmosphere and a heating rate of 10°C / min, compound 19, a reference example, had a 5% weight loss temperature of 294°C, while compound 1 had a 5% weight loss temperature of 290°C, indicating that compound 19 had a higher 5% weight loss temperature. However, in heat resistance evaluation tests conducted under conditions closer to practical use, such as this heat resistance evaluation test, compound 1, which contains a phenyl residue that is the ultraviolet absorber of the present invention, showed high heat resistance.

[0356] The typical molding temperatures for general thermoplastic resins are: polymethyl methacrylate (PMMA): 160°C or higher, polyethylene terephthalate (PET): 260°C or higher, polycarbonate (PC): 220°C or higher, polystyrene (PS): 100°C or higher, and ABS resin: 220°C or higher. The typical thermosetting temperatures for thermosetting resins are: urea resin: 150°C, melamine resin: 150°C, and acrylic melamine resin film: 150°C. Depending on the molding time and thermosetting time of the resin, the UV absorber of the present invention has high heat resistance and can be preferably applied to resins with thermoforming and thermosetting temperatures of 80°C or higher, even 120°C or higher, and especially 160°C or higher.

[0357] [Table 7]

[0358] [Table 8]

[0359] 6. Evaluation of the heat resistance of organic resin compositions containing UV absorbers <1> Preparation of heat resistance evaluation samples • UV absorber / thermoplastic resin (meth)acrylic resin: polymethyl methacrylate resin Compounds 2, 6, 9, 1, and 19, which are the ultraviolet absorbers of the present invention, and compound 19 from Reference Example 5 were dissolved in a chloroform solution of 2.5 wt% polymethyl methacrylate resin (Tokyo Chemical Industries) to a concentration of 10 wt% relative to the acrylic resin. Approximately 0.5 ml of this solution was then dropped onto glass (micro slide glass S1112, manufactured by Matsunami Glass Industry Co., Ltd.), and a film was formed by spin coating to obtain an evaluation sample. • UV absorber / thermoplastic resin: Polycarbonate resin: Polycarbonate Compounds 2, 6, 9, 1, and 19, which are ultraviolet absorbers of the present invention, and compound 19 from Reference Example 5 were dissolved in a 5.0 wt% polycarbonate chloroform solution to a concentration of approximately 10 wt% relative to the acrylic resin. Approximately 0.5 ml of this solution was then dropped onto glass (micro slide glass S1112 manufactured by Matsunami Glass Industry Co., Ltd.), and a film was formed by spin coating to obtain an evaluation sample. • UV absorber / thermosetting resin: Acrylic melamine resin: Acrylic melamine resin Compounds 2, 6, 9, 1, and 19, which are ultraviolet absorbers of the present invention, and compound 19 from Reference Example 5 were dissolved in a 5.0 wt% acrylic melamine resin chloroform solution to a concentration of 10 wt% relative to the acrylic resin. Approximately 0.5 ml of this solution was then dropped onto glass (micro slide glass S1112 manufactured by Matsunami Glass Industry Co., Ltd.), and a film was formed by spin coating to obtain evaluation samples. <2> Evaluation of appearance and heat resistance The evaluation samples obtained above were placed in a constant temperature chamber set to 160°C and heated. After 6 and 12 hours, changes in appearance and transmittance were checked. Changes in appearance were evaluated according to the following criteria. Evaluation Criteria 160℃ heat resistance evaluation ○; Appearance change: No change △; Appearance change: Pale yellow ×; Appearance change: yellow

[0360] The transmittance was determined by measuring the ultraviolet-visible transmission spectrum using a UV-Vis spectrophotometer (Hitachi UH4150). The initial (pre-irradiation) ultraviolet transmittance (T1uv:%) at 380, 390, and 400 nm was measured, and the transmittance at 380, 390, and 400 nm (T2uv:%) was read from the UV-Vis transmission spectrum after heating. The difference in transmittance, ΔTuv(%), was calculated using the following formula.

[0361]

number

[0362] [Table 9]

[0363] Regarding the appearance shown in Table 9, the UV absorbers of Examples 37-40 and the organic resin compositions containing them were transparent due to their good affinity with glass, exhibited excellent heat resistance, and maintained a good appearance both immediately after sample preparation and after 12 hours of heating (they are also suitable as UV shielding films). Compounds 2, 6, 9, and 1 containing thioaryl ring groups showed smaller corresponding ΔTuv values ​​at 380, 390, and 400 nm after 6 and 12 hours compared to reference example compound 19 containing a thioalkyl group (no degradation of UV absorption capacity), exhibited excellent heat resistance, and demonstrated the superiority of the aryl ring group.

[0364] Furthermore, when comparing the ΔTuv values ​​of compounds 2, 6, 9, and 1 at 380, 390, and 400 nm after 6 and 12 hours, the relationship for all resin compositions was as follows: compound 2(Ph-tBu) / organic resin < compound 6(Ph-iPr) / organic resin < compound 9(Ph-Me) / organic resin < compound 1(Ph) / organic resin (for example, polymethacrylate methyl resin, 400 nm, after 6 hours: compound 2:9.5 < compound 6:12.4 < compound 9:18.1 < compound 1:18.4). In other words, organic resin compositions of compounds having a linear or branched alkyl group on an aryl ring group (phenyl residue) exhibited superior light resistance, and among these, the iPr group with 3 carbon atoms and the tBu group with 4 carbon atoms exhibited superior heat resistance compared to the methyl group with 1 carbon atom, and furthermore, the organic resin compositions with the tBu group with 4 carbon atoms exhibited superior heat resistance compared to the iPr group with 3 carbon atoms.

[0365] The rate of change of ΔTuv (ΔTuv(12h) / ΔTuv(6h)) was calculated from ΔTuv(6h) after 6h and ΔTuv(12h) after 12h, and is shown in Table 9. The rate of change of the resin compositions with UV absorber / polymethyl methacrylate resin and UV absorber / polycarbonate was smaller than that of the UV absorber / acrylic melamine resin in thermosetting resins, indicating superior heat resistance.

[0366] 7. Evaluation of lightfastness of glass containing an inorganic (vitreous) UV shielding film. <1> Preparation of lightfastness evaluation samples Compounds 2, 6, 7, 9, 16, 19, and 21, which are ultraviolet absorbers of the present invention, and compound 22 (TINUVIN360, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol], manufactured by Ciba Specialty Chemicals, Inc.) of Comparative Example 2 were mixed with zirconia beads using a paint conditioner and pulverized to obtain fine particles with an average particle size of 100 nm. A 10% by mass aqueous dispersion of UV absorber microparticles was mixed and stirred with pure water, ethyl alcohol, tetraethoxysilane (TEOS), glycidoxypropyltrimethoxysilane (GPTMS; 3-glycidyloxypropyltrimethoxysilane) as a silane coupling agent, triethylene glycol (TEG) as a polyol compound, a polyether phosphate polymer (Solspers 41000, manufactured by Lubrizol Japan) as a polyether compound, an ITO microparticle dispersion (ethyl alcohol solution containing 40% by mass of ITO microparticles; manufactured by Mitsubishi Materials; average particle size (nominal) 100 nm or less), and concentrated hydrochloric acid (35% by mass) to obtain a film-forming solution for UV shielding. The film-forming solution was prepared so that the concentration (content) of each component was as shown in Table 10. Compound 23 of Comparative Example 3 (Uvinul 3050, 2,2',4,4'-tetrahydroxybenzophenone, manufactured by BASF Japan Ltd.) was dissolved in ethyl alcohol beforehand and added to the film-forming solution. TEG and solspers correspond to organic compound C. In some examples, sorbitol polyglycidyl ether (Denacol EX-614, manufactured by Nagase ChemteX Corporation) was used as organic compound C. Sorbitol polyglycidyl ether is a polyepoxy compound, and in the film it becomes a polyol compound having a hydroxyl group generated by the reaction of the glycidyl group. However, in Examples 52 to 54, the oven temperature in the heating and drying process was set to 180°C, which is higher than the melting point of organic compound A, so organic compound A dissolved and was added to the film. Next, this forming solution was applied to a washed soda lime silicate glass substrate (commercially available UV-cut green glass, 100 x 100 mm, 3.1 mm thick) by flow coating at 30% humidity and room temperature.After drying at room temperature for about 5 minutes, the glass was placed in an oven preheated to the oven temperature shown in Table 10 and heated for 15 minutes, then cooled to form an ultraviolet shielding film. Table 10 shows the relationship between the temperature of the film-coated glass and the melting point of the ultraviolet absorber during this heating process. In Examples 41-51, 55, 56, and Comparative Example 2, the temperature of the film-coated glass was lower than the melting point of the ultraviolet absorber, and in this heating process, the temperature of the film-coated glass never exceeded the melting point of the ultraviolet absorber. The UV-cut green glass used had a light transmittance of 40% at a wavelength of 380 nm (T380) and a light transmittance of 77% at a wavelength of 550 nm (T550). This UV-cut green glass contains approximately 0.9% by mass of total iron oxide converted to Fe2O3. In Examples 52-54, the oven temperature during the heating and drying process was set to 180°C, which was higher than the melting point of the ultraviolet absorber, causing the ultraviolet absorber to dissolve and be added to the film. In Comparative Example 2, the ethyl alcohol solution was added to the film-forming solution, so the ultraviolet absorber dissolved and was added to the film.

[0367] [Table 10]

[0368] <2> Optical properties evaluation Optical properties were measured using a spectrophotometer (Shimadzu Corporation, UV-3100PC). The measured properties were the visible light transmittance Tvis according to JIS R3212, measured using a CIE standard A light source, and the ultraviolet transmittance Tvis calculated according to ISO 9050 (1990 edition). UV 380, UV transmittance T calculated according to ISO 13837 (convention A) UV 400, Blue light cut rate BLcut calculated based on the blue light hindrance function of JIS T7330, L of transmitted light measured using a CIE standard C light source according to JIS Z8729. * a * b *The color system, the yellowness YI of transmitted light measured using a CIE standard C light source according to JIS K7373 (2006), the dominant wavelength and stimulation purity of transmitted light measured using a CIE standard C light source according to JIS Z8701 (1999), and the light transmittance T1500 at a wavelength of 1500 nm. UV 380 is based on the transmittance of light rays at wavelengths of 280-380 nm, T UV The value 400 is calculated based on the light transmittance at wavelengths of 300-400 nm, while the blue light cut rate is calculated based on the light transmittance at wavelengths of 380-500 nm. <3> Lightfastness (UV resistance) evaluation Light resistance (UV resistance) was tested using an Iwasaki Electric Co., Ltd. UV irradiation device (EYE SUPER UV TESTER SUV-W13) at a wavelength of 295-450 nm and an illuminance of 76 mW / cm². 2 The test was conducted by applying conditions of a black panel temperature of 83°C and humidity of 50% RH, and irradiating the glass with the UV-shielding film from the side without the glass film for a predetermined time (100 hours). The optical properties (YA, T) after the UV irradiation test were then measured. UV 400) was measured, and the changes (ΔYA, ΔT) before and after the test were measured. UV 400) was calculated.

[0369] [Table 11]

[0370] In the optical properties shown in Table 11, the glasses of Examples 41 to 56 using the UV absorber of the present invention all exhibited good adhesion, high transparency, and T UV 380 is less than 0.3%, T UV 400 is less than 1%, blue light cut rate is less than 40%, L * a * b * a color system * If -9 or more and -8 or less, b * The value is between 5 and 9, and it has optical properties of yellowness YI of 10 or less, and in terms of light resistance, the rate of change in transmittance after ultraviolet irradiation test (T UVThe change rate (400) was 20 or less, and in particular, the UV absorber having a thiophenyl ring group showed a change rate of less than 6. Furthermore, in the comparison of the change rates of UV transmittance in Table 1A and Table 11, in Example 47, where compound 2 was added to a glassy UV shielding film, the change rate was lower than in Example 2, where it was added to a resin film. From these results, it is suggested that the UV absorber of the present invention is suitable for use in a glassy UV shielding film in order to maintain the UV shielding effect for a long period of time. UV region light resistance (change rate of transmittance: T UV 400) Compared with similar compounds, the thioaryl group (-SX) represented by formula (1) in [IV] 1a -(R 1a ) l Compounds 2, 6, 9, and 7, which have ), showed a smaller rate of change than compounds 19 and 21, which have thioalkyl groups, suggesting that the thioaryl group contributes to lightfastness. Among the compounds having thioaryl groups, R 1a However, compounds with 3 to 8 carbon atoms (and those with tertiary and / or quaternary carbon atoms) exhibited superior lightfastness.

[0371] Compared to Comparative Example 2, the T is lower. UV 400 was not obtained, and T was lower than in Comparative Example 3. UV 400 was obtained, but the yellowness YI was high. On the other hand, in each embodiment, while suppressing significant yellow coloration, T UV We were able to reduce 400. Furthermore, from a comparison between Examples 41-42 and Examples 52-53, it was confirmed that adding organic compound A as fine particles improved the light resistance of the film. In addition, when using organic compound A, such as compounds 2, 6, and 7, which have a thioaryl ring group to which a branched linear alkyl group is connected as a substituent on the hydrogen atom, the ΔT of these compounds alone was reduced. UV 400 is not significantly superior, yet the film's ΔT UV We were able to sufficiently suppress the 400.

[0372] 8. Evaluation of the transparency and optical properties of glass containing an organic material UV shielding film. <1> Preparation of lightfastness evaluation samples In a chloroform solution of 2.5 wt% polymethyl methacrylate resin (Tokyo Chemical Industries), compounds 1, 2, 9, and 19, which are ultraviolet absorbers of the present invention, and compound 24 of Comparative Example 4 were dissolved at a concentration of 10 wt% relative to the acrylic resin. 1 ml of this solution was then dropped onto glass (micro slide glass S1112, manufactured by Matsunami Glass Industry Co., Ltd.), and a film was formed using a spin coater (closed spin coater ACT-300AII, manufactured by Active Co., Ltd.) by holding at 1500 rpm for 20 seconds to obtain an evaluation sample of glass containing an ultraviolet shielding film. <2> Evaluation of appearance and optical properties The obtained evaluation samples were visually inspected, and the ultraviolet-visible transmission spectra were measured using a UV-Vis spectrophotometer (Hitachi UH4150), with the ultraviolet transmittance at 380, 390, and 400 nm read. Furthermore, the absolute value of the slope on the longer wavelength side of the absorption peak in the 350-390 nm wavelength range was recorded as described in 1. <1> It was calculated using the same method as before.

[0373] [Table 12]

[0374] Regarding the appearance shown in Table 12, in Examples 57-60, even under conditions where the UV absorber concentration relative to the resin was high at 10 wt%, the UV absorber and glass showed good affinity and adhesion between the glass and the UV shielding film, resulting in a transparent appearance of the glass containing the UV shielding film. Furthermore, the glass containing the UV shielding film in the Examples showed lower transmittance in the 380-400 nm range than the glass in Comparative Example 4, confirming superior long-wavelength absorption. In addition, the absolute value of the slope of the absorption peak of the glass containing the UV shielding film in the Examples was greater than that of the Comparative Example, suggesting a yellow suppression effect.

Claims

1. An ultraviolet absorber used in a composition for forming an ultraviolet shielding film for glass, wherein silicon dioxide in the ultraviolet shielding film accounts for 50% or more by mass of the entire film, The ultraviolet shielding film forming composition comprises a silicon dioxide precursor and the ultraviolet absorber. It consists of a 2-phenylbenzotriazole derivative having a thioalkyl group represented by the following formula (5), The UV absorber is in the form of fine particles, An ultraviolet absorber having an average particle size of 50 to 140 nm. 【Chemistry 1】 (In the formula, PhBzT 1e The benzotriazole skeleton may have substituents, with a thioalkyl group (-S-Y) attached to the phenyl moiety. 1e It exhibits a 2-phenylbenzotriazole skeleton to which ) is bonded, Y 1e (This represents a linear alkyl group having 1 to 22 carbon atoms.)

2. Y 1e The ultraviolet absorber according to claim 1, wherein is a linear alkyl group having 1 to 18 carbon atoms.

3. The ultraviolet absorber according to claim 1 or 2, used in the ultraviolet shielding film forming composition, which contains an ultraviolet absorber represented by formula (5) and an ultraviolet absorber other than formula (5) as organic compound B.

4. The ultraviolet absorber according to claim 3, wherein the organic compound B is in the form of fine particles with an average particle size of 150 nm or less.

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