阅读说明：本技术 耐热性优异和长波长吸收优异的紫外线吸收剂 (Ultraviolet absorber having excellent heat resistance and excellent long-wavelength absorption ) 是由 金子信裕 中村大介 金子恒太郎 河合功治 于 2020-04-27 设计创作，主要内容包括：本发明提供一种紫外线吸收剂,其与现有的紫外线吸收剂相比,耐热性和加热分解时的臭气抑制及长波长的吸收特别优异,并且摩尔吸光系数高。包含具有以下式(I)或(II)表示的键合基团的2-苯基苯并三唑衍生物的紫外线吸收剂：式(I)中,X表示为氮原子、氧原子或从酰胺基中除去了氢原子的残基,l表示为0或1的整数,Y～(1)表示具有或不具有取代基的芳香族烃基,m在X为氮原子或从酰胺基中除去氢原子的残基的情况下表示为1、在X为氧原子的情况下为0,Y～(2)表示为氢原子、具有或不具有取代基的脂肪族烃基、或具有或不具有取代基的芳香族烃基。式(II)中,Y～(3)与氮原子N一起形成具有或不具有取代基的杂环。[化学式1][化学式2](The invention provides an ultraviolet absorber, which is especially excellent in heat resistance, odor suppression during thermal decomposition and long-wavelength absorption, and has a high molar absorption coefficient, compared with conventional ultraviolet absorbers. An ultraviolet absorber comprising a 2-phenylbenzotriazole derivative having a bonding group represented by the following formula (I) or (II): in the formula (I), X represents a nitrogen atom, an oxygen atom or a residue obtained by removing a hydrogen atom from an amide group, l represents an integer of 0 or 1, and Y represents 1 Represents an aromatic hydrocarbon group with or without a substituent, m represents 1 when X is a nitrogen atom or a residue excluding a hydrogen atom from an amide group, 0 when X is an oxygen atom, and Y 2 Represented by a hydrogen atom, an aliphatic hydrocarbon group with or without substituents, or an aromatic hydrocarbon group with or without substituents. In the formula (II), Y 3 Together with the nitrogen atom N, form a heterocyclic ring with or without substituents. [ chemical formula 1] [ chemical formula 2])

1. An ultraviolet absorber, wherein it comprises a 2-phenylbenzotriazole derivative having a bonding group represented by the following formula (I) or (II):

[ chemical formula 1]

In the formula (I), X represents a nitrogen atom, an oxygen atom or a residue obtained by removing a hydrogen atom from an amide group; l represents an integer of 0 or 1; y is¹Represents an aromatic hydrocarbon group with or without a substituent; in the case where X is a nitrogen atom or a residue excluding a hydrogen atom from an amide group, m represents 1; in the case where X is an oxygen atom, m represents 0; y is²Represented by a hydrogen atom, an aliphatic hydrocarbon group with or without substituents, or an aromatic hydrocarbon group with or without substituents,

[ chemical formula 2]

In the above formula (II), Y³To nitrogen atom N-1Form a heterocyclic ring with or without substituents.

2. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) in which l is 0 or 1, and X is a nitrogen atom in the case where l is 1.

3. The ultraviolet absorber according to claim 1,

the bonding group is represented by the above formula (I) wherein l is 1, X is a nitrogen atom, and Y is¹Has a molecular weight of 190 or more.

4. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) in which l is 0 or 1, X is an oxygen atom and Y is¹Containing an oxygen-containing group.

5. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is²Is a hydrogen atom or an aromatic hydrocarbon group with or without a substituent.

6. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) in which Y is¹Is an aromatic hydrocarbon group having a substituent group, wherein the substituent group is an ester group or an amide group, l is 0 or 1, and when l is 1, X is a nitrogen atom.

7. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is¹The aromatic hydrocarbon group being a condensed ring of at least two rings or in an aromaticThe aromatic hydrocarbon group has a substituent and the substituent forms a ring together with the aromatic hydrocarbon group.

8. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is²Is a hydrogen atom at Y¹Having an oxygen-containing group or a nitrogen-containing group.

9. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is²Is an aliphatic hydrocarbon group with or without substituents, or an aromatic hydrocarbon group with or without substituents.

10. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, and X is a nitrogen atom or a residue excluding a hydrogen atom from an amide group.

11. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is¹Contains two or more condensed rings directly bonded to the nitrogen atom of X.

12. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, and Y is¹Containing two or more condensed rings bonded to a sulfur-containing group.

13. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 1 and X is a nitrogen atom，Y¹And a substituent having reactivity on the aromatic hydrocarbon group.

14. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (I) wherein l is 0 and Y is¹Have no substituent, or have an oxygen-containing group or a nitrogen-containing group as a substituent.

15. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (II), wherein in the formula (II), the heterocyclic ring contains more than 1 five-membered ring.

16. The ultraviolet absorber according to claim 15,

the heterocyclic ring is more than 2 rings.

17. The ultraviolet absorber according to claim 1,

the bonding group is represented by the formula (II) in which a heterocyclic ring is polycyclic.

18. The ultraviolet absorber according to claim 1 or 17,

the bonding group is represented by the formula (II), wherein the heterocyclic ring contains 1 or more six-membered rings.

19. The ultraviolet absorber according to claim 18,

the six-membered ring is a benzene ring.

20. The ultraviolet absorber as claimed in any one of claims 1 to 19,

the 2-phenylbenzotriazole derivative is represented by the following formula (A):

[ chemical formula 3]

In the formula (A), R¹～R⁹Each independently represents a monovalent group or a divalent group selected from the group consisting of a bonding group represented by the formula (I) or the formula (II), a hydrogen atom, a hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group and a halogen atom, R⁶～R⁹At least one of them is a bonding group represented by the formula (I) or the formula (II).

21. The ultraviolet absorber according to claim 20,

in the formula (A), in R⁷Or R⁸Having a bonding group represented by the formula (I) or the formula (II), R¹、R²、R³、R⁴、R⁵At least 1 of the above groups is any one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyl group, and when 2 or more are present, each is independently any one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyl group.

22. The ultraviolet absorber according to claim 21,

R¹、R²、R³、R⁴、R⁵at least 1 of them is any one selected from the group consisting of methyl group, t-butyl group and hydroxyl group, and in the case of 2 or more, each is independently any one selected from the group consisting of methyl group, t-butyl group and hydroxyl group.

23. The ultraviolet absorber according to claim 22,

R¹、R²、R³、R⁴、R⁵at least 1 of which is methyl.

24. The ultraviolet absorber as claimed in any one of claims 21 to 23,

R¹～R⁹has a reactive substituent.

25. An organic material composition or an inorganic material composition, wherein,

comprising the ultraviolet absorber of any one of claims 1 to 24 and an organic material, or comprising the ultraviolet absorber of any one of claims 1 to 24 and an inorganic material.

26. An organic resin composition, wherein,

which comprises the ultraviolet absorber as defined in any one of claims 1 to 24 and an organic resin.

Technical Field

The present invention relates to an ultraviolet absorber comprising a benzotriazole compound.

Background

The resin member is deteriorated by the action of ultraviolet rays, and the quality such as discoloration and reduction in mechanical strength is deteriorated, which further hinders long-term use. In order to prevent such quality deterioration or control the wavelength of transmitted light, it is common practice to incorporate an ultraviolet absorber into the resin member.

Heretofore, as organic ultraviolet absorbers, ultraviolet absorbers such as benzotriazole-based, benzophenone-based, triazine-based, cyanoacrylate-based, and salicylate-based ones have been known.

The present inventors have proposed 2-phenylbenzotriazole derivatives having a sulfur-containing group as an ultraviolet absorber capable of sufficiently and effectively absorbing 380 to 400nm harmful light in particular and suppressing absorption of light having a wavelength of 400nm or more, which is a factor of initial yellowing (patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2016/021664.

Patent document 2: international publication No. 2016/174788.

Disclosure of Invention

Problems to be solved by the invention

When a resin composition containing an organic ultraviolet absorber is heated, molded or processed, the ultraviolet absorber is thermally decomposed, which lowers the ultraviolet absorbing ability of the resin member, and in the case of a transparent resin member, the transparency of the resin member is impaired, which may further contaminate the inside of molding or processing equipment. Therefore, an organic ultraviolet absorber having further excellent heat resistance is required. In patent documents 1 and 2, as the sulfur-containing group of the 2-phenylbenzotriazole derivative, a sulfur-containing group in which a hydrocarbon group composed of carbon and hydrogen, such as aliphatic or aromatic, is bonded to sulfur at the base end is synthesized, but when the compound is used for a resin requiring a high processing temperature, there is a fear that the ultraviolet absorption ability is lowered by decomposition of an ultraviolet absorber, and further transparency in a transparent resin member is impaired, or equipment is contaminated during processing, and odor is generated during decomposition. Therefore, there is a demand for an ultraviolet absorber having excellent heat resistance which can be applied to a resin requiring a higher processing temperature and can reduce the contamination of equipment during processing and the generation of odor.

In recent years, it has been pointed out that not only ultraviolet rays having a wavelength of 250 to 400nm or less but also light having a short wavelength of visible light of about 400 to 430nm in sunlight are harmful to organic substances and human bodies. Therefore, a light absorber capable of absorbing light up to a short wavelength region of visible light is required. In patent documents 1 and 2, as the sulfur-containing group of the 2-phenylbenzotriazole derivative, a sulfur-containing group in which a hydrocarbon group composed of carbon and hydrogen, such as aliphatic or aromatic, is bonded to a sulfur at the base end is synthesized, but the absorption in the short wavelength region of visible light is still insufficient. Therefore, a light absorber capable of absorbing light even in a short wavelength region of visible light and absorbing a desired wavelength with high efficiency is required.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an ultraviolet absorber which is particularly excellent in heat resistance, odor suppression during thermal decomposition, and absorption at long wavelengths, and has a high molar absorption coefficient, as compared with conventional ultraviolet absorbers.

To solve the problems

The ultraviolet absorber of the present invention includes a 2-phenylbenzotriazole derivative having a bonding group represented by the following formula (I) or (II).

[ chemical formula 1]

(in the formula, X represents a nitrogen atom, an oxygen atom or a residue obtained by removing a hydrogen atom from an amide group,. l represents an integer of 0 or 1, and Y represents¹Represents an aromatic hydrocarbon group with or without a substituent, wherein m is 1 when X is a nitrogen atom or a residue obtained by removing a hydrogen atom from an amide group, and m is 0 and Y is 0 when X is an oxygen atom²Represents a hydrogen atom, an aliphatic hydrocarbon group with or without substituents, or an aromatic hydrocarbon group with or without substituents. )

[ chemical formula 2]

(in the formula, Y³And the nitrogen atom N together form a heterocyclic ring with or without substituents. )

ADVANTAGEOUS EFFECTS OF INVENTION

By introducing a functional group having a bonding group represented by the formula (I) or the formula (II) into the benzotriazole skeleton, the ultraviolet absorber of the present invention can be excellent in heat resistance, suppression of odor upon thermal decomposition, absorption of long wavelength light, and a high molar absorption coefficient.

Drawings

FIG. 1 is a reference graph showing the slope on the long wavelength side of an absorption peak in a wavelength region of 350 to 430nm in the ultraviolet-visible absorption spectrum.

Detailed Description

The present invention will be described in detail below.

[ substituents etc. ]

In the present invention, the substituent group contains a group capable of adjusting heat resistance, absorption characteristics, refractive index, melting point, light resistance, compatibility with a resin, and the like, such as "a monovalent group or a divalent group selected from a hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom", and examples thereof include the following groups.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may have a hydrogen atom or at least one of both ends interrupted or a carbon-carbon bond interrupted by a monovalent group or a divalent group selected from an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group and a halogen atom. The aliphatic hydrocarbon group is not particularly limited, and specific examples thereof include methyl group, ethan-1-yl group, propan-1-yl group, 1-methylethan-1-yl group, butan-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, 2-methylbutan-1-yl group, hexan-1-yl group, 2-methylpentane-1-yl group, 3-methylpentane-1-yl group, heptan-1-yl group, 3-ethylpentan-1-yl group, 2-methylhexan-yl group, 3-methylhexan-yl group, octane-1-yl group, 2-methylheptan-1-yl group, 3-methylheptan-1-yl group, 4-methylheptan-1-yl group, 2-ethylhexane-1-yl group, 3-ethylhexane-1-yl group, 1,3, 3-tetramethylbutylnonan-1-yl group, 3-ethylheptane-1-yl group, 4-ethylheptane-1-yl group, 2-methyloctane-1-yl group, 3-methyloctane-1-yl group, 4-methyloctane-1-yl group, decane-1-yl group, 4-propylheptane-1-yl group, 3-ethyloctane-1-yl group, 4-ethyloctane-1-yl group, 3-methyloctane-1-yl group, 3-methylheptane-1-yl group, 4-ethyloctane-1-yl group, 3-methyloctane-1-yl group, 3-ethyloctane-1-yl group, and the like, Undecan-1-yl, dodecane-1-yl, 2-methylundecan-1-yl, 2-ethyldecan-1-yl, tridecan-1-yl, tetradecan-1-yl, pentadecan-1-yl, hexadecan-1-yl, heptadecan-1-yl, octadecan-1-yl.

The alicyclic hydrocarbon group may have a carbon-carbon bond which is not interrupted by at least one of a hydrogen atom and both ends thereof, or a carbon-carbon bond, and the number of carbon atoms is preferably 3 to 10, more preferably 3 to 8, by substituting a monovalent group or a divalent group selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom. The alicyclic hydrocarbon group is not particularly limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and groups containing these as a skeleton.

The aromatic hydrocarbon group may have a monovalent group or a divalent group selected from an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, and a halogen atom, in which a hydrogen atom is substituted or at least one of both ends is not interrupted, or a carbon-carbon bond is not interrupted, and an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring is contained, and the number of carbon atoms is preferably 6 to 18, more preferably 6 to 14. The monovalent aromatic hydrocarbon group is not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, a 2,4, 5-trimethylphenyl group, a 2,4, 6-trimethylphenyl group, a 4-biphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 3-ethoxyphenyl group, a 4-ethoxyphenyl group, a 2-chlorophenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, a 2-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 1-naphthyl group, a 2-trifluoromethyl group, a 2-naphthyl group, a 2-trifluoromethyl group, a, 1-anthryl, 2-anthryl, 9-anthryl and the like. The divalent aromatic group is not particularly limited, and examples thereof include 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, 1, 8-naphthylene, 2, 7-naphthylene, 2, 6-naphthylene, 1, 4-naphthylene, 1, 3-naphthylene, 9, 10-anthrylene, 1, 8-anthrylene, 2, 7-anthrylene, 2, 6-anthrylene, 1, 4-anthrylene, and 1, 3-anthrylene.

The unsaturated group includes carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds (for example, carbonyl groups, aldehyde groups, ester groups, carboxyl groups, urethane groups, urea groups, amide groups, imide groups, carbamoyl groups, urethane groups, etc.), carbon-nitrogen double bonds (for example, isocyanate groups, etc.), carbon-nitrogen triple bonds (for example, cyano groups, cyanate groups, etc.), and carbon-carbon or carbon-heteroatom unsaturated bonds, and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8. The unsaturated group is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a maleic acid monoester group, a styryl group, an allyl group, a vinyl group, an alkenyl group, an alkynyl group, a carbonyl group, an aldehyde group, an ester group, a carboxyl group, a urethane group, a urea group, an amide group, an imide group, a carbamoyl group, a cyano group, a cyanate group, an isocyanate group, and a urethane group.

The nitrogen-containing group includes a cyano group, a cyanate group, an isocyanate group, a nitro group, a nitroalkyl group, an amide group, an urea group, a urethane group, an imide group, a carbodiimide group, an azo group, a pyridyl group, an imidazole group, an amine group, a primary amino group, a secondary amino group, a tertiary amino group, an aminoalkyl group, a 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-aminobenzotriazole group, a 3,4,5, 6-tetrahydrophthalimidomethyl group, a 2- [6- (2H-benzotriazol-2-yl-) -4- (1,1,3, 3-tetramethylbutyl) phenol-yl ] -methyl group, and the like, and the number of carbon atoms is preferably 0 to 10.

The sulfur-containing group includes a thiophene-containing group, a thiazole group, a thiol group, a thioether group, a thioalkoxy group, a sulfo group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a sulfonyl group, a sulfo group, a thiocarbonyl group, a thioureyl group, a thiourethane group, a dithiourethane group and the like, and the number of carbon atoms is preferably 0 to 10.

When the oxygen-containing group contains an aromatic hydrocarbon group or an alicyclic hydrocarbon group, the number of carbon atoms of the oxygen-containing group is preferably 6 to 12; when the oxygen-containing group does not contain an aromatic hydrocarbon group or an alicyclic hydrocarbon group, the number of carbon atoms is preferably 0 to 18. The oxygen-containing group is not particularly limited, and examples thereof include a hydroxyl group, an alkoxy group, an acetyl group, an aldehyde group, a carboxyl group, an ether group, a carbonyl group, an ester group, an oxazolyl group, an amide group, a nitro group, a morpholino group, a carbamate group, a carbamoyl group, a polyoxyethylene group, and an oxo group.

The phosphorus-containing group includes phosphine group, phosphite group, phosphonic acid group, phosphinic acid group, phosphoric acid group or phosphate group, and when the phosphorus-containing group contains an aromatic hydrocarbon group or an alicyclic hydrocarbon group, the carbon number of the phosphorus-containing group is preferably 6 to 22; when the phosphorus-containing group does not contain an aromatic hydrocarbon group or an alicyclic hydrocarbon group, the number of carbon atoms is preferably 0 to 6.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The 2-phenylbenzotriazole derivative in the present invention is represented by, for example, the following formula (A).

[ chemical formula 3]

In the formula (A), R¹～R⁹Each independently represents a monovalent or divalent group selected from the group consisting of a bonding group represented by the above formula (I) or formula (II), a hydrogen atom, a hydrocarbon group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group and a halogen atom. R¹～R⁹At least one of them is a bonding group represented by the formula (I) or the formula (II).

In the formula (A), the substitution position of the bonding group represented by the formula (I) or the formula (II) is not particularly limited, and may be R¹～R⁹Is preferably R⁶～R⁹More preferably R⁷、R⁸. The number of substitution of the bonding group represented by the above formula (I) or formula (II) is also not particularly limited, and is, for example, 1 to 2, preferably 1.

Examples of the substituent include the [ substituents ] mentioned above]The monovalent or divalent group described in the column (a). In the case where the above substituent is a divalent group, R¹～R⁹Any 2 (preferably adjacent 2) of them may form a ring together. These substituents may further be mono-or divalent substituents selected from the unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups and halogen atoms exemplified aboveThe group is free of hydrogen atoms or at least one of the two ends, or free of carbon-carbon bonds.

In the above formula (A), in R⁷Or R⁸Wherein R is a group having a bonding group represented by the above formula (I) or formula (II)⁶～R⁹In the above formula (I), the moiety other than the bonding group represented by the formula (II) is preferably a hydrogen atom. In addition, R is¹、R²、R³、R⁴、R⁵Preferred examples of the combinations of (1) are as follows.

[1] The substituent(s) containing 1 or more selected from a hydrocarbon group having 1 to 18 carbon atoms (including a hydrocarbon group having 2 to 18 carbon atoms including an alkenyl group and an alkynyl group), a hydroxyl group, an aromatic hydrocarbon 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, (meth) acryloyloxy group, a polyoxyethylene group having 1 to 20 carbon atoms to which these substituents may be bonded, or a hydrocarbon group having 1 to 18 carbon atoms to which a hydrogen atom, a base end, or a carbon-carbon bond may be unsubstituted with these substituents, and in the case of 2 or more, each is independently selected from the above substituents.

[2] In the above item [1], the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxyl group.

[3] In the above [2], the substituent is at least one selected from a hydrocarbon group having 1 to 6 carbon atoms and a hydroxyl group.

[4] In any one of [1] to [3], the hydrocarbon group as a substituent is a straight-chain alkyl group or a branched-chain alkyl group.

[5] In [4], the substituent is at least one selected from the group consisting of methyl, t-butyl and hydroxyl.

[6] In [5], the substituent is at least one selected from the group consisting of methyl, t-butyl and hydroxyl, and the hydroxyl group is 1 or less.

[7] In [5], at least one methyl group is present as a substituent.

[8] In any one of [1] to [7], the number of substituents is 1 to 4, preferably 2 to 4.

[9]In the following [1]]To [8]]In any one of (1), in R¹～R⁴Has a substituent at any position of (A), and R is other than¹～R⁵Is a hydrogen atom.

[10]In the following [1]]To [ 9]]In any one of (1), in R¹、R²、R⁴Has a substituent at any position of (A), and R is other than¹～R⁵Is a hydrogen atom.

[11]In [10 ]]In, R¹Is hydroxy, R²Is tert-butyl, R⁴Is methyl, R³And R⁵Is a hydrogen atom.

(bonding group represented by the above formula (I) or formula (II))

In the bonding group represented by the above formula (I), X represents a nitrogen atom, an oxygen atom or a residue obtained by removing a hydrogen atom from an amide group, and l represents an integer of 0 or 1. In formula (I), when X is a residue obtained by removing a hydrogen atom from an amide group, it is represented by — C (═ O) -N<Or is>N-C(＝O)-。Y¹Represents an aromatic hydrocarbon group with or without a substituent. When X is a nitrogen atom or a residue excluding a hydrogen atom from an amide group, m is 1, and when X is an oxygen atom, m is 0. Y is²Represented by a hydrogen atom, an aliphatic hydrocarbon group with or without substituents, or an aromatic hydrocarbon group with or without substituents.

Y¹、Y²The aromatic hydrocarbon group (2) is composed of a single ring or a condensed ring, and the number of carbon atoms is preferably 6 to 18, more preferably 6 to 14. The aromatic hydrocarbon group is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

Y²The aromatic hydrocarbon group of (3) preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples thereof include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, and an alicyclic hydrocarbon group. The aliphatic hydrocarbon group is not particularly limited, and examples thereof include methyl, ethan-1-yl, propan-1-yl, 1-methylethan-1-yl, butan-2-yl, 2-methylpropan-1-yl, 2-methylpropan-2-yl, pentan-1-yl, pentan-2-yl, 2-methylbutan-1-yl, hexan-1-yl, 2-methylpentane-1-yl, and 3-methylpentane-1-yl-1-yl, heptan-1-yl, 3-ethylpentan-1-yl, 2-methylhexan-yl, 3-methylhexan-yl, octan-1-yl, 2-methylheptan-1-yl, 3-methylheptan-1-yl, 4-methylheptan-1-yl, 2-ethylhexan-1-yl, 3-ethylhexan-1-yl, 1,1,1,3, 3-tetramethylbutylnonan-1-yl, 3-ethylheptan-1-yl, 4-ethylheptan-1-yl, 2-methyloctan-1-yl, 3-methyloctan-1-yl, 4-methyloctan-1-yl, methyl-1-yl, Decan-1-yl, 4-propylheptan-1-yl, 3-ethyloctan-1-yl, 4-ethyloctan-1-yl, undecan-1-yl, dodecane-1-yl, 2-methylundecan-1-yl, 2-ethyldecan-1-yl, tridecan-1-yl, tetradecan-1-yl, pentadecan-1-yl, hexadecan-1-yl, heptadecan-1-yl, octadecan-1-yl, etc. Among them, a C1-8 linear alkyl group or a branched alkyl group is preferable, and a C1-4 linear alkyl group or a branched alkyl group is more preferable. The alicyclic hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 8 carbon atoms. Examples of the alicyclic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and groups containing these groups as a skeleton.

As Y¹、Y²The substituent(s) is not particularly limited, and examples thereof include the above-mentioned [ substituent(s) and the like]Monovalent or divalent groups described in the following column, and the like. When the substituent is a divalent group, any 2 (preferably adjacent 2) carbon atoms of the aromatic hydrocarbon group or the aliphatic hydrocarbon group may form a ring together.

Preferred examples are as follows.

As the heat resistance and the molar absorption coefficient of the maximum absorption peak in the wavelength region of 350 to 430nm, the following are preferable examples of the bonding group represented by the formula (I).

(1-1) the bonding group is represented by the formula (I) wherein l is 1 and X is an oxygen atom.

(1-2) the bonding group is represented by the formula (I) wherein l is 0 or 1, and X is a nitrogen atom in the case where l is 1.

(1-3) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹Has a molecular weight of 190 or more.

(1-4) the bonding group is represented by the formula (I) wherein l is 0 or 1, X is an oxygen atom in the case where l is 1, and Y is¹Contains an oxygen-containing group.

(1-5) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is²Is a hydrogen atom, or an aromatic hydrocarbon group with or without a substituent.

(1-6) the bonding group is represented by the formula (I) wherein Y is¹The aromatic hydrocarbon group has a substituent group, and the base end of the substituent group is an ester group or an amide group. l is 0 or 1, and in the case where l is 1, X is a nitrogen atom.

(1-7) the bonding group is represented by the formula (I) wherein Y is¹The aromatic hydrocarbon group has a substituent containing at least one selected from the group consisting of a hydroxyl group and a (meth) acryloyl group. The substituent is preferably a hydroxyalkyl group (having 1 to 10 carbon atoms, for example), a (meth) acryloyl group or an alkyl group having a terminal substituted with a (meth) acryloyl group (having 1 to 10 carbon atoms, for example).

(1-8) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹A fused ring skeleton containing at least two rings (the upper limit is not particularly limited, for example, four rings or less) bonded to the sulfur-containing group. The condensed ring skeleton is not particularly limited, and examples thereof include a benzotriazole skeleton. Preferably, Y is¹Is substituted on an aromatic hydrocarbon group (preferably a phenyl group), and the substituent contains the sulfur-containing group. More preferably, the substituent is terminated with the sulfur-containing group.

(1-9) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹The aromatic hydrocarbon group of (2) is a condensed ring of at least two rings, or has a substituent on the aromatic hydrocarbon group, and the substituent forms a ring together with the aromatic hydrocarbon group.

Further, R in the formula (A) is other than any of the above¹～R⁴In any of the above cases where 3 or more substituents are present, from the viewpoint of heat resistance and molar absorption coefficient of the maximum absorption peak in the wavelength region of 350 to 430nm, more preferable is。

As the heat resistance and the molar absorption coefficient of the maximum absorption peak in the wavelength region of 350 to 430nm, the following are preferable examples of the bonding group represented by the formula (II).

The bonding group (2-1) is represented by formula (II), wherein the heterocycle is polycyclic (not particularly limited, for example, bicyclic to tetracyclic).

In addition, from the viewpoint of heat resistance, R in the formula (A) is not particularly limited¹～R⁴Any one of (1) and (3) or more substituents is more preferable.

In the long wavelength absorption, preferable examples of the bonding group represented by the formula (I) include the following.

(3-1) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is²Is a hydrogen atom at Y¹Having an oxygen-containing group or a nitrogen-containing group.

(3-2) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is²Is an aliphatic hydrocarbon group with or without substituents or an aromatic hydrocarbon group with or without substituents.

(3-3) the bonding group is represented by the formula (I) wherein l is 1 and X is a nitrogen atom or a residue excluding a hydrogen atom from an amide group.

Preferred examples of the bonding group represented by the formulae (I) and (II) include the following, in terms of the slope on the long wavelength side of the maximum absorption peak in the wavelength region of 350 to 430 nm.

(4-1) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹An unsubstituted aromatic hydrocarbon group (preferably phenyl) which is monocyclic, Y²Is a hydrogen atom or an aliphatic hydrocarbon group with or without a substituent.

(4-2) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹And fused rings containing at least two rings (the upper limit is not particularly limited, and examples thereof include four rings or less). The condensed ring may be a ring containing the above-mentioned aromatic hydrocarbon group or a ring contained in the above-mentioned aromatic hydrocarbon groupA ring in the substituent (in the latter case, for example, a benzotriazole skeleton may be mentioned). Y is¹Preferably, the fused ring contains at least two rings directly bonded to the nitrogen atom of X. The condensed ring is preferably three or more rings. Preferably, the fused ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

(4-3) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹The fused ring contains 1 or more six-membered rings (the fused ring is, for example, two or more to four or less rings, although not particularly limited). The condensed ring may be a ring containing the aromatic hydrocarbon group or a ring included in a substituent of the aromatic hydrocarbon group (in the latter case, for example, a benzotriazole skeleton). Preferably, the fused ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

(4-4) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹A condensed ring (not particularly limited, for example, two or more and four or less rings) and an oxygen-containing group as a substituent in the condensed ring. The condensed ring may contain the aromatic hydrocarbon group in the skeleton or may not contain the aromatic hydrocarbon group. Preferably, the fused ring thereof contains the aromatic hydrocarbon group in the skeleton.

The (4-5) bonding group is represented by formula (II), in which the heterocyclic ring is polycyclic (not particularly limited, for example, bicyclic or more to tetracyclic or less).

The bonding group (4-6) is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more six-membered rings (not particularly limited, for example, one or more rings to four rings or less). Preferably the heterocyclic ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

The (4-7) bonding group is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more five-membered rings (not particularly limited, for example, one or more to four rings or less). Preferably, the heterocyclic ring is bicyclic or more.

(4-8) the bonding group is represented by the formula (I) wherein l is 0 and Y is¹Is provided with or without an accessAn aryl group (preferably phenyl group). Preferably, Y is¹Having no substituent or having an oxygen-containing group or a nitrogen-containing group as a substituent. More preferably Y¹Having an oxygen-containing group as a substituent.

(4-9) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹A fused ring skeleton containing at least two rings (the upper limit is not particularly limited, and is, for example, four rings or less) bonded to the sulfur-containing group. The condensed ring skeleton is not particularly limited, and examples thereof include a benzotriazole skeleton. Preferably Y¹The aromatic hydrocarbon group (preferably phenyl group) has a substituent, and the substituent contains the sulfur-containing group. More preferably, the terminal end of the substituent is a sulfur-containing group.

(4-10) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹The aromatic hydrocarbon group (preferably phenyl group) has a substituent containing a hydroxyl group, preferably a hydroxyalkyl group (having 1 to 10 carbon atoms, for example).

(4-11) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹Is substituted on an aromatic hydrocarbon group (preferably a phenyl group). The substituent contains a (meth) acryloyl group, preferably a (meth) acryloyl group or an alkyl group having a terminal substituted with a (meth) acryloyl group (the number of carbon atoms in the alkyl group is, for example, 1 to 10).

In terms of compatibility with the resin, preferred examples of the bonding group represented by the formula (I) and the formula (II) include the following.

(5-1) the bonding group is represented by the formula (I) wherein l is 0 and Y is¹Is an aromatic hydrocarbon group (preferably phenyl group) having or not having a substituent.

The (5-2) bonding group is represented by formula (II), and in formula (II), the heterocycle of formula (II) is polycyclic (not particularly limited, for example, bicyclic or more to tetracyclic or less).

The bonding group (5-3) is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more six-membered rings (not particularly limited, for example, one or more rings to four rings or less). Preferably, the heterocyclic ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

The (5-4) bonding group is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more five-membered rings (not particularly limited, for example, one or more to four rings or less). Preferably, the heterocyclic ring is bicyclic or more.

Further, R in the formula (A) is, in addition to the above, R¹～R⁵1 or more of (1) is preferably a methyl group. Preferably R thereof⁴Is methyl.

Preferable examples of the bonding group represented by the formula (I) and the formula (II) in light resistance include the following.

(6-1) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹Having a condensed ring of at least two rings (the upper limit is not particularly limited, and is, for example, four rings or less). The condensed ring may be a ring containing the aromatic hydrocarbon group or a ring included in a substituent of the aromatic hydrocarbon group (in the latter case, for example, a benzotriazole skeleton). Y is¹Preferably, the fused ring contains at least two rings directly bonded to the nitrogen atom of X. The condensed ring is preferably three or more rings. Preferably, the fused ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

(6-2) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹Has a condensed ring skeleton containing 1 or more six-membered rings (not particularly limited, for example, two or more and four or less rings). Preferably Y¹Having a condensed ring containing the aromatic hydrocarbon group in the skeleton. The fused ring preferably contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

(6-3) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹A condensed ring (not particularly limited, for example, two or more and four or less rings) and an oxygen-containing group as a substituent in the condensed ring. The condensed rings may or may not contain the aromatic hydrocarbon group in the skeleton. Preferably, the fused ring thereof contains the aromatic hydrocarbon group in the skeleton.

The bonding group (6-4) is represented by formula (II) in which an unsaturated bond (preferably a double bond) is contained in the heterocyclic ring.

The (6-5) bonding group is represented by formula (II), in formula (II), the heterocyclic ring is polycyclic (not particularly limited, for example, from bicyclic rings to tetracyclic rings).

The (6-6) bonding group is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more six-membered rings (not particularly limited, for example, one or more rings to four rings or less). Preferably, the heterocyclic ring contains 2 or more six-membered rings. The six-membered ring is preferably an aromatic hydrocarbon group (more preferably a phenyl group).

The (6-7) bonding group is represented by formula (II), wherein the heterocyclic ring in formula (II) contains 1 or more five-membered rings (not particularly limited, for example, one or more to four rings or less). Preferably, the heterocyclic ring is bicyclic or more.

(6-8) the bonding group is represented by the formula (I) wherein l is 0 and Y is¹Is an aromatic hydrocarbon group (preferably phenyl group) having or not having a substituent. Preferably Y¹Having no substituent or having an oxygen-containing group or a nitrogen-containing group as a substituent. More preferably Y¹Having an oxygen-containing group or a nitrogen-containing group as a substituent.

(6-9) the bonding group is represented by the formula (I) wherein l is 1, X is a nitrogen atom, Y is¹A fused ring skeleton having a bicyclic or higher ring form (the upper limit is not particularly limited, and is, for example, four or lower) bonded to a sulfur-containing group. The condensed ring skeleton is not particularly limited, and examples thereof include a benzotriazole skeleton. Preferably Y¹The aromatic hydrocarbon group (preferably phenyl group) has a substituent, and the substituent contains the sulfur-containing group. More preferably, the terminal end of the substituent is the sulfur-containing group.

Further, R in the formula (A) is, in addition to the above, R¹～R⁵1 or more of (1) is preferably a methyl group. Preferably R thereof⁴Is methyl.

When the bonding group of the formula (I) or (II) or the reactive substituent(s) contained in the formula (A) is used by being added to an organic material or an inorganic material, the bonding group is bonded to the organic material or the inorganic material to prevent bleedingAnd the like, and the strength of the organic material is preferably secured. The reactive substituent is not particularly limited as long as it can react with a functional group of an organic material or an inorganic material, and examples thereof include an isocyanate group, an epoxy group, a carboxyl group, a carbonyl group, a hydroxyl group, an alkenyl group, an alkynyl group, an ether group, a thioisocyanate group, a thioepoxy group, a thiocarboxyl group, a thiocarbonyl group, a thiol group, an amino group, a vinyl group, a vinyloxy group, an allyl group, a (meth) acryloyl group, a maleoyl group, a styryl group, a cinnamoyl group, a hydrocarbon group (for example, a carbon number of 1 to 20, preferably an alkyl group) to which these groups are bonded, a polyoxyalkylene group (for example, a carbon number of 1 to 20), and the like. Further, hydroxyl groups, (meth) acryloyl groups, and hydrocarbon groups and polyoxyalkylene groups to which these groups are bonded are preferable. For example, among the bonding groups represented by the above formula (I), Y is preferred¹The aromatic hydrocarbon group of (3) contains a reactive substituent, and from the viewpoint of reactivity, an aromatic hydrocarbon group in which an alkyl group having a reactive substituent at the end is bonded to an aromatic group is more preferable.

In a preferred embodiment, the bonding group is represented by formula (I) wherein l is 1, X is a nitrogen atom, Y is¹And a reactive substituent on the aromatic hydrocarbon group.

In the bonding group represented by the above formula (II), Y³Together with the nitrogen atom N, form a heterocyclic ring with or without substituents. Examples of the atom constituting the heterocyclic ring include, in addition to a nitrogen atom and a carbon atom, a heteroatom such as a sulfur atom, a nitrogen atom, and an oxygen atom. Preferred is a heterocyclic ring in which the heteroatom is at least one selected from a nitrogen atom and an oxygen atom, and more preferred is a heterocyclic ring in which the heteroatom is a nitrogen atom. Further, more preferred are fused rings of two or more rings.

Specific examples of the organic solvent include, but are not particularly limited to, aziridine, 1H-aziridine, pyrrole, pyrrolidine, piperidine, hexamethyleneimine, azacycloheptatriene, azacyclooctane (azocane), azacyclononane (azone), azacyclononalene (azonine), pyrazole, imidazoline, morpholine, thiazine, triazole, tetrazole, carbazole, phenazine, phenoxazine, phenothiazine, pyrroline, indole, isoindole, benzimidazole, purine, benzotriazole, porphyrin, chlorin, choline, adenine, guanine, cytosine, thymine, uracil, pyrrolidone, and imidazole, among which pyrrole, carbazole, piperidine, indole, and phenothiazine are preferable, pyrrole, carbazole, indole are more preferable, carbazole, indole are further more preferable, and carbazole is particularly preferable.

When an ultraviolet absorber is reacted with an organic material such as a resin and an inorganic material under heating, mixed and kneaded, or when a resin member containing the ultraviolet absorber is processed and molded by heating, the ultraviolet absorber may decompose when the thermal decomposition temperature of the ultraviolet absorber is low, and the effect of absorbing ultraviolet rays may not be sufficiently exhibited, and the device may be contaminated, and when the resin member is transparent, an ultraviolet absorber having a high thermal decomposition temperature is preferable in order to prevent loss of transparency. In addition, in the case of thermal decomposition (oxidative decomposition), an ultraviolet absorber containing no sulfur atom which is a main cause of odor is preferable from the viewpoint of odor suppression. The ultraviolet absorber of the present invention has improved heat resistance by introducing the bonding group represented by the above formula (I) or formula (II) into the 2-phenylbenzotriazole derivative. The 5% weight loss temperature of the 2-phenylbenzotriazole derivative in the present invention is preferably 250 ℃ or higher, more preferably 280 ℃ or higher, still more preferably 300 ℃ or higher, and particularly preferably 340 ℃ or higher. Since the 5% weight reduction temperature in the present invention is higher than the softening temperature of a general resin, i.e., 100 to 250 ℃ (easily understandable plastic (よくわかるプラスチック) which is a major edition of Japan Plastic industry Union, published by Japan Industrial Press), the present invention can be applied to thermosetting resins and thermoplastic resins having a molding temperature of 100 to 200 ℃ in the first place, and can also be applied to thermoplastic resins requiring a molding temperature higher than 200 to 250 ℃.

It is pointed out that not only ultraviolet rays of 250 to 400nm or less in sunlight but also light in a short wavelength region of visible light of about 400 to 430nm may damage organic substances (for example, a general organic resin composition, protection of a blue light emitting element in an organic EL display device such as a display, etc.) and a human body. In addition, in the same manner as in the case of LED lighting, a light absorber capable of absorbing light up to a short wavelength region of visible light is required, and preferably has an absorption peak at 355nm or more, more preferably at 370nm or more, still more preferably at 390nm or more, and particularly preferably at 400nm or more in a long wavelength region of 380 to 430 nm.

When absorbing visible light of 400 to 430nm, it is preferable that light having a wavelength of more than 430nm is transmitted in order to suppress deterioration of appearance (for example, yellowing) of the resin member, display color of the display, and emission color of the LED. In this case, although there are various criteria, for example, the transmittance at 400nm is preferably 10% or less, more preferably 1% or less, the transmittance at 430nm is preferably 75% or less, and the transmittance at 440nm is preferably 53% or more, more preferably 75% or more. The required absorption region is different depending on the field, and the wavelength of the absorption peak is also different depending on the field, but the selectivity of the absorption wavelength and the absorption efficiency are important in many fields. Focusing on the shape of the absorption peak, a sharp absorption peak having a large slope of the absorption peak may selectively absorb light of a specific wavelength, and the absolute value of the slope of the wavelength of the maximum absorption peak in the wavelength region of 350 to 430nm as measured with 50 μ M chloroform or 100 μ M chloroform is preferably 0.015 or more, more preferably 0.020 or more, further preferably 0.025 or more, particularly preferably 0.030 or more, and further preferably 0.034 or more. Within such a range, light having a wavelength of 400 to 430nm can be selectively absorbed. In order to efficiently absorb the wavelength in this region, the molar absorption coefficient of the maximum absorption peak in the wavelength region of 350 to 430nm as measured with 50. mu.M chloroform or 100. mu.M chloroform is preferably 17200L/(mol. cm) or more, more preferably 18000L/(mol. cm) or more, still more preferably 20000L/(mol. cm) or more, and particularly preferably 30000L/(mol. cm) or more.

For inhibiting deterioration of ultraviolet absorbent, and organic material composition or inorganic material composition and organic resin composition containing the ultraviolet absorbentThe optical properties are important, but the conditions (wavelength 300 to 400nm, illuminance 42W/m) described in the evaluation of light resistance in the following example (7)²Or blackboard temperature 63 ℃ or the like), the ultraviolet absorber of the present invention preferably has a transmittance difference of 76% or less, more preferably 45% or less, further preferably 30% or less, particularly preferably 15% or less, still more preferably 10% or less, and very preferably 5% or less, in all of 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, and 430nm after irradiation for 100 hours.

In the ultraviolet absorption characteristics, the molar absorption coefficient affects the amount of the ultraviolet absorber added, that is, the larger the value of the molar absorption coefficient, the more efficiently the absorption wavelength required to be absorbed is absorbed. In addition, if the slope of the absorption peak is large, the long wavelength region is not absorbed, and a desired wavelength region can be selectively absorbed. For example, depending on the field, in order to suppress absorption of visible light, the ultraviolet absorber of the present invention is required to absorb wavelengths of 400 to 430nm, and even when the ultraviolet absorber of the present invention is added, coloring such as yellowing of the material can be suppressed. The ultraviolet absorber of the present invention having excellent light resistance is very useful because of its durability.

The 2-phenylbenzotriazole derivative has good compatibility with resin, and R is¹～R⁵The substituent(s) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl or tert-butyl group, and still more preferably a group having at least 1 methyl group. In addition, the position thereof is preferably R²、R⁴。

(composition)

In the present specification, the term "composition" encompasses a composition including the ultraviolet absorber of the present invention regardless of its state such as solid, fluid, gel, sol, etc., and encompasses a material for producing the member in addition to the member.

In the present specification, the term of the member is not particularly limited, and includes, for example, a shaped object having an arbitrary shape. The use of the composition for a member or the like containing the ultraviolet absorber of the present invention includes, for example, the use described below.

Examples of the material of 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 materials and inorganic materials, and when the ultraviolet absorber of the present invention is mixed, dissolved, dispersed, coated, or coated, a uniform composition or member can be obtained, and particularly when a transparent member is used, a member having excellent transparency can be obtained. Particularly, the applicability to organic materials is high.

The composition containing the ultraviolet absorber of the present invention includes an organic material composition and an inorganic material composition (in the present invention, these organic material composition in the case of containing an organic material and inorganic material composition in the case of containing an inorganic material are collectively referred to as an organic material composition or an inorganic material composition containing an organic material or an inorganic material). The shape of the organic material composition and the inorganic material composition is not particularly limited, and examples thereof include a coating film, a laminated film, a sheet, a plate, a powder, a granule, a pellet, a tablet, a molded article, and the like.

In the organic material composition and the inorganic material composition containing the ultraviolet absorber of the present invention, the ultraviolet absorber of the present invention can provide an organic material composition and an inorganic material composition having excellent heat resistance and can suppress deterioration. In addition, the affinity with organic materials, inorganic materials, especially organic materials is good.

According to the characteristics of the ultraviolet absorber of the present invention, the organic material composition and the inorganic material composition containing the ultraviolet absorber can effectively absorb harmful light in a wavelength range of 250 to 430nm, and for example, the organic material composition and the inorganic material composition have excellent appearance, and are excellent in heat resistance, capable of suppressing a decrease in ultraviolet absorption ability due to decomposition of the ultraviolet absorber, a loss of transparency in the composition, and a contamination of a device during processing or generation of odor during decomposition even under a high processing temperature condition.

The organic material composition contains 0.001% by mass or more of the organic material, preferably 0.01% by mass or more of the organic material, more preferably 0.1% by mass or more of the organic material, and further preferably 1% by mass or more of the organic material, based on the total amount of all materials except water and the solvent.

The inorganic material composition contains 0.001% by mass or more of an inorganic material, preferably 0.01% by mass or more of an inorganic material, more preferably 0.1% by mass or more of an inorganic material, and further preferably 1% by mass or more of an inorganic material, based on the total amount of all materials except water and a solvent.

The composition containing the ultraviolet absorber of the present invention may be a composition obtained by adding and mixing raw materials for finally forming an organic material, an inorganic material, a member, and the like. The composition containing the ultraviolet absorber of the present invention may be a composition obtained by dispersing, dissolving or mixing an organic material composition or an inorganic material composition containing the ultraviolet absorber of the present invention in a liquid such as water or an organic solvent.

The organic material is not particularly limited, and examples thereof include organic resins, animal and plant-derived materials, crude oil-derived materials, 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 contained in the organic material composition.

The organic resin is not particularly limited, and conventionally known resins can be widely used, and examples thereof include thermoplastic resins, thermosetting resins, and the like, each of which includes a polymer having 1 kind of repeating unit and a copolymer containing a plurality of repeating units.

In the present specification, the terms of the thermoplastic resin (polymer and copolymer) and the thermosetting resin (polymer and copolymer) are allowed to include, in the respective kinds of the resins exemplified below, in addition to the original repeating unit in the meaning of the general term of the resin, other repeating units in an amount of 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 2% by mass or less with respect to the total amount of the resin. The content of the other resin is allowed to be 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less with respect to the total amount of the mixture.

The thermoplastic resin is not particularly limited, and examples of the polymer include (meth) acrylic resins, olefin resins, styrene resins, ester resins, ether resins, vinyl chloride resins, fluorine resins, vinyl resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimide resins, polymaleimide resins, polyvinylpyrrolidone resins, polyurethane resins, polysulfone resins, polyphenylene sulfide resins, and cycloolefin resins; examples of the copolymer include a butadiene-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, a styrene-isoprene copolymer, a styrene-acrylic copolymer, and a vinyl chloride-vinylidene chloride-acrylonitrile copolymer. These may be used alone or in combination of two or more.

The polymer of the thermoplastic resin is not particularly limited, and examples thereof include the following polymers.

The (meth) acrylic resin is not particularly limited, and examples thereof include poly (meth) acrylic acid, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, and poly (meth) acrylonitrile.

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

The styrene resin is not particularly limited, and examples thereof include polystyrene.

The ester-based resin is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycaprolactone, polyethylene succinate, polylactic acid, polymalic acid, and polyglycolic acid.

The ether resin is not particularly limited, and examples thereof include polyacetal, polyphenylene ether, polyether ketone, polyether ether ketone, polyether ketone, polyether ether ketone, polyether sulfone, and polyether imide.

The vinyl chloride resin is not particularly limited, and examples thereof include polyvinyl chloride and polyvinylidene chloride.

The fluorine-based resin is not particularly limited, and examples thereof include polytetrafluoroethylene, polyvinyl fluoride, and polyvinylidene fluoride.

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

The polycarbonate-based resin is not particularly limited, and examples thereof include polycarbonate and the like.

The polyamide resin is not particularly limited, and examples thereof include polyamide, nylon 6, nylon 66, nylon 11, nylon 12, and the like.

The polyimide resin is not particularly limited, and examples thereof include polyimide and the like.

The polyamide-imide resin is not particularly limited, and examples thereof include polyamide-imide.

The polymaleimide resin is not particularly limited, and examples thereof include polymaleimide and poly-N-phenylmaleimide.

The polyvinylpyrrolidone-based resin is not particularly limited, and examples thereof include polyvinylpyrrolidone.

The urethane resin is not particularly limited, and examples thereof include polyurethane.

The polysulfone-based resin is not particularly limited, and examples thereof include polysulfone.

The polyphenylene sulfide resin is not particularly limited, and examples thereof include polyphenylene sulfide resins.

The cycloolefin resin is not particularly limited, and examples thereof include cycloolefin polymers and the like.

The copolymer of the thermoplastic resin is not particularly limited, and a copolymer of a plurality of raw material monomers including the above-exemplified polymers is exemplified, and the following copolymers are exemplified.

The butadiene-styrene copolymer is not particularly limited, and examples thereof include a butadiene-styrene copolymer.

The acrylonitrile-styrene copolymer is not particularly limited, and examples thereof include an acrylonitrile-styrene copolymer.

The acrylonitrile-butadiene-styrene copolymer is not particularly limited, and examples thereof include an acrylonitrile-butadiene-styrene copolymer and the like.

The styrene-isoprene copolymer is not particularly limited, and examples thereof include a styrene-isoprene copolymer and the like.

The styrene-acrylic copolymer is not particularly limited, and examples thereof include styrene-acrylic copolymers and the like.

The vinyl chloride-vinylidene chloride-acrylonitrile copolymer is not particularly limited, and examples thereof include a vinyl chloride-vinylidene chloride-acrylonitrile copolymer and the like.

The thermosetting resin is not particularly limited, and examples of the polymer include phenolic resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and episulfide resin, and examples of the copolymer include acrylic melamine resin and acrylic urethane resin. These resins may be used alone or in combination of two or more.

The polymer of the thermosetting resin is not particularly limited, and examples thereof include the following polymers.

The phenolic resin is not particularly limited, and examples thereof include phenolic resins.

The urea resin is not particularly limited, and examples thereof include urea resins.

The melamine resin is not particularly limited, and examples thereof include melamine resins.

The unsaturated polyester resin is not particularly limited, and examples thereof include unsaturated polyester resins.

The alkyd resin is not particularly limited, and examples thereof include alkyd resins.

The epoxy resin is not particularly limited, and examples thereof include epoxy resins.

The episulfide resin is not particularly limited, and examples thereof include episulfide resins and the like

The copolymer of the thermosetting resin is not particularly limited, and examples thereof include the following copolymers.

The acrylic melamine resin is not particularly limited, and examples thereof include acrylic melamine resins.

The acrylic urethane resin is not particularly limited, and examples thereof include acrylic urethane resins.

The ultraviolet absorber of the present invention is preferably used in the production and processing of organic and inorganic materials containing an ultraviolet absorber, because it is less discolored and reduced in weight and can suppress odor even when it is left in a heated environment for a long period of time (at a constant temperature). The organic resin to be combined with the ultraviolet absorber of the present invention is not particularly limited, and examples thereof include the above thermoplastic resins (polymers and copolymers) and thermosetting resins (polymers and copolymers). Examples of the thermoplastic resin include, among polymers of thermoplastic resins, (meth) acrylic resins (polymethyl methacrylate), ester resins (polyethylene terephthalate: PET), polycarbonate ester resins (polycarbonate: PC), styrene resins (polystyrene: PS), cycloolefin resins (cycloolefin polymer: COP); among the copolymers of the thermoplastic resin, an acrylonitrile-butadiene-styrene copolymer (acrylonitrile-butadiene-styrene copolymer: ABS) can be preferably used, and among the thermosetting resins, for example, a urea-formaldehyde resin (urea-formaldehyde resin), a melamine resin (melamine resin), and an acrylic melamine resin (acrylic melamine resin) can be preferably used. Among them, a thermoplastic resin is preferably used. Among thermosetting resins, copolymers are preferably used, and for example, acrylic melamine resins (acrylic melamine resins) can be preferably used.

By combining with the ultraviolet absorber of the present invention, an organic resin composition capable of sufficiently and efficiently absorbing light having a wavelength in the range of 250 to 430nm can be obtained. Further, since the ultraviolet absorber of the present invention is excellent in heat resistance, compatibility with an organic resin, and affinity, the organic resin composition containing the ultraviolet absorber of the present invention has excellent appearance, and can maintain no discoloration, maintain transparency, and inhibit yellowing even when used under heating, high temperature, and/or ultraviolet exposure environment during production and processing.

The organic resin composition of the present invention preferably contains the organic resin in an amount of 0.001 mass% or more, more preferably 0.01 mass% or more, and particularly preferably 0.1 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, a composition obtained by mixing, dispersing or dissolving the ultraviolet absorber of the present invention and an organic resin, or a composition obtained by mixing, dispersing or dissolving an ultraviolet absorber in an organic resin. An inorganic compound used for a filler, a silane coupling agent, a primer, and the like may be added to the organic resin composition.

The inorganic material is not particularly limited, and examples thereof include silica materials obtained by a sol-gel method, glass, water glass, low-melting glass, quartz, and silicone resinsAlkoxysilanes, silane coupling agents, metals, metal oxides, minerals, inorganic compounds, and the like. The glass is not particularly limited, and examples thereof include silica, alkali-free glass, and soda glass. The water glass is not particularly limited, and examples thereof include aqueous solutions of water-soluble alkali metal salts, for example, sodium silicate and potassium silicate. The low-melting glass is not particularly limited, and includes, for example, lead oxide (PbO) and anhydrous boric acid (B)₂O₃) Glass as a main component, and the like. The silicone resin is not particularly limited, and examples thereof include methyl silicone resin, methylphenyl silicone resin, and silicone resin modified with an organic resin modified with an epoxy resin, alkyd resin, polyester resin, or the like. The alkoxysilane is not particularly limited, and examples thereof include dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3,3, 3-trifluoropropylmethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. The silane coupling agent is not particularly limited, and examples thereof include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-glycidyloxypropyltrimethoxysilane, N-glycidyloxypropylmethyldimethoxysilane, N-2- (aminoethyl) -3-glycidyloxypropyltrimethoxysilane, and mixtures thereof, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropylethoxysilane and the like. The metal is not particularly limitedExamples thereof include Zn, Fe, Cu, Ni, Ag, Si, Ta, Nb, Ti, Zr, Al, Ge, B, Na, Ga, Ce, V, P and Sb. The metal oxide is not particularly limited, and examples thereof include zinc oxide, titanium oxide, cerium oxide, iron oxide, tin oxide, indium oxide, and antimony oxide. Examples of the mineral include smectite, bentonite, hectorite, and montmorillonite.

Shape of the structural member

The shape of the member is not particularly limited, and may be any shape, and examples thereof include a coating layer, an adhesive, a binder, a flexible film or a rigid plate (plate) member, a powder-like, granular, tablet-like (tablet) member, a master batch, and a molded article.

[1] Coating layer

Specific examples of the application include a coating layer on the surface of a member such as a resin or glass. The coating method is not particularly limited, and examples thereof include a method of applying, spraying, or forming a film on the surface of a member, or a method of preparing a coating film containing the ultraviolet absorber of the present invention, by mixing, dissolving, or dispersing the ultraviolet absorber of the present invention, a resin, a paint, a silica material, glass, a solvent dispersion, or the like.

[2] Adhesive agent

Specific examples of the application are not particularly limited, and examples thereof include adhesives obtained by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in an organic adhesive (organic resin, synthetic rubber, starch, glue, and the like) or an inorganic adhesive (silica, ceramics, cement, solder, water glass, and the like) applied to various materials and members.

[3] Adhesive agent

Specific examples of the application are not particularly limited, and include adhesives obtained by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in adhesives (organic resins, organic oligomers, organic resin monomers, rubber adhesives, starch, glue, silicone adhesives, silane coupling agent adhesives, and the like) applied to various materials and members.

[4] Film

Specific examples of the application are not particularly limited, and examples thereof include a member obtained by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in a film-like resin, glass, or a silicon oxide precursor having flexibility or pliability. The film may be a single layer film, a base film, a multilayer film having one or more layers formed on a substrate according to various uses, or a substrate with a film, and when a plurality of layers are formed, at least one layer of the film contains the ultraviolet absorber of the present invention. It can also be used for a film-like resin containing the ultraviolet absorber of the present invention, glass, or an interlayer film of a multi-layer glass.

[5] Board

Specific examples of the application are not particularly limited, and examples thereof include a member obtained by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in a plate-like (plate) resin or glass.

[6] Powder, granule, tablet (tablet)

Specific examples of the application are not particularly limited, and include, for example, a member obtained by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in a resin or glass in the form of powder, granule, or tablet.

[7] Master batch

Specific examples of the application are not particularly limited, and include, for example, a resin composition in the form of particles or granules obtained by mixing, dissolving or dispersing a coloring material such as an ultraviolet absorber or a pigment of the present invention in a resin or the like as needed. It may be melt-mixed with other resins and used.

[8] Molded article

Specific examples of the application are not particularly limited, and examples thereof include articles molded by mixing, dissolving, and dispersing the ultraviolet absorber of the present invention in a resin or glass.

Additive agent

The composition and member containing the ultraviolet absorber of the present invention may contain various additives to such an extent that the properties thereof are not deteriorated, and the additives are not particularly limited, and examples thereof include additives such as an antioxidant, a heat stabilizer, a weather stabilizer, a light stabilizer, a pigment, a dye, a filler, a plasticizer, an antistatic agent, a nucleating agent, a wetting agent, an antiseptic, a fungicide, a defoaming agent, a stabilizer, an antioxidant, and a chelating agent.

The ultraviolet absorber of the present invention is used in a field where high heat resistance is required, and the kind, shape, use, and the like of a composition and a member are not limited.

The composition and member containing the ultraviolet absorber of the present invention can be a composition containing an ultraviolet absorber having excellent heat resistance, and for example, a transparent resin containing the ultraviolet absorber of the present invention, a coating film or film for transparent glass, or the like can be formed into a coating film or film which does not suffer from yellowing, discoloration, a decrease in ultraviolet absorption ability, or a decrease in transparency for a long period of time from the production to the use.

The use of the ultraviolet absorber of the present invention is not particularly limited, and the ultraviolet absorber can be suitably used in applications where exposure to light having a wavelength of 380 to 400nm, particularly 380 to 430nm, light including sunlight or ultraviolet rays, or light emission from an LED is possible.

The present invention is not particularly limited, and can be used for members and articles used in houses, facilities, transportation materials, displays, and the like; interior and exterior materials such as houses, facilities, and transportation facilities, interior and exterior coatings, and coating films, adhesives, and binders formed from the coatings; films and members for shielding electromagnetic waves and the like generated from precision machinery, electronic and electrical equipment members and various displays; containers or packaging materials for foods, chemicals, pharmaceuticals, cosmetics, and the like; sheets or films for agricultural industry; discoloration inhibitors such as printed matters, dyed materials and dyed pigments; protective films for resin members or various devices; a glass interlayer; a cosmetic; fiber products for clothing and fibers; household interior equipment such as curtains, carpets, wallpaper and the like; a plastic lens; medical instruments such as contact lenses and artificial eyes; optical lenses such as an optical pickup lens, a camera lens, and a biconvex lens; optical filters, backlight display films, prisms, mirrors, photographic materials, displays, and other optical articles and protective films for optical articles; an optical material; a film having a functional optical layer (for example, various optical disk substrate protective films, reflection films, antireflection films, orientation films, polarizing layer protective films, phase difference films, light diffusion films, viewing angle improving films, electromagnetic wave shielding films, antiglare films, light shielding films, brightness improving films, and the like), members, adhesives, and adhesives; optical molded articles such as optical fibers and information recording substrates; a surface protective film for a solar cell; stationery; a marking plate, a marker and the like and a surface coating material thereof; a glass substitute or a surface coating material thereof; glass such as houses, facilities, or transportation materials, and coating materials for glass; lighting glass; members such as fluorescent lamps, mercury lamps, halogen bulbs, and LED lamps; a member for a light source and a coating material for a light source protective glass; window glass such as houses, facilities and transportation materials, window films, and interlayer films for laminated glass.

The organic material composition is not particularly limited except for the use of the organic resin composition, and may be used as a discoloration inhibitor for cosmetics, printed matter, dyed matter, dye and pigment, for example.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(1) Synthesis of ultraviolet absorber

< Synthesis of intermediate Compound >

Intermediates 1 to 5 represented by the following formulae were synthesized.

< intermediate 1>

[ chemical formula 4]

4-bromo-2-nitroaniline (10.0g, 46.1mmol), water (35mL), sodium di (2-ethylhexyl) sulfosuccinate (0.0041g, 0.092mmol, 62.5% aqueous sulfuric acid solution (25mL) were added, and after dissolving by heating, 36% sodium nitrite aqueous solution (10mL) was added dropwise over 30 minutes under ice-cooling, and the mixture was reacted for 30 minutes, then, the previous diazonium salt aqueous solution was added dropwise to an aqueous solution (100mL) containing 2-tert-butyl-p-cresol (7.95g, 48.4mmol) and sodium hydroxide (12.38g, 309.6mmol) under ice-cooling over 1 hour, after the reaction, the reaction mixture was acidified with hydrochloric acid, and the precipitate was filtered, and the filtrate was washed with isopropyl alcohol, thereby obtaining the following intermediate 2.

< intermediate 2>

[ chemical formula 5]

Intermediate 2(3.50g, 8.92mmol), 2m naoh aqueous solution (14mL), zinc powder (5.60g, 85.66mmol) in toluene (30mL) and reacted under heating reflux for 3 hours. After cooling to room temperature, intermediate 1 was obtained by washing with water, solvent distillation, and column purification.

< intermediate 3>

[ chemical formula 6]

A solution of benzoyl chloride (7.05g, 50mmol) in 15mL of DMF was added dropwise to a solution of 4-aminophenol (5.45g, 50mmol) in 20mL of DMF in an ice bath. After the end of the dropwise addition, the mixture was stirred at room temperature for 2 hours and a half. After completion of the reaction, the solution having a pH of 7 was dropped into 500mL of ion-exchanged water, and the precipitated solid was recovered to obtain intermediate 3 as a white solid.

< intermediate 4>

[ chemical formula 7]

Benzoyl chloride (21.4mL, 185mmol) was added dropwise to a solution of 1, 4-phenylenediamine (20.1g, 185mmol), triethylamine (30mL, 284mmol) in 500mL of dichloromethane in an ice bath. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 and a half hours. After the reaction was completed, filtration was performed, water was added to the filtrate to recover the precipitated solid, which was washed with water and recrystallized to obtain intermediate 4 as a white solid.

< intermediate 5>

[ chemical formula 8]

2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (5.00g, 15.8mmol), 4-aminobenzenethiol (2.97g, 23.8mmol), potassium carbonate (4.81g, 34.8mmol) and potassium iodide (0.18g, 1.11mmol) were reacted in 30g DMF at 135 ℃ for 3 hours. After the reaction was complete and after pH adjustment, filtration, water washing, MeOH washing and recrystallization were carried out to give intermediate 5 as a pale yellow solid.

< Synthesis of ligand Compound >.

A ligand represented by the following formula was synthesized.

< ligand >

[ chemical formula 9]

2-aminobiphenyl (13.57g, 80mmol) and triethylamine (9.1g, 90mmol) were dissolved in 300mL THF and oxalyl chloride (5.08g, 40mmol) was slowly added dropwise while stirring on ice. After the end of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the solvent was distilled off, and after suspending the obtained solid in water, a yellow solid was obtained by filtration. The solid was washed with water, cooled diethyl ether to give the ligand as a white solid.

< Synthesis example 1> Synthesis of Compound 1

[ chemical formula 10]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.17g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (45.8mg, 0.05mmol), Xphos (2-dicyclohexylphosphonium-2 ',4',6 '-triisopropylbiphenyl: 2-Dicyclohexylphosphino-2',4',6' -trisisopropylphenyl) (95.1mg, 0.2mmol), potassium hydroxide (786mg, 14mmol), aniline (1.09mL, 12mmol), and ion-exchanged water (5mL) were stirred under Ar conditions at 100 ℃ for 5 hours. After the reaction was completed, ethyl acetate and hydrochloric acid were added, and a solid component was removed by suction filtration, and the solvent was distilled off from the filtrate. MeOH was added to the obtained oily product, and the obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2975cm^-1: O-H telescopic vibration 1412cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),2.38(s,3H,-CH ₃),5.98(s,1H,NH),7.05(t,1H),7.14(s,1H),7.17(d,1H),7.21(d,2H),7.35(t,2H),7.41(s,1H),7.80(t,1H),8.02(s,1H),11.72(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),97.9,118.5,119.0,119.5,122.5,123.2,128.1,129.6(CH_{Fragrance composition}),125.6,139.0,141.9,143.2,144.1(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),139.1(-C _{Fragrance composition}-C-(CH₃)₃),146.4(-C _{Fragrance composition}-OH)。

< Synthesis example 2> Synthesis of Compound 2

[ chemical formula 11]

After stirring palladium acetate (22.2mg, 0.1mmol), Xphos (95.2mg, 0.2mmol), ion-exchanged water (10. mu.L), and tert-butanol 20mL under Ar at 110 ℃ for 2 minutes, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.14g, 10mmol), potassium carbonate (1.93g, 14mmol), and p-anisidine (1.35g, 11mmol) were further added, and the mixture was heated and stirred for 2 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2961cm^-1: O-H telescopic vibration 1448cm^-1，1310cm^-1: extension vibration of triazole ring 1034cm^-1: C-O-C symmetric expansion and contraction.

¹H-NMR(CDCl₃:400MHz):δ1.48(s,9H,-C-(CH ₃)₃),2.37(s,3H,-CH ₃),3.84(s,3H,-CH ₃),5.76(s,1H,-NH-),6.93(d,2H),7.07(d,1H),7.12(s,1H),7.13(s,1H),7.19(d,2H),7.76(d,1H),7.99(s,1H),11.72(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),55.6(-O-CH₃),95.3,114.9,118.4,119.0,122.4,123.8,128.0(CH_{Fragrance composition}),125.6,134.4,138.7,144.3,145.3,146.4,156.3(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),138.9(-C _{Fragrance composition}-C-(CH₃)₃)。

< Synthesis example 3> Synthesis of Compound 3

[ chemical formula 12]

After stirring palladium acetate (22.0mg, 0.1mmol), Xphos (95.2mg, 0.2mmol), ion-exchanged water (10. mu.L), and 20mL of t-butanol under Ar at 110 ℃ for 2 minutes, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), potassium carbonate (1.93g, 14mmol), and 4-nitroaniline (1.52g, 11mmol) were further added, and the mixture was stirred with heating for 2 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2977cm^-1: O-H telescopic vibration 1569cm^-1，1373cm-¹: N-O telescopic vibration 1441cm^-1，1322cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.50(s,9H,-C-(CH ₃)₃),2.39(s,3H,-CH ₃),6.46(s,1H,-NH-),7.10(d,2H),7.19(s,1H),7.31(d,1H),7.69(s,1H),7.64(d,1H),8.06(d,1H),8.20(d,2H),11.67(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),105.6,114.9,119.2,124.3,126.2,128.8(CH_{Fragrance composition}),119.3,140.3,146.7,149.0(C _{Fragrance composition}),128.4(C _{Fragrance composition}-CH₃),139.2(-C _{Fragrance composition}-C-(CH₃)₃)。

< Synthesis example 4> Synthesis of Compound 4

[ chemical formula 13]

After stirring 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (45.6mg, 0.05mmol), Xphos (95.2mg, 0.2mmol), potassium hydroxide (785mg, 14mmol), 1-naphthylamine (1.58g, 11mmol) and ion-exchanged water (5mL) under Ar conditions at 100 ℃ for 30 minutes, 3mL of toluene was added and the mixture was stirred with heating for 5 hours. After completion of the reaction, toluene and hydrochloric acid were added and washed with water, solid components were removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography to obtain the objective substance as a yellow solid.

FT-IR：2953cm^-1: O-H stretching vibration; 1437cm^-1，1396cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.47(s,9H,-C-(CH ₃)₃),2.36(s,3H,-CH ₃),6.16(s,1H,-NH-),7.05(s,1H),7.12(s,1H),7.24(d,1H),7.47～7.55(m,4H),7.79(t,1H),7.81(d,1H),7.91(d,1H),7.99(s,1H),8.05(d,1H),11.67(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.3(-C-(CH₃)₃),97.7,118.4,119.0,122.1,122.7,124.8,126.0,126.2,126.4,128.0,128.6(CH_{Fragrance composition}),125.6,134.8,137.6,144.1,145.2.146.4(C _{Fragrance composition}),128.6(C _{Fragrance composition}-CH₃),138.9(-C _{Fragrance composition}-C-(CH₃)₃)。

< Synthesis example 5> Synthesis of Compound 5

[ chemical formula 14]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (9.48g, 30mmol), tris (dibenzylideneacetone) dipalladium (0) (140mg, 0.15mmol), Xphos (283mg, 0.6mmol), potassium hydroxide (2.34g, 42mmol), N-methylaniline (5.00mL, 47mmol), and ion-exchanged water (15mL) were heated and stirred under Ar conditions at 100 ℃ for 2 hours and 30 minutes. After completion of the reaction, ethyl acetate and hydrochloric acid were added to remove the solid content by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the target substance as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1412cm^-1，1359cm^-1: the triazole ring vibrates telescopically.¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),2.38(s,3H,-C-CH ₃),3.42(s,3H,-N-CH ₃),7.13～7.19(m,6H),7.36(t,2H),7.65(d,1H),8.02(s,1H),11.74(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),41.1(-N-CH₃),99.3,117.3,124.0,128.0(CH_{Fragrance composition}),125.6,138.7,144.3,148.6,148.7(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),138.9(-C _{Fragrance composition}-C-(CH₃)₃),146.4(-C _{Fragrance composition}-OH)。

< Synthesis example 6> Synthesis of Compound 6

[ chemical formula 15]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (9.87g, 31mmol), tris (dibenzylideneacetone) dipalladium (0) (137mg, 0.15mmol), Xphos (287mg, 0.6mmol), potassium hydroxide (2.39g, 43mmol), diphenylamine (8.32g, 49mmol), ion-exchanged water (15mL) were heated with stirring under Ar conditions at 100 ℃ for 24 hours. After completion of the reaction, ethyl acetate and hydrochloric acid were added, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1412cm^-1，1370cm^-1: the triazole ring vibrates telescopically.¹H-NMR(CDCl₃:400MHz):δ1.48(s,9H,-C-(CH ₃)₃),2.37(s,3H,-CH ₃),7.10(t,2H),7.13～7.16(m,5H),7.28～7.34(m,6H),7.75(d,1H),8.00(s,1H),11.63(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),107.3,117.8,119.1,123.8,125.0,126.7,128.3,129.5(CH_{Fragrance composition}),125.3,125.5,128.1,129.0,139.7,143.8,147.4,147.8(C _{Fragrance composition}),128.2(C _{Fragrance composition}-CH₃),139.0(-C _{Fragrance composition}-C-(CH₃)₃),146.5(-C _{Fragrance composition}-OH)。

< Synthesis example 7> Synthesis of Compound 7

[ chemical formula 16]

After stirring palladium acetate (44.0mg, 0.2mmol), Xphos (192.2mg, 0.4mmol), ion-exchanged water (10. mu.L), and 20mL of t-butanol under Ar at 110 ℃ for 2 minutes, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), potassium carbonate (3.86g, 28mmol), and 1, 4-phenylenediamine (540.7mg, 5mmol) were further added, and the mixture was heated and stirred for 24 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2978cm^-1: O-H stretching vibration; 1449cm^-1，1375cm^-1: the triazole ring vibrates telescopically.¹H-NMR(CDCl₃:400MHz):δ1.49(s,18H,-C-(CH ₃)₃),2.38(s,6H,-CH ₃),5.90(s,2H,-NH-),7.13～7.17(m,4H),7.24(s,4H),7.32(s,2H),7.81(d,2H),8.02(s,2H),11.71(s,2H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),96.7,118.5,119.0,122.1,122.8,128.1(CH_{Fragrance composition}),146.4(C _{Fragrance composition}),125.6(C _{Fragrance composition}-CH₃),139.0(-C _{Fragrance composition}-C-(CH₃)₃)。

< Synthesis example 8> Synthesis of Compound 8

[ chemical formula 17]

After stirring 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (45.8mg, 0.05mmol), Xphos (95.3mg, 0.2mmol), potassium hydroxide (786mg, 14mmol), 2' -aminoacetophenone (1.8mL, 12mmol), and ion-exchanged water (5mL) under Ar conditions at 100 ℃ for 30 minutes, 3mL of toluene was added, and the mixture was stirred with heating for 4 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2949cm^-1: O-H stretching vibration; 1632cm^-1: c ═ O stretching vibration; 1455cm^-1，1390cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.50(s,9H,-C-(CH ₃)₃),2.39(s,3H,-CH ₃),2.68(s,3H,-CH ₃),6.85(t,1H),7.16(s,1H),7.35(d,1H),7.40(t,1H),7.46(d,1H),7.73(s,1H),7.86～7.90(m,2H),8.05(s,1H),10.77(s,1H,-NH-),11.65(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),28.2(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),105.7,115.0,117.9,118.5,119.2,126.1,128.2,128.5,132.6,134.7(CH_{Fragrance composition}),120.1,125.5,140.1,140.2,143.6,146.6,146.7(C _{Fragrance composition}),128.2(C _{Fragrance composition}-CH₃),139.1(-C _{Fragrance composition}-C-(CH₃)₃),201.6(-(C＝O)-)。

< Synthesis example 9> Synthesis of Compound 9

[ chemical formula 18]

After 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (46.0mg, 0.05mmol), Xphos (95.2mg, 0.2mmol), potassium hydroxide (787mg, 14mmol), 2-aminobenzophenone (2.38g, 12mmol) and ion-exchanged water (5mL) were stirred under Ar conditions at 100 ℃ for 30 minutes, 3mL of toluene was further added, and the mixture was stirred with heating for 4 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2969cm^-1: O-H stretching vibration; 1743cm^-1: c ═ O stretching vibration; 1451cm^-1，1359cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.50(s,9H,-C-(CH ₃)₃),2.39(s,3H,-CH ₃),6.85(t,1H),7.16(s,1H),7.38(d,1H),7.39(t,1H),7.50(t,2H),7.56～7.61(m,3H),7.74～7.76(m,3H),7.88(d,2H),8.06(s,1H),10.24(s,1H,-NH-),11.66(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),104.0,115.9,118.1,118.6,119.2,125.4,128.2,128.4,129.6,131.8,134.2,134.9(CH_{Fragrance composition}),121.3,125.6,139.4,139.9,140.6,143.7,146.5,146.6(C _{Fragrance composition}),128.2(C _{Fragrance composition}-CH₃),139.1(-C _{Fragrance composition}-C-(CH₃)₃),199.2(-(C＝O)-)。

< Synthesis example 10> Synthesis of Compound 10

[ chemical formula 19]

Intermediate 4(317mg, 1.49mmol), intermediate 1(369mg, 1.17mmol), tris (dibenzylideneacetone) dipalladium (0) (92.8mg, 0.1mmol), 4, 5-bis diphenylphosphino-9, 9-dimethylxanthene (120mg, 0.21mmol), cesium carbonate (658mg, 2.02mmol) were dissolved in 5ml of dmf and stirred under Ar conditions at 150 ℃ for 20 h. After completion of the reaction, the solid content was removed by filtration, and the solvent was distilled off from the filtrate. The obtained oily product was separated and purified by column chromatography and recrystallization to obtain the target specific substance as a yellow solid.

FT-IR：2974cm^-1: O-H stretching vibration; 1639cm^-1: c ═ O stretching vibration; 1412cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),2.38(s,3H,-CH ₃),7.14～7.17(m,2H),7.24(d,2H),7.37(d,1H),7.52(t,2H),7.58(t,1H),7.64(d,2H),7.79～7.82(m,2H),7.90(d,2H),8.02(s,1H),11.71(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),97.4,118.5,119.0,120.6,121.8,122.9,127.0,128.1,128.8,131.9(CH_{Fragrance composition}),125.6,132.9,135.0,138.5,139.0,143.5,144.1(C _{Fragrance composition}),139.0(-C _{Fragrance composition}-C-(CH₃)₃),146.4(-C _{Fragrance composition}-OH),165.6(-CONH-)。

< Synthesis example 11> Synthesis of Compound 11

[ chemical formula 20]

After stirring 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (46.0mg, 0.05mmol), Xphos (95.1mg, 0.2mmol), potassium hydroxide (787mg, 14mmol), 2-aminobenzophenone (3.00g, 13mmol) and ion-exchanged water (5mL) under Ar conditions at 100 ℃ for 30 minutes, 3mL of toluene was added, and the mixture was stirred with heating for 4 hours. After completion of the reaction, toluene and hydrochloric acid were added, and after washing with water, the solid content was removed by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the target substance as a red solid.

FT-IR：2970cm^-1: O-H stretching vibration; 1742cm^-1: c ═ O stretching vibration; 1437cm^-1，1359cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.51(s,9H,-C-(CH ₃)₃),2.40(s,3H,-CH ₃),7.19(s,1H),7.44(d,1H),7.61(t,1H),7.74(d,1H),7.76～7.84(m,4H),7.96(d,2H),8.08(d,2H),8.31(d,1H),8.35(d,1H),11.59(s,1H,-NH-),11.61(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),108.4,118.7,118.9,119.3,120.3,126.3,127.0,128.8,1336,134.2,135.2(CH_{Fragrance composition}),133.1,134.7,134.9,139.2,140.6,143.5,146.7,148.3(C _{Fragrance composition}),128.3(C _{Fragrance composition}-CH₃),139.1(-C _{Fragrance composition}-C-(CH₃)₃),185.9(-(C＝O)-)。

< Synthesis example 12> Synthesis of Compound 12

[ chemical formula 21]

After stirring palladium acetate (22.0mg, 0.1mmol), Xphos (95.2mg, 0.2mmol), ion-exchanged water (10. mu.L) and 20mL of t-butanol under Ar at 110 ℃ for 2 minutes, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), potassium carbonate (1.93g, 14mmol) and benzamide (1.33g, 11mmol) were further added, and the mixture was heated and stirred for 24 hours. After the reaction was completed, water was added to recover a solid by suction filtration, and the solid was dissolved in toluene to recover a solid. The obtained crude product was purified by recrystallization to obtain the target substance as a white solid.

FT-IR：2957cm^-1: O-H stretching vibration; 1649cm^-1: c ═ O stretching vibration; 1440cm^-1，1360cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.50(s,9H,-C-(CH ₃)₃),2.39(s,3H,-CH ₃),7.18(s,1H),7.51～7.56(m,3H),7.59(t,1H),7.91～7.94(m,3H),7.98(s,1H),8.08(s,1H),8.50(a,1H),11.65(s,1H,-NH-)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),106.4,118.3,119.4,123.0,127.1,128.7,130.0,132.2(CH_{Fragrance composition}),125.5,134.7,137.0,140.3,143.2(C _{Fragrance composition}),128.3(C _{Fragrance composition}-CH₃),139.2(-C _{Fragrance composition}-C-(CH₃)₃),146.7(-C _{Fragrance composition}-OH),165.9(-CONH-)。

< Synthesis example 13> Synthesis of Compound 13

[ chemical formula 22]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (46.8mg, 0.05mmol), Xphos (97.3mg, 0.2mmol), potassium hydroxide (790mg, 14mmol), pyrrole (1.50mL, 22mmol), ion-exchanged water (5mL) were heated under Ar conditions and at 100 ℃ with stirring for 24 hours. After completion of the reaction, toluene and hydrochloric acid were added to remove the solid content by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1412cm^-1，1358cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.50(s,9H,-C-(CH ₃)₃),2.40(s,3H,-CH ₃),6.23(t,2H),7.19～7.20(m,3H),7.62(d,1H),7.84(s,1H),7.99(d,1H),8.08(s,1H),11.58(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),106.8,111.2,118.9,119.4,119.8,123.1,129.0(CH_{Fragrance composition}),125.4,140.0,141.0,143.1(C _{Fragrance composition}),128.4(C _{Fragrance composition}-CH₃),139.2(-C _{Fragrance composition}-C-(CH₃)₃),146.8(-C _{Fragrance composition}-OH)。

< Synthesis example 14> Synthesis of Compound 14

[ chemical formula 23]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.23g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (48.9mg, 0.05mmol), Xphos (97.9mg, 0.2mmol), potassium hydroxide (768mg, 14mmol), carbazole (2.51g, 22mmol), ion-exchanged water (5mL) were heated and stirred under Ar conditions at 100 ℃ for 30 minutes, and then toluene was added and heated and stirred for 24 hours. After completion of the reaction, toluene and hydrochloric acid were added to remove the solid content by suction filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1402cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.52(s,9H,-C-(CH ₃)₃),2.42(s,3H,-CH ₃),7.23(s,1H),7.34(t,2H),7.43～7.50(d,4H),7.69(d,1H),8.13～8.16(m,5H),11.61(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ21.0(-CH₃),29.6(-C-(CH₃)₃),35.5(-C-(CH₃)₃),109.8,115.1,119.2,119.5,120.5,120.5,126.2,127.6,129.2(CH_{Fragrance composition}),123.7,125.4,137.0,140.8,141.7,143.2(C_{Fragrance composition}),128.5(C _{Fragrance composition}-CH₃),139.3(-C _{Fragrance composition}-C-(CH₃)₃),146.9(-C _{Fragrance composition}-OH)。

< Synthesis example 15> Synthesis of Compound 15

[ chemical formula 24]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (1.60g, 5mmol), tris (dibenzylideneacetone) dipalladium (0) (68.7mg, 0.075mmol), Xphos (73.0mg, 0.15mmol), sodium-tert-butoxide (1.44g, 15mmol), piperidine (852mg, 10mmol), toluene (10mL) were heated under Ar conditions at 70 ℃ with stirring for 4 hours. After completion of the reaction, hydrochloric acid was added to wash with water, the solid content was removed by filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1401cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),1.62～1.67(_m,2H,-N-CH₂-CH₂-CH ₂),1.77(quin,4H，-N-CH₂-CH ₂-CH₂-),2.37(s,3H，-CH ₃),3.25(t,4H),-N-C ₂H-CH₂-CH₂-),7.06(s,1H),7.13(ts,1H),7.31(d,1H),7.74(d,2H),8.01(s,1H),11.75(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),24.2(-N-CH₂-CH₂-CH ₂),25.8(-N-CH₂-CH₂-CH₂-),29.6(-C-(CH₃)₃),35.3(-C-(CH₃)₃),51.2(-N-CH₂-CH₂-CH₂-),98.1,117.5,119.0,123.9,127.9(CH_{Fragrance composition}),125.7,128.0,138.5,144.3,152.2(C _{Fragrance composition}),127.9(C _{Fragrance composition}-CH₃),138.9(-C _{Fragrance composition}-C-(CH₃)₃),147.3(-C _{Fragrance composition}-OH)。

< Synthesis example 16> Synthesis of Compound 16

[ chemical formula 25]

Intermediate 3(409mg, 1.92mmol), intermediate 1(424mg, 1.17mmol), copper iodide (22.3mg, 1.17X 10mmol)^-2mmol), ligand (52.2mg, 1.33X 10^-2mmol), tripotassium phosphate (538mg, 2.53mmol) were dissolved in 4mL of DMF and stirred under Ar at 100 ℃ for 24 hours. After the reaction was completed, the reaction mixture was diluted, filtered, separated, distilled to remove the solvent, and subjected to column chromatography and recrystallization to obtain the target substance as a white solid. The characteristic values thereof are expressed as follows.

FT-IR：2974cm^-1: O-H stretching vibration; 1643cm^-1: c ═ O stretching vibration; 1402cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),2.38(s,3H,-CH ₃),7.14～7.16(m,3H),7.26(s,1H),7.30(d,1H),7.52(t,2H),7.58(t,1H),7.70(d,2H),7.84(s,1H,CONH),7.90(m,3H),8.03(s,1H),11.58(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),102.1,119.0,119.2,120.5,122.1,122.5,127.0,128.6,128.9,132.0(CH_{Fragrance composition}),125.5,134.4,134.9,139.7,143.3,152.7,157.7(C _{Fragrance composition}),128.2(C _{Fragrance composition}-CH₃),139.1(-C _{Fragrance composition}-C-(CH₃)₃),146.6(-C _{Fragrance composition}-OH),165.7(-CONH-)。

< Synthesis example 17> Synthesis of Compound 17

[ chemical formula 26]

Phenylboronic acid (1.35g, 11mmol), 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (3.15g, 10mmol), tris (dibenzylideneacetone) dipalladium (0) (90mg, 0.1mmol), Xphos (190mg, 0.4mmol), potassium carbonate (3.32g, 24mmol) were added to 150mL of 1-butanol and stirred under Ar at 100 ℃ for 2 h. After the reaction was completed, the reaction mixture was filtered, and the filtrate was cooled to obtain a product as a white solid.

FT-IR：2962cm^-1: O-H stretching vibration; 1443cm^-1，1392cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.51(s,9H,-C-(CH ₃)₃),2.40(s,3H,-CH ₃),7.19(s,1H),7.42(t,1H),7.51(t,2H),7.69(d,2H),7.75(d,1H),7.99(d,1H),8.08(s,1H),8.12(s,1H),11.77(s,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),114.9,117.7,119.4,127.5,127.9,128.4,128.8,129.0(CH_{Fragrance composition}),125.5,140.6,141.0,142.2,143.3(C _{Fragrance composition}),128.3(C _{Fragrance composition}-CH₃),139.2(-C _{Fragrance composition}-C-(CH₃)₃),146.8(-C _{Fragrance composition}-OH)。

< Synthesis example 18> Synthesis of Compound 18

[ chemical formula 27]

Phenylboronic acid (2.70g, 22mmol), 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (7.15g, 20mmol), tris (dibenzylideneacetone) dipalladium (0) (180mg, 0.2mmol), Xphos (380mg, 0.8mmol), potassium carbonate (6.64g, 48mmol) were added to 200mL of 1-butanol and stirred under Ar at 100 ℃ for 2 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was cooled to obtain a product as a white solid.

FT-IR：2959cm^-1: O-H stretching vibration; 1457cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.41(s,9H,-C-(CH ₃)₃),1.53(s,9H,-C-(CH ₃)₃),7.42～7.44(m,2H),7.51(t,2H),7.70(d,2H),7.76(d,1H),8.00(d,1H),8.10(s,1H),8.31(s,1H),11.78(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ29.6,31.5(-C-(CH₃)₃),34.6,35.7(-C-(CH₃)₃)114.9,116.1,117.8,125.2,127.5,127.9,128.3,129.0(CH_{Fragrance composition}),125.3,140.7,140.8,142.2,143.3(C _{Fragrance composition}),138.6,141.7(-C _{Fragrance composition}-C-(CH₃)₃),146.7(-C _{Fragrance composition}-OH)。

< Synthesis example 19> Synthesis of Compound 19

[ chemical formula 28]

Intermediate 1(0.10g, 0.28mmol), 4- (benzyloxycarbonyl) phenylboronic acid (0.0746g, 0.29mmol), palladium acetate (0.0025g, 0.0111mmol), triphenylphosphine (0.0087g, 0.0333mmol), and sodium carbonate (0.0706g, 0.0666mmol) were added, and after drying under reduced pressure for 2 hours, propanol/water (7.7mL/0.3mL) was added under a nitrogen atmosphere, and the mixture was heated and stirred at 90 to 100 ℃ for 24 hours. After the reaction was completed, the precipitate obtained by the acid treatment was filtered and subjected to column purification to obtain the target substance as a white solid.

FT-IR：2866cm^-1: O-H stretching vibration; 1716cm^-1: c ═ O stretching vibration; 1447cm^-1，1357cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.51(s,9H,-C-(CH ₃)₃),2.40(s,3H,-CH ₃),5.41(s,2H,-CH ₂-),7.20(s,1H),7.40～7.44(m,3H),7.48(d,2H),7.75(d,3H),8.00(d,2H),8.11(d,2H),8.21(d,2H),11.68(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),115.6,118.1,119.5,128.3,128.7,129.0,130.5(CH_{Fragrance composition}),66.9,127.5,128.0,128.2,136.1,143.2,145.1(C _{Fragrance composition}),128.2(C _{Fragrance composition}-CH₃),139.3(-C _{Fragrance composition}-C-(CH₃)₃),146.9(-C _{Fragrance composition}-OH),167.0(-COO-)。

< Synthesis example 20> Synthesis of Compound 20

[ chemical formula 29]

Intermediate 1(0.10g, 0.28mmol), 4- (phenylcarbamoyl) phenylboronic acid (0.0746g, 0.29mmol), palladium acetate (0.0025g, 0.0111mmol), triphenylphosphine (0.0087g, 0.0333mmol), and sodium carbonate (0.0706g, 0.0666mmol) were added, and after drying under reduced pressure for 2 hours, propanol/water (7.7ml/0.3ml) was added under a nitrogen atmosphere, and the mixture was heated and stirred at 90 to 100 ℃ for 24 hours. After the completion of the reaction, the precipitate obtained by the acid treatment was filtered and subjected to column purification to obtain the target substance as a white solid.

FT-IR：2952cm^-1: O-H stretching vibration; 1656cm^-1: c ═ O stretching vibration; 1441cm^-1，1355cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.51(s,9H,-C-(CH ₃)₃),2.41(s,3H,-CH ₃),7.21(s,1H,CONH),7.12～7.21(m,1H),7.41(t,1H),7.68(d,2H),7.77(d,1H),7.83(m,3H),8.05(m,3H),8.15(d,2H),11.67(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),115.6,119.5,119.5,120.5,127.5,128.2,128.7,129.0,130.5,136.0(CH_{Fragrance composition})66.9,125.5,134.4,134.9,139.3,139.7,143.3,145.1,157.7(C_{Fragrance composition}),128.4(C _{Fragrance composition}-CH₃),139.3(-C _{Fragrance composition}-C-(CH₃)₃),146.9(-C _{Fragrance composition}-OH),166.2(-CONH-)。

< Synthesis example 21> Synthesis of Compound 21

[ chemical formula 30]

Palladium acetate (22.0mg, 0.1mmol), Xphos (95.2mg, 0.2mmol), ion-exchanged water (10. mu.L), t-butanol 7.5g, toluene 7.5g, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), potassium carbonate (1.93g, 14mmol), and xylidine (3.95g, 20mmol) were added, and the mixture was stirred under heating for 48 hours. After the reaction, water, toluene, and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2974cm^-1: O-H stretching vibration; 1454cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.47(s,9H,-C-(CH ₃)₃),2.34(s,6H,-CH ₃),2.36(s,3H,-CH ₃),7.05(d,4H),7.06～7.12(m,5H),7.26(m,1H),7.70(d,1H),7.99(s,1H),11.66(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),105.4,117.5,119.0,125.3,126.2,128.1,130.1(CH_{Fragrance composition}),125.6,133.6,138.9,143.9,144.9,148.2(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),139.4(-C _{Fragrance composition}-C-(CH₃)₃),146.5(-C _{Fragrance composition}-OH)。

< Synthesis example 22> Synthesis of Compound 22

[ chemical formula 31]

Palladium acetate (11.0mg, 0.05mmol), Xphos (48mg, 0.1mmol), ion-exchanged water (5. mu.L), t-butanol 7.5g, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (1.57g, 5mmol), potassium carbonate (1.93g, 14mmol), intermediate 5(2.02g, 5mmol) were added, and the mixture was stirred under heating for 24 hours. After the reaction, water, toluene and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2974cm^-1: O-H stretching vibration; 1428cm^-1，1359cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.48(s,9H,-C-(CH ₃)₃),1.49(s,9H,-C-(CH ₃)₃),2.37(s,3H,-CH ₃),2.38(s,3H,-CH ₃),6.12(s,1H,-NH-),7.16(s,2H),7.21～7.27(m,3H),7.36(dd,1H),7.51～7.56(m,4H),7.82(d,1H),7.86(d,1H),8.34(s,2H),11.59(s,1H,-OH),11.66(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),100.5,114.4,117.8,118.7,119.0,119.1,119.3,123.6,128.4,128.5,128.7,136.0(CH_{Fragrance composition}),123.7,125.4,125.5,139.0,139.1,141.4,141.7,143.3,143.8(C _{Fragrance composition}),128.2,128.3(C _{Fragrance composition}-CH₃),139.47,139.51(-C _{Fragrance composition}-C-(CH₃)₃),146.5,146.7(-C _{Fragrance composition}-OH)。

< Synthesis example 23> Synthesis of Compound 23

[ chemical formula 32]

Palladium acetate (112mg, 0.5mmol), Xphos (476mg, 1.0mmol), ion-exchanged water (50. mu.L), t-butanol 80g, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (15.8g, 50mmol), potassium carbonate (9.67g, 70mmol), and 4-aminophenol (9.82g, 90mmol) were added, and they were stirred with heating for 4 hours. After the reaction, water, toluene and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：3219cm^-1，3034cm^-1: O-H stretching vibration; 1441cm^-1，1373cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.48(s,9H,-C-(CH ₃)₃),2.36(s,3H,-CH ₃),4.75(s,1H,-OH),5.74(s,1H,-NH-),6.86(d,2H),7.05～7.15(m,5H),7.75(d,1H),7.99(s,1H),11.71(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.3(-C-(CH₃)₃),95.2,116.3,118.4,122.4,123.9,128.0(CH_{Fragrance composition}),125.6,134.5,138.7,144.2,145.2,152.1(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),138.9(-C _{Fragrance composition}-C-(CH₃)₃),146.4(-C _{Fragrance composition}-OH)。

< Synthesis example 24> Synthesis of Compound 24

[ chemical formula 33]

Palladium acetate (112mg, 0.5mmol), Xphos (476mg, 1.0mmol), ion-exchanged water (50. mu.L), t-butanol 80g, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (15.8g, 50mmol), potassium carbonate (9.67g, 70mmol), and 2- (4-aminophenyl) ethanol (10.36g, 75mmol) were added, and the mixture was stirred with heating for 4 hours. After the reaction, water, toluene and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：3237cm^-1，3042cm^-1: O-H stretching vibration; 1453cm^-1，1375cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.42(t,1H,-OH),1.49(s,9H,-C-(CH ₃)₃),2.37(s,3H,-CH ₃),2.87(t,2H,-CH ₂-),3.88(q,2H,-CH ₂-),5.92(s,1H,-NH-),7.16～7.23(m,6H),7.36(s,1H),7.79(d,1H),8.01(s,1H),11.70(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),38.6,63.8(-CH₂-),93.74,118.5,119.0,120.1,123.0,128.1,130.1(CH_{Fragrance composition}),125.6,132.8,138.9,139.0,140.3,143.5,144.1,148.2(C _{Fragrance composition})146.4(-C _{Fragrance composition}-OH)。

< Synthesis example 25> Synthesis of Compound 25

[ chemical formula 34]

After adding compound 23(1.94g, 5mmol), triethylamine (660mg, 6.5mmol) and toluene 20mL to a beaker, methacryloyl chloride (590mg, 5.5mmol) was added and the mixture was stirred at room temperature for 30 minutes. After the reaction, hexane was added, and the solid which had precipitated was recovered and, after washing with methanol, the solid was dissolved in ethyl acetate. After the organic layer was washed with water, the desired substance was obtained as a yellow solid by recrystallization.

FT-IR：3043cm^-1: O-H stretching vibration; 1755cm^-1: c ═ O stretching vibration; 1444cm^-1，1375cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),2.08(s,3H,-CH ₃),2.37(s,3H,-CH ₃),5.77(s,1H),5.95(s,1H,-NH-),6.37(s,1H),7.10～7.23(m,6H),7.37(s,1H),7.80(d,1H),8.02(s,1H),11.68(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ18.4,20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),97.8,118.6,119.0,120.6,122.6,123.0,128.2(CH_{Fragrance composition}),125.6(＝CH₂),135.9,139.0,139.1,143.3,144.0,146.0,146.4(C _{Fragrance composition}),127.2(C _{Fragrance composition}-CH₃),139.5(-C _{Fragrance composition}-C-(CH₃)₃),166.1(-CO-)。

< Synthesis example 26> Synthesis of Compound 26

[ chemical formula 35]

After adding compound 24(2.09g, 5mmol), triethylamine (660mg, 6.5mmol) and toluene to 20mL of the beaker, methacryloyl chloride (590mg, 5.5mmol) was further added, and the mixture was stirred at room temperature for 20 hours. After the reaction, hexane was added to recover the precipitated solid. The solid was dissolved in a mixture of ethyl acetate, toluene, hexane, and methanol, and the upper layer liquid was recovered and then dissolved in ethyl acetate. After the organic layer was washed with water, the desired substance was obtained as a yellow solid by recrystallization.

FT-IR：3041cm^-1: O-H stretching vibration; 1762cm^-1: c ═ O stretching vibration; 1451cm^-1，1353cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.49(s,9H,-C-(CH ₃)₃),1.95(s,3H,-CH ₃),2.37(s,3H,-CH ₃),2.98(t,2H,-CH ₂-),4.36(t,2H,-CH ₂-),5.57(s,1H),5.92(s,1H,-NH-),6.11(s,1H),7.13～7.17(m,4H),7.23(d,2H),7.36(s,1H),7.79(d,1H),8.01(s,1H),11.69(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ18.3,20.9(-CH₃),29.5(-C-(CH₃)₃),34.5,65.3(-CH₂-),35.6(-C-(CH₃)₃),97.4,118.5,119.0,119.9,123.1,130.1(CH_{Fragrance composition}),125.5(＝CH₂),132.3,136.4,138.9,140.3,143.4,144.1,146.4(C _{Fragrance composition}),128.1(C _{Fragrance composition}-CH₃),139.0(-C _{Fragrance composition}-C-(CH₃)₃),166.1(-CO-)。

< Synthesis example 27> Synthesis of Compound 27

[ chemical formula 36]

Palladium acetate (22.0mg, 0.1mmol), Xphos (95.2mg, 0.2mmol), ion-exchanged water (10. mu.L), t-butanol 7.5mL, toluene 7.5mL, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (3.16g, 10mmol), potassium carbonate (1.93g, 14mmol), indole (2.34g, 20mmol) were added, and they were stirred under heating for 24 hours. After the reaction, water, toluene and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid.

FT-IR：2976cm^-1: O-H stretching vibration; 1437cm^-1，1372cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.51(s,9H,-C-(CH ₃)₃),2.41(s,3H,-CH ₃),6.76(d,1H),7.21～7.28(m,3H),7.44(d,1H),7.64～7.74(m,3H),8.00(s,1H),8.07(d,1H),8.12(s,1H),11.60(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ21.0(-CH₃),29.6(-C-(CH₃)₃),35.4(-C-(CH₃)₃),104.6,110.5,111.3,119.0,119.5,120.9,121.4,122.8,125.8,127.9,129.1(CH_{Fragrance composition}),125.4,129.5,135.9,139.1,141.2,143.1(C _{Fragrance composition}),128.5(C _{Fragrance composition}-CH₃),139.3(-C _{Fragrance composition}-C-(CH₃)₃),146.8(-C _{Fragrance composition}-OH)。

< Synthesis example 28> Synthesis of Compound 28

[ chemical formula 37]

Palladium acetate (44.0mg, 0.2mmol), Xphos (192mg, 0.4mmol), ion-exchanged water (20. mu.L), tert-butanol (15g), toluene (15g), 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (6.31g, 20mmol), potassium carbonate (3.86g, 28mmol), and phenothiazine (5.18g, 26mmol) were added thereto, and the mixture was stirred under heating for 24 hours. After the reaction, water, toluene and hydrochloric acid were added, and after washing with water, the solvent was distilled off from the filtrate. The obtained crude product was purified by recrystallization to obtain the target substance as a yellow solid. The 5% weight loss temperature of the present compound was 348 ℃ and the wavelength of the maximum absorption peak (maximum absorption wave) of the present compound in the wavelength region of 350 to 430nm was confirmedLength: lambda [ alpha ]_max) Is 354 nm.

FT-IR：2957cm^-1: O-H stretching vibration; 1465cm^-1，1310cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.55(s,9H,-C-(CH ₃)₃),2.41(s,6H,-CH ₃),6.39(d,2H),6.87～6.94(m,4H),7.11(d,2H),7.21(s,1H),7.45(d,1H),7.95(s,1H),8.12(m,2H),11.66(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ20.9(-CH₃),29.5(-C-(CH₃)₃),35.4(-C-(CH₃)₃),117.4,117.6,119.5,119.9,123.3,127.0,127.2,129.1,129.9(CH_{Fragrance composition}),122.1,125.4,140.8,141.7,143.8,146.8(C _{Fragrance composition}),128.5(C _{Fragrance composition}-CH₃),139.3(-C _{Fragrance composition}-C-(CH₃)₃)。

< Synthesis example 29> Synthesis of Compound 31

[ chemical formula 38]

2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (1.58g, 5mmol), tris (dibenzylideneacetone) dipalladium (0) (68.7mg, 0.075mmol), Xphos (73.1mg, 0.15mmol), sodium tert-butoxide (1.44g, 15mmol), diethylamine (732mg, 10mmol), toluene (10mL) were heated under Ar conditions at 70 ℃ with stirring for 4 hours. After the reaction was completed, hydrochloric acid was added to carry out water washing, and solid components were removed by filtration, and the solvent was distilled off from the filtrate. The obtained crude product was purified by column chromatography and recrystallization to obtain the desired product as a yellow solid.

FT-IR：2975cm^-1: O-H stretching vibration; 1401cm^-1，1370cm^-1: the triazole ring vibrates telescopically.

¹H-NMR(CDCl₃:400MHz):δ1.24(t,6H,-CH₂-CH ₃),1.50(s,9H,-C-(CH ₃)₃),2.38(s,3H,-CH ₃),2.46(q,4H,-CH ₂-CH₃)6.77(s,1H),7.11(s,1H),7.14(d,1H),7.73(d,2H),8.00(s,1H),11.87(s,1H,-OH)。

¹³C-NMR(CDCl₃:400MHz):δ12.6(-N-CH₂-CH₃),20.9(-CH₃),29.6(-C-(CH₃)₃),35.3(-C-(CH₃)₃),45.0(-N-CH₂-CH₃),92.1,117.8,118.9,119.7,127.6(CH_{Fragrance composition}),117.6,123.7,137.1,145.0,146.3(C _{Fragrance composition}),127.9(C _{Fragrance composition}-CH₃),138.4(-C _{Fragrance composition}-C-(CH₃)₃),147.6(-C _{Fragrance composition}-OH)。

Further, as the compounds 29 and 30, reagents manufactured by tokyo chemical industry co.

(2) 5% weight loss temperature

The compound of the present invention was prepared using a differential thermal gravimetric simultaneous measurement apparatus (TG/DTA 6200, manufactured by SII) at a temperature rise temperature: 10 ℃/min, measurement range: weight change measurements were made at 25 ℃ to 550 ℃ and the temperature at which weight change (TG) was reduced by 5% by weight was read (tables 1A-D).

With compound 29, compound 30, compound having no Y as a 2-phenylbenzotriazole derivative having no bonding group represented by formula (I) or (II)¹(Y¹Alkyl group) was compared with Compound 31(244 ℃ C.) of comparative example 3, and it was confirmed that the compound had a structure containing Y¹The ultraviolet absorber compounds 1 to 28 of the present invention having the formula (I) or the formula (II) have a 5% weight loss temperature of 250 ℃ or higher, and are excellent in heat resistance.

Among them, compound 20(380 ℃) is related to compound 16(352 ℃) and compound 1(292 ℃) is related to compound 17(271 ℃), and therefore, in formula (I), the order of X oxygen atom < l ═ 0< X nitrogen atom is excellent in heat resistance.

Further, compound 1(292 ℃), compound 2(322 ℃), compound 3(300 ℃), compound 4(326 ℃), compound 5(284 ℃), compound 6(290 ℃), compound 7(348 ℃), compound 8(280 ℃), compound 10(374 ℃), compound 11(382 ℃), compound 12(319 ℃), compound 14(329 ℃), compound 16(352 ℃), compound 19(346 ℃), compound 20(380 ℃), compound 21(324 ℃), compound 22(356 ℃), compound 23(302 ℃), compound 24 (326 ℃), compound 25(339 ℃), compound 26(336 ℃), compound 27(297 ℃), compound 28(348 ℃) had a 5% weight loss temperature of 280 ℃ or more, compound 2(322 ℃), compound 3(300 ℃), compound 4 (348 ℃), compound 7(2 ℃), and, The 5% weight loss temperature of Compound 10(374 ℃ C.), Compound 11(382 ℃ C.), Compound 12(319 ℃ C.), Compound 14(329 ℃ C.), Compound 16(352 ℃ C.), Compound 19(346 ℃ C.), Compound 20(380 ℃ C.), Compound 21(324 ℃ C.), Compound 22(356 ℃ C.), Compound 23(302 ℃ C.), Compound 24(327 ℃ C.), Compound 25(339 ℃ C.), Compound 26(336 ℃ C.) and Compound 28(348 ℃ C.) is 300 ℃ or higher. In addition, Y in the compound of formula (I) (l ═ 1, X is a nitrogen atom)¹A compound having a molecular weight of 190 or more (compound 7: 348 ℃, compound 10: 374 ℃, compound 11: 382 ℃, compound 22: 356 ℃), a compound having a molecular weight of 1 or more, wherein X is an oxygen atom, or a compound having a molecular weight of 0 or more, and Y is a hydrogen atom¹A compound having an oxygen-containing group introduced thereto (compound 16: 352 ℃, compound 19: 346 ℃, compound 20: 380 ℃), Y in the formula (I)¹The compound having a heterocycle or condensed ring containing a hetero atom (nitrogen atom or oxygen atom) having two or more rings (excellent in the compound 7: 348 ℃, the compound 11: 382 ℃, the compound 22: 356 ℃, particularly the compound 11 having three or more rings) and the heterocyclic compound containing a hetero atom (sulfur atom) in the formula (II) (excellent in the compound 28: 348 ℃) are excellent in heat resistance because the 5% weight reduction temperature is 340 ℃ or more.

In addition, due to the presence of Compound 1(292 ℃ C.)>Compound 6(290 ℃ C.)>Compound 5(284 ℃) and is present as Y²Is a hydrogen atom>Aromatic hydrocarbon radical>The order of aliphatic hydrocarbon groups, Compound 14 (tricyclic: 329 ℃ C.), Compound 28 (tricyclic: 348 ℃ C.)>Chemical combinationObject 27 (bicyclic 297 ℃ C.)>Since Compound 15 (monocyclic: 260 ℃ C.) and Compound 13 (monocyclic: 258 ℃ C.) are related, it is suggested that the heat resistance is improved as the number of constituent rings of the polycyclic ring of formula (II) is increased.

In addition, since Compound 19(346 ℃ C.), Compound 20(380 ℃ C.) were present>Compound 17(271 ℃ C.) is related to and present in Compound 10(374 ℃ C.)>Relationship between Compound 1(292 ℃ C.), and Presence of Compound 22(356 ℃ C.), Compound 7(348 ℃ C.)>Compound 1(292 ℃ C.), accordingly, in formula (I), Y¹An aromatic hydrocarbon group having a substituent of an ester group or an amide group at the base end, or in the formula (I), Y¹The aromatic hydrocarbon group having a substituent containing a sulfur group or a nitrogen group at the base end thereof is excellent in heat resistance.

Owing to the presence of Compound 11(382 ℃ C.), Compound 4(326 ℃ C.)>Compound 1(292 ℃ C.) is suggested, therefore, in formula (I), Y¹The aromatic hydrocarbon group has two or more condensed rings or has a substituent on the aromatic hydrocarbon group, and the substituent forms a ring together with the aromatic hydrocarbon group, thereby improving the heat resistance.

(3) The wavelength of the maximum absorption peak in the wavelength region of 350 to 430nm, the molar absorption coefficient, and the slope (absolute value) of the peak

Compounds 1,2, 4 to 6, 8 to 21, 23 to 27, and 29 to 31 were diluted with 100. mu.M chloroform, compounds 3, 7, and 22 were diluted with 50. mu.M chloroform and contained in 10mm quartz cuvettes, absorption spectra were measured using an ultraviolet-visible infrared spectrophotometer (manufactured by Hitachi high-tech science, Japan, UH4150V), and the wavelength of the maximum absorption peak in the wavelength region of 350-430nm (maximum absorption wavelength: lambda.) was read from these spectra_max) (tables 1A-D). Further, the molar absorptivity (maximum molar absorptivity:. epsilon.: ε) of each of these peaks was determined by the following formula_max) (tables 1A-D).

Molar absorptivity: epsilon_max(L/(mol · cm)) ═ a: absorbance/[ c: molar concentration (mol/L). times.l: optical path length of cuvette (cm)]。

The intersection of the absorption spectrum and the base line (line where the slope of the absorption spectrum at 350 to 550nm is 0) was defined as the peak end (example: FIG. 1), and the absolute value of the slope on the long wavelength side of the absorption peak in the wavelength region of 350 to 430nm was determined by the following formula (tables 1A to D).

With respect to compound 11, since it also has absorption after 430nm, it is difficult to draw a baseline. Therefore, the end point of the maximum absorption peak in the wavelength region of 350 to 430nm is defined as the peak end.

A slope of | (absorbance at peak end-absorbance at maximum absorption peak in wavelength region of 350 to 430 nm)/(absorption wavelength at peak end-wavelength at maximum absorption peak in wavelength region of 350 to 430 nm) |.

As a result, the compounds 1 to 27 of the present invention have absorption peaks in the ultraviolet wavelength region to the visible light short wavelength region, and have a function as an ultraviolet absorber when added to a film or a resin, for example.

The benzotriazole compounds 1 to 27 of the present invention, in which the formulas (I) and (II) were introduced into benzotriazole in the absorption peak in the wavelength region of 350 to 430nm, were found to have absorption peaks at 355nm or more in the longer wavelength region and excellent ultraviolet absorption, as compared with the conventional long-wavelength absorption type ultraviolet absorber (compound 29). Among them, the absorption peaks of compound 1(386nm), compound 4(387nm), compound 11(380nm), compound 14(376nm), compound 15(375nm), compound 22(380nm), compound 23(389nm), compound 24(388nm), compound 25(385nm), compound 26(388nm), and compound 27(370nm) were 370nm or more, the absorption peaks of compound 2(390nm), compound 3(396nm), compound 5(391nm), compound 7(395nm), and compound 10(391nm) were 390nm or more, the absorption peaks of compound 6(406nm), compound 8(401nm), compound 9(411nm), and compound 21(413nm) were 400nm or more, and the long-wavelength absorption was excellent.

In formula (I), l is 1, X is a nitrogen atom, and Y is²In the case of a hydrogen atom, at Y, in comparison with Compound 1¹In which a compound having an oxygen-containing group or a nitrogen-containing group, or Y¹Is a benzene ring in the benzeneThe absorption peaks of the compounds having 1 substituent on the ring (compounds 2, 3, 7, 8, 9,10, 22 to 26) are shifted to a long wavelength and are all 380nm or more.

In addition, in Y²The absorption peak of the compound having hydrogen atom introduced therein (compound 1: 386nm) is 375nm or more, but the absorption peak is determined by adding hydrogen atom to Y²When an aliphatic hydrocarbon group (compound 5: 391nm) is introduced, an absorption peak having a long wavelength shifted to 390nm or more is obtained; in addition, by adding in Y²When an aromatic hydrocarbon group (compound 6: 406nm, compound 21: 413nm) was introduced, an absorption peak shifted to 400nm or more in the long wavelength was obtained.

On the other hand, the absorption peaks in the wavelength region of 350 to 430nm were confirmed to shift toward a long wavelength in the order of compound 10> compound 20> compound 16; and shifted toward a long wavelength in the order of compound 1> compound 12> compound 17; x is highly useful because long-wavelength shift is performed in the order of (l ═ 1, X is a nitrogen atom) > (l ═ 1, X is an amide group) > (l ═ 0) > (l ═ 1, X is an oxygen atom). Further, since the compound of formula (II) has a relationship of 13 to 15, 27< compounds 1 to 11, 21 to 26, the compound of formula (I) in which l is 1 and X has a nitrogen atom introduced therein has a superior long-wavelength absorption than the compound of formula (II).

Regarding the molar absorptivity, R in benzotriazole represented by the formula (A)⁶～R⁹Among the above compounds having a substituent, it is confirmed that the benzotriazole-based compounds 1 to 27 of the present invention, to which the compounds of the formulae (I) and (II) have been introduced, have a molar absorption coefficient of 17200L/(mol. cm) or more, have a higher molar absorption coefficient than conventional long-wavelength absorption-type ultraviolet absorbers (compound 29: 15300L/(mol. cm)) and ultraviolet absorbers of similar structure (compound 31: 17100L/(mol. cm)), and have excellent ultraviolet absorbability at an absorption peak located in a wavelength region of 350 to 430nm, and can efficiently absorb light of a wavelength of interest even in a small amount of addition. Wherein, the compounds 15 and 23 are 18000L/(mol cm) or more, the compounds 1,4 to 6, 8 to 14, 16 to 20 and 24 to 27 are 20000L/(mol cm) or more, the compounds 3, 7 and 22 are 30000L/(mol cm) or more, the molar absorption coefficient is high, and the ultraviolet absorption capability is excellent. I.e. is confirmedCompounds 7 and 22 having 2 benzotriazole skeletons among the compounds are considered, and particularly, although 1 benzotriazole skeleton is contained in the compound, the compound is considered to be represented by Y¹The compound 3 having a nitro group has a high molar absorption coefficient and is excellent.

Regarding the slope (absolute value) of the peak, it was confirmed that the absolute values of the slopes on the long wavelength side of the absorption peaks of the benzotriazole compounds 1 to 27 of the present invention having the formulas (I) and (II) introduced into benzotriazole in the wavelength region of 350 to 430nm were all 0.015 or more, which was larger than the slope of compound 29 (comparative example 1: 0.011) of the conventional long-wavelength absorber type ultraviolet absorber. Wherein, the slope of the compounds 1, 3-6, 8-27 is more than 0.020, and the slope of the compounds 1, 4-6, 8-12, 14-20, 22-27 is more than 0.025. The compound 1,4, 5, 11, 14, 18 to 20, 22, 24 to 27 has a slope of 0.030 or more and a ratio Y¹The compound 31 (comparative example 3: 0.028), which is a similar compound not constituting a heterocyclic ring of an aliphatic hydrocarbon group, has a large slope, and particularly, the compounds 1,4, 11, 14, 18, 19, 24 to 26 have a slope of 0.034 or more, which is larger than that of the compound 30 (comparative example 2), and thus, it is suggested that the selectivity of the wavelength is excellent.

In the formula (I), l ═ 1, X, and Y are each a nitrogen atom or the like¹Aromatic hydrocarbon radical (phenyl) which is monocyclic and has no substituents, Y²Compounds 1(0.034) and Y being hydrogen atoms²Compound 5(0.031) which is an aliphatic hydrocarbon group, l ═ 1, X is a nitrogen atom, Y is a nitrogen atom¹Compound 11(0.095) which is a fused ring having three or more rings directly bonded to the nitrogen atom was confirmed to have a slope of 0.030 or more.

In addition, in the formula (I), Y¹The slopes of compound 11(0.095) and compound 22(0.031) which contain 1 or more (or 2 or more) six-membered rings (aromatic hydrocarbon groups: phenyl groups) as condensed rings were confirmed to be as high as 0.030 or more. Wherein at Y¹The slope of the compound 11 having an oxygen-containing group in the condensed ring of (2) is particularly high as 0.095.

The slopes of compound 13(0.022), compound 14(0.034) and compound 27(0.037) containing one or more five-membered rings were as high as 0.015 or more. In formula (II), the slope of compound 14(0.034) or compound 27(0.037) in which the heterocycle is bicyclic or more is larger than that of compound 13(0.022) or compound 15(0.025) in which the heterocycle is monocyclic; the slope of compound 15 (1: 0.025), compound 14 (2: 0.034), and compound 27 (1: 0.037) each having 1 or more six-membered rings in the heterocycle was larger than that of compound 13(0.022) each having 0 ring. In addition, in the compounds having 1 six-membered ring, aromatic hydrocarbon group-containing compound 27 (1: 0.037) had a larger slope than aromatic hydrocarbon group-free compound 15 (1: 0.025).

In formula (I), l is 0, Y¹The slopes of compound 17(0.028), compound 18(0.034), compound 19(0.034) and compound 20(0.033) which are aromatic hydrocarbon groups (phenyl groups) are 0.025 or more, wherein R in formula (A) is¹、R²、R⁴In comparison with compounds 19(0.034) and 20(0.033) having the same substituents at Y¹The slope of the compound 19 or 20 having an oxygen-containing group or a nitrogen-containing group in the aromatic hydrocarbon group (phenyl group) in (1) is as high as 0.030 or more, and the slope of the compound 20 having an oxygen-containing group is 0.033.

In formula (I), it is confirmed that l ═ 1, X have a nitrogen atom, and Y¹Is a compound 22(0.031) containing a sulfur-containing aromatic hydrocarbon group (phenyl), Y¹Is compound 24(0.034) of an aromatic hydrocarbon group (phenyl) containing hydroxyalkyl group, Y¹The slopes of compound 25(0.040) and compound 26(0.040) each being an aromatic hydrocarbon group (phenyl) containing a (meth) acryloyl group were as high as 0.030 or more.

[ Table 1A ]

[ Table 1B ]

[ Table 1C ]

[ Table 1D ]

(4) Transmittance of light

As shown in Table 1, compounds 1 to 27 and compounds 29 to 31 were diluted with chloroform at a given concentration of 30 to 2000. mu.M, and stored in a 10mm quartz cuvette, and transmission spectra were measured using an ultraviolet-visible-infrared spectrophotometer (UH 4150V, manufactured by Hitachi high-tech science, Japan) and transmittance at 400 to 450nm was read from these spectra (tables 1A to D).

Benzotriazole-based compound 2 (100. mu.M, 400 nm: 3%, 430 nm: 46%, 440 nm: 73%) of the present invention of the formula (I) or (II), compound 3 (50. mu.M, 400 nm: 2%, 430 nm: 31%, 440 nm: 60%), compound 7 (30. mu.M, 400 nm: 8%, 430 nm: 35%, 440 nm: 55%), compound 8 (40. mu.M, 400 nm: 9%, 430 nm: 45%, 440 nm: 77%), compound 10 (100. mu.M, 400 nm: 1%, 430 nm: 40%, 440 nm: 74%), compound 15 (100. mu.M, 400 nm: 8%, 430 nm: 69%, 440 nm: 87%), compound 23 (100. mu.M, 400 nm: 2%, 430 nm: 49%, 440 nm: 77%), transmittance at 400 nm: 10% or less, 430nm transmittance: 75% or less, 440nm transmission: 53% or more, and is excellent in absorption of light having a wavelength of up to 430nm, and also excellent in transmittance of light having a wavelength in the visible light region of 440 nm.

In addition, Compound 1 (120. mu.M, 400 nm: 1%, 430 nm: 72%, 440 nm: 91%), Compound 4 (100. mu.M, 400 nm: 1%, 430 nm: 56%, 440 nm: 85%), Compound 5 (100. mu.M, 400 nm: 1%, 430 nm: 45%, 440 nm: 79%), Compound 14 (2000. mu.M, 400 nm: 0%, 430 nm: 59%, 440 nm: 89%), Compound 24 (100. mu.M, 400 nm: 1%, 430 nm: 64%, 440 nm: 87%), Compound 26 (100. mu.M, 400 nm: 1%, 430 nm: 65%, 440 nm: 92%), its 400nm transmittance: 1% or less, 430nm transmittance: 75% or less, 440nm transmission: 75% or more, and the above-mentioned optical properties are excellent, and particularly, the compounds 4,5, 24 and 26 can be realized at a low concentration.

(5) Compatibility with the resin.

As the thermoplastic resin, polymethyl methacrylate as a (meth) acrylic resin, polyethylene terephthalate as an ester-based resin, polystyrene as a styrene-based resin, polycarbonate as a polycarbonate-based resin, an acrylonitrile-butadiene-styrene copolymer as an acrylonitrile-butadiene-styrene copolymer, a cycloolefin polymer as a cycloolefin-based resin; as the thermosetting resin, acrylic melamine resin as acrylic melamine resin, urea resin as urea resin, and melamine resin as melamine resin were used, and compatibility was confirmed.

(5-1) compatibility with resin (A)

The compatibility (transparency) of the film and the resin member of the compound of the present invention was confirmed by the following method (table 2).

(preparation of polymethyl methacrylate film)

After 0.1g of each of compound 17 and compound 18 was uniformly mixed with 0.1g of polymethyl methacrylate and 4g of chloroform, the mixture was dropped onto a glass slide, and heated in an oven at 45 ℃ for 2 hours to remove the solvent, thereby preparing a polymethyl methacrylate film.

A blank polymethyl methacrylate film having a film thickness of 50 to 300 μm was prepared by uniformly mixing 0.1g of polymethyl methacrylate and 4g of chloroform in the same manner as described above.

(preparation of acrylic Melamine resin film)

Compound 17 and compound 18, each 4.5mg, were dissolved in 0.1mL of THF, and mixed with 0.1mL of a bake-drying topcoat (ACRYCITE UB-63 CLEAR: manufactured by TOKIDA PAISHI CO., LTD.), and 0.2mL of the above mixture was coated on a 1.5X 1.5cm glass slide. After heating the slide glass in an oven for 30 minutes to raise the temperature from 25 ℃ to 150 ℃, the slide glass was allowed to stand at 150 ℃ for 2 hours, thereby producing a melamine acrylate resin film containing 10 wt% of compound 17 or compound 18.

Further, 0.1mL of a melamine acrylate monomer and 0.1mL of THF were uniformly mixed, and the same procedure as described above was carried out, thereby preparing a melamine acrylate resin film as a blank sample having a film thickness of 100 to 150. mu.m.

The appearance of the above-mentioned film prepared was visually observed and evaluated according to the following criteria.

Evaluation criteria

O: compared with a blank sample, the transparent liquid has equal transparency.

And (delta): there was a slight haze compared to the blank sample.

X: there was severe blurring compared to the blank sample.

With respect to the acrylic film, it was confirmed that both of compounds 17 and 18 were able to obtain a film having good transparency without cloudiness.

Further, it was confirmed that the compound 17 (Y) was contained in the acrylic melamine film¹：Ph-、R²、R⁴The substituent (b): methyl, t-butyl) and Y¹X is the same, R¹～R⁵Compound 18 (Y) having different substituents¹：Ph-、R²、R⁴The substituent (b): t-butyl group, t-butyl group) can give a film having good transparency (good compatibility) without cloudiness, and R is a group represented by¹～R⁵The compound having a methyl group is excellent in compatibility.

[ Table 2]

(5-2) compatibility with resin (B)

The compatibility (transparency) of the film and the resin member of the compound of the present invention was confirmed by the following method (table 3).

(preparation of polymethyl methacrylate film)

0.001g each of compound 14, compound 29, and compound 31 was uniformly mixed with 0.099g of polymethyl methacrylate and 12g of chloroform, and about 1mL of the mixture was spin-coated on a glass substrate at 1500rpm for 20 seconds, and then heated in an oven at 45 ℃ for 2 hours to remove the solvent, thereby preparing an acrylic film having a film thickness of 50 to 300 μm containing 1 wt% of compound 14, compound 29, or compound 31.

A blank polymethyl methacrylate film having a film thickness of 50 to 300 μm was prepared by uniformly mixing 0.1mL of an acrylic resin and 12g of chloroform in the same manner as described above.

(preparation of polyethylene terephthalate (PET) film)

0.0004g each of the compound 14, the compound 29 or the compound 31 and 0.0396g of polyethylene terephthalate chips were kneaded at 280 ℃ respectively, and the mixture was coated on a glass slide substrate and air-cooled to prepare a polyethylene terephthalate film having a film thickness of 20 to 200 μm and containing 1 wt% of the compound 14, the compound 29 or the compound 31.

0.045g of polyethylene terephthalate chips were dissolved and the same procedure as described above was carried out to prepare a polyethylene terephthalate film as a blank sample having a film thickness of 20 to 200 μm.

(production of Polystyrene (PS) film).

After 0.001g each of compound 14, compound 29 and compound 31 was uniformly mixed with 0.099g of a polystyrene resin (Kanto chemical, Japan) and 4g of chloroform, the chloroform was concentrated to about 2 to 3g, 50. mu.L of the concentrate was applied to a glass slide, and the glass slide was heated in an oven at 45 ℃ for 2 hours to remove the solvent, whereby a polystyrene film having a film thickness of 10 to 50 μm and containing 1 wt% of compound 14, compound 29 or compound 31 was prepared.

Further, a polystyrene film as a blank sample having a film thickness of 10 to 50 μm was prepared by uniformly mixing 0.1g of a polystyrene resin and 4g of chloroform in the same manner as described above.

(preparation of Polycarbonate (PC) film)

A polycarbonate film containing 1 wt% of compound 14, compound 29 or compound 31 and having a film thickness of 10 to 50 μm was prepared by uniformly mixing 0.001g of each of compound 14, compound 29 and compound 31 with 0.099g of a polycarbonate resin (Kanto chemical, Japan) and 4g of chloroform, concentrating the chloroform to about 2 to 3g, applying 25. mu.L of the concentrate onto a glass slide, and heating the glass slide in an oven at 45 ℃ for 2 hours to remove the solvent.

A polycarbonate film as a blank sample having a film thickness of 10 to 50 μm was prepared by uniformly mixing 0.1g of a polycarbonate resin and 4g of chloroform in the same manner as described above.

(preparation of Acrylonitrile-butadiene-styrene resin (ABS) film)

An ABS film containing 1 wt% of compound 14, compound 29 or compound 31 and having a film thickness of 10 to 50 μm was prepared by uniformly mixing 0.001g each of compound 14, compound 29 or compound 31 with 0.099g of ABS resin (TOYOLAC 950-X01: Toray corporation, Japan) and 20g of chloroform, concentrating the chloroform, dropping 25 μ L of the concentrate on a glass slide, and heating in an oven at 45 ℃ for 2 hours to remove the solvent.

In addition, an ABS resin (0.1 g) and chloroform (20 g) were uniformly mixed without adding additives, and the same operation was performed to prepare an ABS film having a thickness of 10 to 50 μm.

(preparation of a Urea-Formaldehyde resin film)

A monomer solution was prepared by dissolving 1mL of a 37 wt% formaldehyde solution, 0.25g of urea, and 0.16g of ammonium acetate. Next, 0.007g each of compound 14, compound 29 or compound 31 was dissolved in 20mL each of THF, 0.2mL each of the mixture was uniformly mixed with 0.1mL each of the monomer solution, and 0.3mL each of the mixture was coated on a 1.5 × 1.5cm slide glass. The slide glass was placed in an oven and heated at 150 ℃ for 5 hours to prepare a urea-formaldehyde resin film having a film thickness of 40 to 80 μm and containing 1 wt% of compound 14, compound 29 or compound 31.

Further, 0.1mL of the monomer solution and 0.2mL of THF were uniformly mixed, and the same procedure was carried out as described above to prepare a urea-formaldehyde resin film as a blank sample having a film thickness of 40 to 80 μm.

(preparation of Melamine resin film)

A hexamethylolmelamine solution was prepared by adding 1g of melamine and 24.60g of water to 5.15g of a formaldehyde solution prepared to ph7.5 with sodium hydroxide and carrying out a heating reaction. Then, 0.0057g of each compound of example 14, example 29, or example 31 was dissolved in 0.1mL of THF, and each solution was uniformly mixed with 0.2mL of hexamethylolmelamine solution, followed by coating 0.3mL of the solution on a 1.5X 1.5cm slide glass. The slide glass is put into an oven and reacted for 5 hours at 150 ℃, thereby preparing a melamine resin film with a film thickness of 10-50 μm and containing 1 wt% of compound 14, compound 29 or compound 31.

A melamine resin film as a blank sample having a film thickness of 10 to 50 μm was prepared by uniformly mixing 0.2mL of the monomer solution and 0.1mL of THF in the same manner as described above.

(preparation of acrylic Melamine resin film)

In order to form a film, 0.0045g each of compound 14, compound 29, or compound 31 was dissolved in 1mL of THF so that the concentration of compound 14, compound 29, or compound 31 became 1 wt%, and 0.1mL of each of the above-mentioned mixtures was uniformly mixed with 0.1mL of a bake-drying topcoat (melamine acrylate): Acrycite UB-63Clear, manufactured by Katsuoki paint Co., Ltd.), and 0.2mL of the mixture was coated on a 1.5X 1.5cm glass slide. The slide glass was placed in an oven and heated at 150 ℃ for 2 hours to prepare a melamine acrylate resin film having a film thickness of 100 to 150 μm and containing 1 wt% of compound 14, compound 29 or compound 31.

Further, 0.1mL of a melamine acrylate monomer and 0.1mL of THF were uniformly mixed and subjected to the same operation as described above to prepare a melamine acrylate resin film as a blank sample having a film thickness of 100 to 150 μm.

(preparation of cycloolefin Polymer (COP) resin film)

0.001g each of compound 14, compound 29, and compound 31 was kneaded at 280 ℃ with 0.099g of COP resin, and the mixture was coated on a glass slide substrate and air-cooled to prepare a COP film containing 1 wt% of compound 14, compound 29, or compound 31 and having a film thickness of 20 to 200 μm.

In addition, 0.045gCOP resin is dissolved and the same operation is carried out to prepare a COP film as a blank sample with a film thickness of 20-200 μm.

The appearance of the above-mentioned film prepared was visually observed and evaluated according to the following criteria.

Evaluation criteria

O: compared with a blank sample, the transparent liquid has equal transparency.

And (delta): there was a slight haze compared to the blank sample.

X: there was severe blurring compared to the blank sample.

It was confirmed that the film containing compound 14 of the present invention had transparency equivalent to or slightly hazy with respect to the blank, and had good transparency, even in any resin. Among the resins shown in table 3, the resins using a melamine acrylate resin, which is a copolymer of a thermoplastic resin (polymer, copolymer), polyethylene terephthalate, polystyrene, polycarbonate, polymethyl methacrylate, ABS, a cycloolefin polymer, and a thermosetting resin, were excellent in transparency. This suggests that the 2-phenylbenzotriazole derivative of the present invention has excellent compatibility particularly with thermoplastic resins (polymers, copolymers) and copolymers of thermosetting resins.

Further, compound 14 of the ultraviolet absorber of the present invention, which has a heterocyclic ring of two or more rings in formula (II) and contains an aromatic hydrocarbon group (phenyl group) having 2 six-membered rings or a 5-membered ring, is more excellent in compatibility with a resin as a whole, as compared with compound 29 of the conventional ultraviolet absorber and compound 31 of the analogous compound of the comparative example.

[ Table 3]

(6) Confirmation of odor caused by thermal decomposition

The compound (2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-octylthiobenzotriazole) having a sulfur-containing group introduced into a 2-phenylbenzotriazole derivative and the compound having a bonding group represented by the above formulae (I) and (II) introduced thereinto were heated at 350 ℃ for 1 to 20 minutes in a muffle furnace for 10 minutes to confirm odor.

As a result, although the compounds containing a sulfur-containing group in the 2-phenylbenzotriazole derivative generate odor during decomposition, the compounds 1 to 20 having the bonding groups represented by the above formulae (I) and (II) introduced therein do not generate odor, which suggests that the resin composition can be applied to resins requiring a higher molding processing temperature and that odor generated during processing can be reduced.

(7) Evaluation of light resistance

Mixing the components in a weight ratio of compounds 8, 13, 14, 17, 18 and 27 (resin: compound) of 1: 1. the weight ratio of compounds 9, 15, 19, 31 (resin: compound) was 2: 1. the weight ratio of compound 11 (resin: compound) was 3: 1. the weight ratio of compound 20 (resin: compound) was 4: 1. the weight ratio of the compounds 7, 10 and 22 (resin: compound) is 6: mode 1 was added to a 2.5 wt% acrylic resin chloroform solution, and the mixture was thinned by a spin coater (manufactured by Mikasa, MS-B150) at 1500rpm for 15 seconds, and the organic solvent was distilled off to prepare a thin film. The ultraviolet-visible transmission spectrum of the film was measured with an ultraviolet-visible infrared spectrophotometer (UH 4150V, high tech science, japan), and the initial ultraviolet transmittance (%) at 370 to 430nm was read: A. then, an ultraviolet irradiation device (aging tester Ci3000+ W manufactured by Attapus) was used to irradiate the sample at a wavelength of 300 to 400nm and an illuminance of 42W/m²Irradiating ultraviolet rays at a blackboard temperature of 63 ℃, measuring an ultraviolet-visible transmission spectrum after the irradiation time is 100 hours, and reading the transmittance (%) at 370-430 nm: b, calculating a difference Δ T in transmittance before and after irradiation: B-A (%) (Table 4).

[ Table 4]

With R in benzotriazole represented by the formula (A)⁶～R⁹Has a substituent on it, X is a nitrogen atom, Y¹Compared with the compound 31 of the comparative example which is an aliphatic hydrocarbon group and does not form a heterocyclic ring, the difference of the transmittance before and after irradiation at 370-430 nm of the compounds 7-11, 13-15, 17-20, 22, 27 is small, and the light resistance is excellent. Among them, the difference in transmittance of compounds 8, 10, and 22 was 45% or less, the difference in transmittance of compound 9 was 30% or less, the difference in transmittance of compound 13 was 15% or less, the difference in transmittance of compounds 11, 18, and 27 was 10% or less, and the difference in transmittance of compounds 14, 17, 19, and 20 was 5% or less, and all of them were excellent in light resistance.

In the formula (I), l ═ 1, X, and Y are each a nitrogen atom or the like¹The compound 11 having a three-or more-ring condensed ring has a difference in transmittance of 10% or less before and after irradiation, and is excellent in light resistance.

In addition, in the formula (I), Y¹In the case of a condensed ring, the difference in transmittance between compounds 11 and 22 (having a benzotriazole skeleton as a condensed ring) containing 1 or more six-membered rings (aromatic hydrocarbons) in the condensed ring is 45% or less, and the light resistance is excellent. Wherein at Y¹The compound 11 having an oxygen-containing group in the six-membered ring has a difference in transmittance of 10% or less and is excellent in light resistance.

On the other hand, in formula (II), it was confirmed that compounds 13 (15% or less), 14 (5% or less), and 27 (10% or less) containing an unsaturated bond in the heterocyclic ring had smaller transmittance differences than compound 15 containing no unsaturated bond. Further, compounds 14 (5% or less) and 27 (10% or less) in which the heterocyclic ring is bicyclic or more are superior in light resistance to compound 13 (15% or less) containing 1 heterocyclic ring; among them, compound 14 (5% or less) having 2 six-membered rings (aromatic hydrocarbon groups) in the heterocyclic ring is more excellent in light resistance than compound 27 (10% or less) having 1 six-membered ring in the heterocyclic ring. Further, compound 13 (15% or less), compound 14 (5% or less), and compound 27 (10%) each having a five-membered ring in the heterocyclic ring are superior to compound 15 not having a five-membered ring in light resistance.

In formula (I), l is confirmed to be 0 and Y is confirmed¹The difference in transmittance between compounds 17 (5% or less), 18 (10% or less), 19 (5% or less) and 20 (5% or less) each having an aromatic hydrocarbon group (phenyl group) is 10% or less, wherein Y is¹The compounds 19(5 wt% or less) and 20(5 wt% or less) containing an oxygen-containing group and a nitrogen-containing group in an aromatic hydrocarbon group have a difference in transmittance of 5% or less and are more excellent in light resistance. In addition, R of the formula (A)²Is butyl, R⁴Compound 17 (5% or less), 19 (5% or less) or 20 (5% or less) which is a methyl group is used as the ratio R²、R⁴Compound 18 (10% or less) which is butyl is excellent in light resistance.

In the formula (I), l is 1, X is nitrogen atom, Y¹The difference in transmittance of the compound 22 which is an aromatic hydrocarbon group (phenyl group) having a sulfur-containing group is 45% or less, and the light resistance thereof is superior to that of the compound 31.

(8) Evaluation of reactivity

The compounds having reactive functional groups were tested for their reactivity with isocyanate compounds.

Polymerization was carried out by mixing compound 23(200mg, 0.52mmol) or compound 24(290mg, 0.70mmol) with hexamethylene diisocyanate (1.0g, 5.9mmol) and tetrahydrofuran (15g), respectively, and then adding dibutyltin dilaurate (0.3mg, 0.48. mu. mol) as a catalyst, and heating and stirring at 60 ℃ for 24 hours.

As a result, it was found that the reactivity of the compound 23 and the compound 24 of the present invention was good from the results of — C (═ O) -stretching vibration derived from a urea bond newly observed by the infrared spectroscopy.

In addition, a reactivity test with a (meth) acrylic compound was performed. The polymerization reaction was carried out by mixing compound 26(73mg, 0.15mmol), methyl methacrylate (0.5g, 5.0mmol) and toluene (1.0g), adding 2, 2' -azobis (isobutyronitrile) (2.5mg, 0.015mmol) as a polymerization initiator, and heating and stirring at 90 ℃ for 6 hours.

As a result, the polymer obtained was passed¹It was confirmed that the reaction proceeded by the disappearance of the peak ascribed to the hydrogen atom of the carbon-carbon double bond of the monomer in the H-NMR measurement, and it was found that the reactivity of the compound 26 of the present invention was good.

From this, it was confirmed that the compound having a reactive substituent in the formula (a) is excellent in preventing bonding to an organic material, bleeding, and the like, and securing the strength of an organic material.