JP7371847B2 - Glass plate with coating film and composition for forming the same - Google Patents

Description

The present invention relates to a glass plate with a coating film, particularly a glass plate for transportation equipment with a vitreous coating film. The present invention also relates to a composition for forming a coating film for forming this glass plate.

Glass plates are required to block ultraviolet rays while allowing visible rays to pass through. Particularly in the window glass applications of transportation equipment, there is a high demand for glass sheets with ultraviolet-shielding properties, due to demands for sun protection. By increasing the proportion of iron oxide in the glass composition constituting the glass plate, the ultraviolet shielding properties of the glass plate are improved. However, there is a limit to the improvement of the ultraviolet shielding properties by adding an inorganic ultraviolet shielding component such as iron oxide, and it is not possible to sufficiently shield UVA, which is ultraviolet light in the long wavelength range. For this reason, a glass plate has been proposed in which the ultraviolet shielding properties are improved by forming a coating film on the glass plate to which an organic ultraviolet shielding component made of an organic substance is added.

For example, International Publication No. 2006/137454 pamphlet (Patent Document 1) describes a glass plate in which a coating film containing silicon oxide as a main component, an organic ultraviolet shielding component, and a hydrophilic organic polymer is formed on the glass plate. is disclosed. In Patent Document 1, a film is formed by a sol-gel method, and a lower alcohol, which is a polar solvent, is used as a solvent for a solution for forming the film. Patent Document 1 uses an organic ultraviolet shielding component that dissolves in lower alcohol.

Japanese Unexamined Patent Publication No. 2009-184882 (Patent Document 2) discloses a glass plate provided with a coating film containing an ultraviolet shielding component formed from a solution containing a nonpolar solvent. This film is formed from a film-forming solution containing low-temperature curing polysilazane, and a non-polar solvent such as xylene is used as the solvent for this solution. Also in Patent Document 2, the organic UV-shielding component added to the film is used after being dissolved in a solvent.

In order to uniformly add the UV-shielding component to the film, it is advantageous to add the UV-shielding component as a solute. For this reason, as disclosed in Patent Documents 1 and 2, unlike inorganic UV screening agents that are difficult to dissolve in film-forming solutions, organic UV-screening agents are difficult to dissolve in film-forming solutions. was added to the membrane. On the other hand, International Publication No. 2012/107968 pamphlet (Patent Document 3) discloses a glass plate on which a coating film containing an organic ultraviolet shielding component added as fine particles is formed. By adding it as fine particles, the sustainability of the ultraviolet shielding effect of the organic ultraviolet shielding component is greatly improved.

International Publication No. 2006/137454 pamphlet JP2009-184882A International Publication No. 2012/107968 pamphlet

Ultraviolet A waves (UVA) in the long wavelength range reach deep into the skin and cause damage to the skin, so effective shielding is desired. Particularly in recent years, in addition to transmittance T _UV 380 in the ultraviolet region where the end on the long wavelength side is 380 nm, T _UV 400, which is the transmittance in the wavelength range 300 nm to 400 nm with the end on the long wavelength side 400 nm, has been sufficiently increased. There is a need for a glass plate that can be lowered. Patent Document 3 discloses a benzenethiol copper complex as an ultraviolet shielding component that can meet this demand (see Example B series). However, when the benzenethiol copper complex is added to an extent that T _UV 400 is sufficiently reduced, the coating film containing the UV-shielding component becomes strongly colored yellow, which is the complementary color of light in the visible short wavelength range, and the visible light transmittance decreases. YA decreases.

In general, and particularly in window glass applications, strong yellow coloring of glass plates tends to be undesirable. Therefore, an object of the present invention is to provide a glass plate with a coating film containing an ultraviolet shielding component, which can reduce the transmittance of light near a wavelength of 400 nm while suppressing noticeable yellow coloring. . Another object of the present invention is to provide a coating film-forming composition suitable for forming the above-mentioned coating film.

From one aspect of the present invention,
A glass plate for transportation equipment with a vitreous coating film containing an additive that imparts ultraviolet absorption ability,
comprising a glass plate and a coating film in contact with the main surface of the glass plate,
The coating film contains silicon oxide as a main component and the additive,
the additive contains an organic compound A,
A glass plate is provided, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR, where R is an organic group.

From another aspect of the present invention,
A composition for forming a coating film for a glass plate for transportation equipment with a vitreous coating film containing an additive that imparts ultraviolet absorption ability,
Contains a silicon oxide precursor and an organic compound A that is an additive that imparts ultraviolet absorption ability,
The organic compound A has the form of fine particles,
Provided is a composition for forming a coating film, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to the 2-phenylbenzotriazole skeleton. .
However, the thioorganic group is a group represented by -SR, where R is an organic group.

From another aspect of the present invention,
A fine particle dispersion composition used for forming a glassy coating film of a glass plate for transportation equipment with a glassy coating film containing an additive that imparts ultraviolet absorption ability,
Contains organic compound A, which is an additive that imparts ultraviolet absorption ability,
The organic compound A has the form of fine particles with an average particle size of 150 nm or less,
A fine particle dispersion composition, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR, where R is an organic group.

According to the present invention, there is provided a glass plate with a coating film suitable for reducing the transmittance of light in the vicinity of a wavelength of 400 nm while suppressing noticeable yellow coloring, and a composition suitable for forming the coating film. , it becomes possible to provide.

FIG. 1 is a sectional view showing one form of a glass plate according to the present invention. FIG. 2 is a plan view showing a form when the glass plate according to the present invention is used as door glass. It is a top view which shows another form when the glass plate by this invention is used as door glass. FIG. 2 is a partially sectional plan view showing a form when the glass plate according to the present invention is used as door glass.

Preferred embodiments of the present invention will be described below, but the following description is not intended to limit the present invention to specific embodiments.

One aspect of the present invention is as follows.
A glass plate with a coating film containing an additive that imparts ultraviolet absorption ability,
comprising a glass plate and a coating film in contact with the main surface of the glass plate,
The coating film contains silicon oxide as a main component and the additive,
the additive contains an organic compound A,
A glass plate, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR, where R is an organic group.

In one form of the glass plate according to the present invention, the organic compound A includes a unit represented by the following formula (1). However, in formula (1), A ¹ to A ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom. It is an atom or group corresponding to at least one selected from the containing groups, and at least one of A ¹ to A ⁹ is a thioorganic group. The sulfur atom-containing group other than the thioorganic group is a group that contains a sulfur atom and is not connected to the 2-phenyl-benzotriazole skeleton through a sulfide bond (-S-).

In one form of the glass plate according to the invention, at least one of A ⁶ to A ⁹ is a thioorganic group. In another form of the glass plate according to the invention, at least one of A ¹ to A ⁵ is a thioorganic group.

In one form of the glass plate according to the present invention, the thioorganic group is a thioalkyl group which may have a hydrogen atom substituent, or a thioaryl ring group which may have a hydrogen atom substituent. Here, the thioalkyl group is a group represented by -S-Alk when an alkyl group that may have a hydrogen atom substituent is expressed as Alk, and the thioaryl ring group is a group represented by -S-Alk, which may have a hydrogen atom substituent. This is a group represented by -S-Ary when the optional aryl ring group is represented by Ary. However, the thioorganic group may be other than a thioalkyl group and a thioaryl ring group.

In one form of the glass plate according to the present invention, the alkyl group which may have a substituent for the hydrogen atom contained in the thioalkyl group is an alkyl group having 1 to 18 carbon atoms, or a phenyl group as a substituent for the hydrogen atom. It is an alkyl group having 1 to 6 carbon atoms. The alkyl group may be acyclic or cyclic, and when it is acyclic, that is, chain-like, it may be a straight-chain alkyl group or a branched alkyl group.

In one form of the glass plate according to the present invention, the organic compound A includes two 2-phenylbenzotriazole skeletons, the two 2-phenylbenzotriazole skeletons are connected via a thioorganic group, and the thioorganic group is It is connected to each of the two 2-phenylbenzotriazole skeletons via a sulfide bond.

The thioorganic group interposed between two 2-phenylbenzotriazole skeletons is an alkylene group (Alk) which may have a substituent on a hydrogen atom, an arylene group (Alk) which may have a substituent on a hydrogen atom, When a cyclic group is represented as (Ary), it may be a group represented by any of the following.
・-S-(Alk)-S-
・-S-(Ary)-S-
・-S-(Ary)-(Ary)-S-
・-S-(Ary)-S-(Ary)-S-
・-S-(Ary)-(Alk)-(Ary)-S-
・-S-(Ary)-S-(Ary)-S-(Ary)-S-

In one form of the glass plate according to the invention, the thioorganic group is a thioaryl ring group.

In one form of the glass plate according to the present invention, the thioaryl ring group has an alkyl group having 4 to 9 carbon atoms as a substituent for the hydrogen atom. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group. In one form of the glass plate according to the present invention, the thioaryl ring group has a branched chain alkyl group containing a quaternary carbon atom and having 4 to 9 carbon atoms as a substituent.

In one form of the glass plate according to the present invention, the aryl ring contained in the thioaryl ring group is a benzene ring and/or a naphthalene ring.

In one form of the glass plate according to the present invention, the alkyl group contained in the thioalkyl group is a cyclohexyl group which may have a hydrogen atom substituent. In this case, the thioalkyl group is a thiohexyl ring group, and is a group represented by -S-Cy when a cyclohexyl group which may have a hydrogen atom substituent is represented by Cy.

In one embodiment of the glass plate according to the present invention, the number of carbon atoms in the alkyl group contained in the thioalkyl group and the aryl ring group contained in the thioaryl ring group is in the range of 1 to 18.

In one form of the glass plate according to the present invention, the hydrogen atom substituent that may be included in the thioalkyl group or thioaryl ring group is a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, An atom or group corresponding to at least one selected from a phosphorus atom-containing group and a sulfur atom-containing group. The same applies to the substituents on the hydrogen atom that may be included in the thioalkylene group or the thioarylene ring group, and the substituents on the hydrogen atom described below.

A substituent for a hydrogen atom that may be contained in a cyclic thioorganic group, particularly a thioaryl ring group or a thiohexyl ring group, is a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group. It may be. The number of carbon atoms in the hydrocarbon group and the hydroxy group is preferably 2 or more, 3 or more, especially 4 or more, and 12 or less, 9 or less, especially 8 or less. The hydrocarbon group may be acyclic or cyclic, for example a linear or branched alkyl group having 4 to 9 carbon atoms, 3 to 8 carbon atoms, or 4 to 8 carbon atoms, especially a branched chain alkyl group. It is a chain alkyl group having The number of hydrogen atom substituents that may be included in the cyclic thioorganic group is preferably 0 to 5, more preferably 1 to 5, and particularly preferably 1 to 2.

When the thioorganic group interposed between two 2-phenylbenzotriazole skeletons is represented by -S-(Ary)-(Alk)-(Ary)-S-, the alkylene group represented by (Alk) is carbon It is preferably a linear or branched alkylene group of 3 to 12, and more preferably a branched alkylene group, and may also be an alkylene group containing a quaternary carbon atom.

In one form of the glass plate according to the present invention, the organic compound A is a thioaryl ring group optionally having a substituent for a hydrogen atom, represented by any one of the following formulas (2-1) to (2-3). Or a 2-phenylbenzotriazole derivative having a thiohexyl ring group.
PhBzT ^1a -S-X ^1a -(R ^1a ) _l (2-1)
(In the formula, PhBzT ^1a represents a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-X ^1a -...), which may have the above-mentioned substituent for a hydrogen atom, is bonded, and X ^1a is phenyl Represents a ring or naphthyl ring residue, l R ^1a each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and 1 represents a residue of 0 to 5 carbon atoms. (Indicates an integer.)
PhBzT ^1b -S-Cy-(R ^1b ) _m (2-2)
(In the formula, PhBzT ^1b represents a 2-phenylbenzotriazole skeleton to which a thiocyclohexyl ring group (-S-Cy-...), which may have the above-mentioned substituent for a hydrogen atom, is bonded, and Cy is a cyclohexyl ring (m R ^1b each independently represent a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and m represents an integer of 0 to 5.)
PhBzT ^1c -S-A ^1c -S-PhBzT ^2c (2-3)
(In the formula, PhBzT ^1c and PhBzT ^2c each independently represent a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-A ^1c -S-) is bonded, which may have the above-mentioned substituent, A ^1c is the following formula:
- [X ^1c - (R ^1c ) _n ] - (A ^2c ) _q - [X ^2c - (R ^2c ) _p ] -
(In the formula, X ^1c and X ^2c each independently represent a phenyl ring or naphthyl ring residue, and n R ^1c and p R ^2c each independently represent a hydrocarbon group having 1 to 18 carbon atoms, a carbon It represents an alkoxy group or a hydroxy group of numbers 1 to 18, n and p represent integers of 0 to 4, and A ^2c is an aromatic group, an unsaturated group, a nitrogen atom-containing group, a sulfur atom-containing group, or an oxygen atom. A hydrogen atom is substituted with a monovalent or divalent group selected from a containing group, a phosphorus atom-containing group, an alicyclic group, and a halogen atom, or at least one of both ends is interrupted, or a carbon- represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or a sulfide bond, in which the carbon bond may be interrupted, and q represents an integer of 0 or 1.) or represents a phenyl or naphthyl ring residue. )

Also in the 2-phenylbenzotriazole derivatives represented by any of formulas (2-1) to (2-3), substituents for hydrogen atoms include, for example, halogen atoms, hydrocarbon groups, aromatic groups, and unsaturated groups. , an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group.

In one form of the glass plate according to the present invention, the organic compound A is represented by the formula (2-1) or the formula (2-3), and X ^1a , X ^1c and X ^2c are phenyl ring residues. where l, n and p represent 0.

In one form of the glass plate according to the present invention, the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton has a hydroxy group at the 2-position and an alkyl group having 1 to 6 carbon atoms at the 5-position. In other words, in formula (1), A ¹ is a hydroxy group and A ⁴ is an alkyl group having 1 to 6 carbon atoms. This alkyl group is, for example, a methyl group or a 1,1-dimethylethyl group (tert-butyl group), especially a methyl group. The phenyl group may have hydrogen atoms in the 4- and 6-positions and an alkyl group having 1 to 6 carbon atoms in the 3-position, such as a methyl group or a tert-butyl group, especially a tert-butyl group. In other words, in the phenyl group of formula (1), for example, A ¹ is a hydroxy group, A ² is an alkyl group having 1 to 6 carbon atoms, especially a tert-butyl group, A ³ is a hydrogen atom, and A ⁴ is a carbon number 1 -6 alkyl group, especially methyl group, A ⁵ is a hydrogen atom.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n and p represent integers of 1 to 5.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a branched chain alkyl group having 3 to 8 carbon atoms, and l, n and p represent integers of 1 to 3.

In one form of the glass plate according to the present invention, the organic compound A is represented by the formula (2-1) or the formula (2-3), and X ^1a , X ^1c and X ^2c are phenyl ring residues. R ^1a , R ^1c and R ^2c each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n and p represent 1.

In one embodiment of the glass plate according to the present invention, the organic compound A is represented by the formula (2-1), where X ^1a represents a phenyl ring residue, and R ^1a represents a linear chain having 4 to 9 carbon atoms. or a branched alkyl group.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n and p represent 2.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms containing a tertiary carbon and/or a quaternary carbon; p represents an integer from 1 to 5.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1), where X ^1a represents a residue of a phenyl ring, and R ^1a represents the number of carbon atoms including quaternary carbon. It represents a chain alkyl group having 4 to 9 branches, and l, n and p represent integers of 1 to 5.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent an alkoxy group containing a linear or branched alkyl group having 1 to 18 carbon atoms.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a phenyl ring. and R ^1a , R ^1c and R ^2c represent a hydroxy group.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1) or formula (2-3), and X ^1a , X ^1c and X ^2c represent residues of a naphthyl ring. show.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-2), and m represents 0.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-2), R ^1b represents a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 5. shows.

In one form of the glass plate according to the present invention, the organic compound A is represented by the formula (2-3), where X ^1c and X ^2c represent phenyl group residues, A ^2c represents a sulfide bond, q indicates 1.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-3), where X ^1c and X ^2c represent residues of a phenyl group, and A ^2c has 1 to 8 carbon atoms. represents a hydrocarbon group, and q represents 1.

In one form of the glass plate according to the present invention, the organic compound A is represented by the formula (2-3), where X ^1c and X ^2c represent phenyl group residues, and q represents 0.

In one form of the glass plate according to the present invention, the organic compound A is represented by the formula (2-1), where X ^1a represents a phenyl group residue, and R ^1a represents a linear chain having 1 to 18 carbon atoms. or a branched chain alkyl group, and l represents an integer of 0 to 5. In this case, X ^1a may be connected to the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton, or may be directly connected to the same skeleton. Further, R ^1a represents a linear or branched alkyl group having 4 to 9 carbon atoms, and 1 may represent 1 or 2. Further, R ^1a represents a branched chain alkyl group having 4 to 9 carbon atoms, and at least one of R ^1a may be a chain alkyl group containing quaternary carbon.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1), and X ^1a is connected to the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton. R ^1a is an alkoxy group containing a linear or branched alkyl group having 1 to 18 carbon atoms, or a hydroxy group, and 1 is 1 or 2.

In one form of the glass plate according to the present invention, the organic compound A is represented by formula (2-1), and has a hydroxy group and a phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton. Methyl groups are connected to each other. This phenyl group may have a hydroxy group at the 2-position and a methyl group at the 5-position. Further, a hydroxy group, a 1,1-dimethylethyl group, and a methyl group may each be connected to this phenyl group. Furthermore, this phenyl group may have a hydroxy group at the 2-position, a 1,1-dimethylethyl group (tert-butyl group) at the 3-position, and a methyl group at the 5-position.

In one form of the glass plate according to the present invention, the coating film further includes an organic compound B, the organic compound B includes a 2-phenylbenzotriazole skeleton, and no thioorganic group is connected to the 2-phenylbenzotriazole skeleton. It has a molecular structure.

In one form of the glass plate according to the present invention, the organic compound B has the form of fine particles with an average particle size of 150 nm or less. Moreover, in one form of the glass plate according to the present invention, the organic compound A has the form of fine particles with an average particle size of 150 nm or less.

One form of the glass plate according to the invention has a T _UV 400 calculated according to ISO 13837 (convention A) of 2% or less, and a visible light transmittance YA measured using a CIE standard A light source of 70% or more. In one form of the glass plate according to the present invention, transmitted light from a CIE standard C light source is displayed using the L ^* a ^* b ^* color system, and a ^* of -15 or more and 0 or less and b ^* of 12 or less are expressed. have In one form of the glass plate according to the present invention, the yellowness YI defined in JIS K7373:2006 of transmitted light from a CIE standard C light source is 14 or less. In one embodiment of the glass plate according to the present invention, the ultraviolet transmittance T _UV 400 after irradiation with ultraviolet rays having a wavelength of 295 to 450 nm and an illuminance of 76 mW/cm ² for 100 hours is determined by the ultraviolet transmittance T _UV 400 before irradiating with the ultraviolet rays. The subtracted difference ΔT _UV 400 is 2% or less.

Another aspect of the present invention is as follows.
A composition for forming a coating film for a coated glass plate containing an additive that imparts ultraviolet absorption ability,
Contains a silicon oxide precursor and an organic compound A that is an additive that imparts ultraviolet absorption ability,
The organic compound A has the form of fine particles,
A composition for forming a coating film, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and a thioorganic group connected to the 2-phenylbenzotriazole skeleton via a sulfide bond.

In one embodiment of the composition for forming a coating film according to the present invention, the average particle size of the fine particles is 150 nm or less.

Another aspect of the present invention is as follows.
A fine particle dispersion composition used for forming the coating film of a coated glass plate containing an additive that imparts ultraviolet absorption ability,
Contains organic compound A, which is an additive that imparts ultraviolet absorption ability,
The organic compound A has the form of fine particles with an average particle size of 150 nm or less,
A fine particle dispersion composition, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR, where R is an organic group.

Hereinafter, one form of the glass plate according to the present invention will be described in more detail with reference to the drawings.

The glass plate of this embodiment shown in FIG. 1 includes a glass plate 1 and a coating film 2 containing an ultraviolet shielding component formed directly on the surface of the glass plate 1. Coating film 2 contains silicon oxide and organic compound A. It is preferable that the coating film 2 has silicon oxide as a main component. As used herein, the term "main component" refers to a component that accounts for 50% or more, preferably 60% or more, on a mass basis. Silicon oxide is a component that imparts durability and practically necessary hardness to the film 2. Organic compound A functions as an ultraviolet shielding component. Organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thioorganic group connected to this skeleton. Note that the 2-phenylbenzotriazole skeleton is the portion of formula (1) excluding the functional groups A ¹ to A ⁹ .

Although the quality of the coating film is arbitrary, it is preferably glassy. In this specification, the term "glassy" in a film means that the main component of the film is glassy, ie, amorphous, and does not mean that the film is free of crystals. Therefore, even a "glassy" film may contain crystalline components derived from organic compound A, organic compound B described below, ITO fine particles, and the like.

Coating film 2 may contain components other than silicon oxide and organic compound A. Optional components of the film 2 include an organic compound B, which is an ultraviolet shielding component that does not correspond to the organic compound A, and an organic compound C, which is a hydrophilic organic compound. Organic compound C may be a polymer. The coating film 2 may further contain other components such as structural units derived from the silane coupling agent. The structural unit derived from the silane coupling agent is a silane coupling agent derivative produced by the reaction of the silane coupling agent with other organic and/or inorganic substances.

It is preferable that organic compound A is added as fine particles. When added as fine particles, the sustainability of the ultraviolet shielding effect is improved compared to when added as a solute. In order to suppress the haze rate of the film, the average particle size of the fine particles is preferably adjusted to 150 μm or less. As the organic compound A, an organic compound that is solid at room temperature is suitable. In this specification, "normal temperature" is a term meaning 25°C.

In addition, as an ultraviolet shielding component that is solid at room temperature, a polymer obtained by polymerizing a polymerizable ultraviolet absorber is also known. However, such UV-shielding components are manufactured by polymerizing UV absorbers into which polymerizable functional groups such as (meth)acrylic groups are introduced, so when compared per unit mass, the UV-shielding effect is lower than that of low-molecular-weight UV rays. Inferior to absorbent.

The molecular weight of the organic compound A is preferably 5,000 or less, more preferably 3,000 or less, even more preferably 2,000 or less, particularly preferably 1,500 or less, in some cases 1,300 or less, further 1,200 or less, particularly 900 or less, particularly 800 or less. Good too. The molecular weight of organic compound A is preferably 200 or more, more preferably 300 or more. It is preferable that the organic compound A does not contain a polymerizable carbon-carbon double bond in the molecule. Examples of the polymerizable carbon-carbon double bond include double bonds contained in polymerizable functional groups such as vinyl groups, vinylene groups, and vinylidene groups.

Organic compound A is represented by the following formula (1), for example.

A ¹ to A ⁹ are each independently at least one selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group. is the applicable atom or group. However, at least one of A ¹ to A ⁹ is a thioorganic group. A ¹ to A ⁹ may contain a sulfur atom-containing group that does not correspond to a thioorganic group. A sulfur atom-containing group that does not correspond to a thioorganic group is a group that contains a sulfur atom and is not connected to the 2-phenylbenzotriazole skeleton via a sulfide bond (-S-).

To be more precise, A ¹ to A ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group. It is a group corresponding to at least one selected from the following. A ¹ to A ⁹ may correspond to two or more of the above groups. For example, a phenyl group is both a hydrocarbon group and an aromatic group, and a group represented by the formula: -S-(CH ₂ ) ₂ -OH is both an oxygen atom-containing group and a sulfur atom-containing group, and is a thioorganic group. This also applies to the base. Preferably, at least one of A ⁶ to A ⁹ is a thioorganic group. However, A ⁶ to A ⁹ may not contain a thioorganic group, and at least one of A ¹ to A ⁵ may be a thioorganic group.

Note that the organic compound A may be composed of one type of compound or may contain multiple types of compounds.

The above atoms and groups other than hydrogen atoms will be explained below.
(halogen atom)
Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms.

(hydrocarbon group)
A hydrocarbon group is a group composed of carbon atoms and hydrogen atoms. The hydrocarbon group may be an aliphatic group or an aromatic group, and may have an unsaturated group such as a carbon-carbon double bond. Since the aromatic group, which is a hydrocarbon group, will be described later, the aliphatic group will be explained here. An aliphatic group may be acyclic or cyclic, for example a straight-chain or branched alkyl group, alkenyl group or alkynyl group, and for example a hydrogen atom may be substituted with an alkyl group. cycloalkyl group or cycloalkenyl group. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 10, particularly preferably 4 to 9. Preferred examples of hydrocarbon groups include straight-chain or branched alkyl groups having 1 to 20 carbon atoms, 1 to 9 carbon atoms, even 4 to 9 carbon atoms or 1 to 3 carbon atoms, especially branched alkyl groups having 4 to 9 carbon atoms. It includes an alkyl group and a cyclic alkyl group having 3 to 10 carbon atoms, and even 3 to 8 carbon atoms.

Straight chain or branched alkyl groups are not particularly limited, but include, for example, methyl group, benzyl group, α,α-dimethylbenzyl group, ethan-1-yl group, propan-1-yl group, 1-methylethane-yl group. 1-yl group, butan-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 yl group, hexan-1-yl group, heptane-1-yl group, octan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, nonan-1-yl group, decane- 1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecan-1-yl group -yl group and octadecane-1-yl group. Examples of linear or branched alkenyl groups include vinyl group, prop-1-en-1-yl group, allyl group, isopropenyl group, but-1-en-1-yl group, but-2-en-yl group, and 1-yl group, but-3-en-1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, pent-1-en-1-yl group yl group, pent-2-en-1-yl group, pent-3-en-1-yl group, pent-4-en-1-yl group, 3-methylbut-2-en-1-yl group, 3 -Methylbut-3-en-1-yl group, hex-1-en-1-yl group, hex-2-en-1-yl group, hex-3-en-1-yl group, hex-4-ene -1-yl group, hex-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group, hept-1-en-1 -yl group, hept-6-en-1-yl group, oct-1-en-1-yl group, oct-7-en-1-yl group, non-1-en-1-yl group, non- 8-en-1-yl group, dec-1-en-1-yl group, dec-9-en-1-yl group, undec-1-en-1-yl group, undec-10-en-1-yl group yl group, dodec-1-en-1-yl group, dodec-11-en-1-yl group, tridec-1-en-1-yl group, tridec-12-en-1-yl group, tetradec-1 -en-1-yl group, tetradec-13-en-1-yl group, pentadec-1-en-1-yl group, pentadec-14-en-1-yl group, hexadec-1-en-1-yl group group, hexadec-15-en-1-yl group, heptadec-1-en-1-yl group, heptadec-16-en-1-yl group, octadec-1-en-1-yl group, octadec-9- Examples include en-1-yl group and octadec-17-en-1-yl group. Examples of straight-chain or branched alkynyl groups include ethynyl, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1-yn-1-yl group, but-3 -yn-1-yl group, 1-methylprop-2-yn-1-yl group, pent-1-yn-1-yl group, pent-4-yn-1-yl group, hex-1-yn-1 -yl group, hex-5-yn-1-yl group, hep-1-yn-1-yl group, hep-6-yn-1-yl group, oct-1-yn-1-yl group, oct- 7-yn-1-yl group, non-1-yn-1-yl group, non-8-yn-1-yl group, deca-1-yn-1-yl group, deca-9-yn-1-yl group yl group, undec-1-yn-1-yl group, undec-10-yn-1-yl group, dodec-1-yn-1-yl group, dodec-11-yn-1-yl group, trideca-1 -yn-1-yl group, tridec-12-yn-1-yl group, tetradec-1-yn-1-yl group, tetradec-13-yn-1-yl group, pentadec-1-yn-1-yl group group, pentadec-14-yn-1-yl group, hexadec-1-yn-1-yl group, hexadec-15-yn-1-yl group, heptadec-1-yn-1-yl group, heptadec-16-yl group Examples thereof include an yn-1-yl group, an octadec-1-yn-1-yl group, and an octadec-17-yn-1-yl group.

Examples of preferred cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

(aromatic group)
The aromatic group is a group containing an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, etc. The aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. Examples of aromatic groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethyl Phenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group , 2-anthracenyl group, 9-anthracenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 2-chlorophenyl group 2-fluorophenyl and 4-fluorophenyl groups.

(unsaturated group)
An unsaturated group is a group containing an unsaturated bond. Unsaturated bonds are carbon-carbon unsaturated bonds such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, carbon-nitrogen triple bonds, or carbon-heteroatoms. It is an unsaturated bond. Carbon-oxygen double bonds may be included in carbonyl groups, aldehyde groups, carboxyl groups, etc. Carbon-nitrogen double bonds may be included in isocyanate groups, etc. Carbon-nitrogen triple bonds may be included in a cyano group, cyanato group, etc. The total number of carbon atoms and heteroatoms contained in the unsaturated group is preferably 1 to 10, more preferably 1 to 8. Examples of unsaturated groups include acryloyl, methacryloyl, maleic acid monoester, styryl, allyl, vinyl, amide, carbamoyl, cyano, and isocyanate groups.

(oxygen atom-containing group)
The oxygen atom-containing group is a group containing an oxygen atom. An oxygen atom-containing group usually contains a carbon atom and/or a hydrogen atom along with an oxygen atom. The number of carbon atoms contained in the oxygen atom-containing group is 6 to 20 when it contains an aromatic ring group and/or an alicyclic group, particularly 6 to 12, and when it does not contain an aromatic ring group and an alicyclic group. 0 to 20, more preferably 0 to 12, particularly preferably 0 to 6. Examples of oxygen atom-containing groups include hydroxy, alkoxy, acetoxy, acetyl, aldehyde, carboxy, carbamoyl, urethane, amide, imide, urea, ether, carbonyl, and ester groups. , oxazole groups and morpholine groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, phenylmethoxy and phenylethoxy. Examples of preferred oxygen atom-containing groups include a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, an ether group having 1 to 18 carbon atoms, an ester group having 1 to 18 carbon atoms, and a polyoxyethylene group having 1 to 20 carbon atoms. is included.

(phosphorus atom-containing group)
A phosphorus atom-containing group is a group containing a phosphorus atom. A phosphorus atom-containing group usually contains a carbon atom and/or a hydrogen atom along with a phosphorus atom. The number of carbon atoms contained in the phosphorus atom-containing group is 6 to 20, especially 6 to 12, when it contains an aromatic ring group and/or an alicyclic group, and when it does not contain an aromatic ring group and an alicyclic group. 0 to 20, more preferably 0 to 12, particularly preferably 0 to 6. Examples of phosphorus atom-containing groups include phosphine, phosphite, phosphonic acid, phosphinic acid, trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, and methylphosphine. group, ethyl phosphite group, phenyl phosphite group, phosphonic acid group, phosphinic acid group, phosphoric acid group and phosphoric ester group.

(Sulfur atom-containing group)
A sulfur atom-containing group is a group containing a sulfur atom. A sulfur atom-containing group usually contains a carbon atom and/or a hydrogen atom along with a sulfur atom. The number of carbon atoms contained in the sulfur atom-containing group is 6 to 20 when it contains an aromatic ring group and/or an alicyclic group, more preferably 6 to 12, especially 6 to 10, and the number of carbon atoms contained in an aromatic ring group and/or an alicyclic group Examples of sulfur atom-containing groups include thiol groups, sulfide groups, disulfide groups, sulfonyl groups, and sulfonyl groups. thiocarbonyl, thiocarbamoyl, thiourea, thioalkoxy, thiocarboxy, thiophene and thiazole groups.

The sulfur atom-containing group connected to the 2-phenylbenzotriazole skeleton via a sulfide bond (-S-) is a thioorganic group. The thioorganic group is, for example, a thioalkyl group (-S-Alk) which may have a substituent on a hydrogen atom, or a thioaryl ring group (-S-Ary) which may have a substituent on a hydrogen atom. It is. The alkyl group (Alk) may be acyclic or cyclic. When the alkyl group is a cyclic alkyl group, the thioorganic group may be a thiohexyl ring group (-S-Cy) which may have a hydrogen atom substituent.

The substituent for the hydrogen atom in the thioorganic group is an atom corresponding to at least one selected from a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group. Or it may be a group. Examples of these substituents are as described above.

A thioorganic group suitable for reducing the transmittance of light near a wavelength of 400 nm over a long period of time is a thioaryl ring group which may have a hydrogen atom substituent. Organic compound A containing this thioaryl ring group has excellent light resistance. When a branched chain alkyl group, particularly a chain alkyl group having 4 to 9 carbon atoms, is used as a substituent for the hydrogen atom of the thioaryl ring group, light resistance is significantly improved.

Regarding the thioorganic group interposed between two 2-phenylbenzotriazole skeletons, a group containing a unit represented by -S-(Ary)-(Alk)- is also advantageous from the viewpoint of light resistance. As described above, (Ary) is an arylene ring group which may have a hydrogen atom substituent, and (Alk) is an alkylene group which may have a hydrogen atom substituent. In this case as well, (Alk) is preferably a branched chain alkyl group, particularly a branched chain alkyl group having 4 to 9 carbon atoms.

To explain from another aspect, organic compound A is a thioaryl ring group or thiohexyl ring group which may have a hydrogen atom substituent and is represented by any one of formulas (2-1) to (2-3). It may also be a 2-phenylbenzotriazole derivative having the following. Preferred substituents of the 2-phenylbenzotriazole skeleton (see formula (2-1)) that this derivative has will be explained.

In formula (2-1), at least one of R ¹ to R ⁹ is independently a thioaryl ring group or a thiocyclohexyl ring group, and the others are hydrogen atoms or substituents thereof. The substitution position of the thioaryl ring group or thiocyclohexyl ring group is not particularly limited and may be any of R ¹ to R ⁹ , preferably R ⁶ to R ⁹ , and more preferably R ⁷ and R ⁸ . The number of substitutions of the thioaryl ring group or thiocyclohexyl ring group is also not particularly limited, but is preferably 1 to 2, particularly 1.

Note that at least one of A ¹ to A ⁵ of the organic compound A is preferably an oxygen atom-containing group. In particular, at least A ¹ or A ⁵ is preferably an oxygen atom-containing group. A preferred oxygen atom-containing group is a hydroxy group. At least two of A ¹ to A ⁵ of organic compound A are preferably alkyl groups having 1 to 4 carbon atoms. In particular, at least A ² and A ⁴ are preferably alkyl groups having 1 to 4 carbon atoms. A ² and A ⁴ may be a combination of a methyl group and a tert-butyl group.

From the viewpoint of increasing light resistance, the following combinations of substituents are preferred. Preferred examples of combinations of R ⁶ , R ⁷ , R ⁸ and R ⁹ in formula (2-1) are as follows.
A-1 At least one of R ⁶ , R ⁷ , R ⁸ and R ⁹ in formulas (2-1) and (2-3) is a thioaryl ring group. Furthermore, at least one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ in formula (2-2) is a thiocyclohexyl ring group (-S-Cy-...).
A-2 In A-1, X ^1a , X ^1c , and X ^2c of the thioaryl ring group are phenyl ring or naphthyl ring residues.
A-3 In A-1 and A-2, one thioaryl ring group or thiocyclohexyl ring group is bonded to PhBzT ^1a , PhBzT ^1b , PhBzT ^1c , and PhBzT ^2c .
A-4 In any one of A-1 to A-3, one thioaryl ring group or thiocyclohexyl ring group is bonded to R ⁷ or R ⁸ .
A-5 In any one of A-1 to A-4, R ⁶ to R ⁹ other than the thioaryl ring group or the thiocyclohexyl ring group are all hydrogen atoms.
A-6 In any one of A-1 to A-5, X ^1a , X ^1c and X ^2c of the thioaryl ring group are phenyl ring residues.
A-7 In any one of A-1 to A-5, X ^1a , X ^1c and X ^2c of the thioaryl ring group are naphthyl ring residues.

Preferred examples of combinations of R ¹ , R ² , R ³ , R ⁴ and R ⁵ in formulas (2-1) to (2-3) are as follows. Note that R ¹ , R ² , R ³ , R ⁴ , and R ⁵ of PhBzT ^1c and PhBzT ^2c in formula (2-3) may be independently different or the same.
A-1 Hydrocarbon group having 1 to 18 carbon atoms (including hydrocarbon groups having 2 to 18 carbon atoms including alkenyl groups and alkynyl groups), hydroxy group, aromatic group having 6 to 18 carbon atoms, 1 carbon number ~18 ether groups, C1-18 alkoxy groups, C1-18 ester groups, (meth)acryloyloxy groups, and/or C1-20 polyoxyethylene groups, or substituents thereof. It contains one or more substituents selected from hydrocarbon groups having 1 to 18 carbon atoms, in which a hydrogen atom may be substituted, a radical end may be interrupted, or a carbon-carbon bond may be interrupted.
I-2 In I-1, the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group.
I-3 In I-2, the substituent is at least one selected from a hydrocarbon group having 1 to 8 carbon atoms and a hydroxy group.
I-4 In any one of I-1 to I-3, the hydrocarbon group of the substituent is a straight chain or branched alkyl group.
I-5 In I-4, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group.
I-6 In I-5, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group, and the number of hydroxy groups is one or less.
I-7 In any one of I-1 to I-6, the number of substituents is 1 to 4.
I-8 In any one of I-1 to I-7, R ¹ to R ⁴ have a substituent at any position, and the other R ¹ to R ⁵ are hydrogen atoms.
I-9 In any one of I-1 to I-8, R ¹ , R ² or R ⁴ has a substituent at any position, and the other R ¹ to R ⁵ are hydrogen atoms.
I-10 In I-9, R ¹ is a hydroxy group, R ² is a t-butyl group, R ⁴ is a methyl group, and R ³ and R ⁵ are hydrogen atoms.
I-11 In any one of I-1 to I-9, R ¹ or R ⁴ has a substituent at either position, and the other R ¹ to R ⁵ are hydrogen atoms.
I-12 In I-11, R ¹ is a hydroxy group, R ⁴ is a methyl group, and R ² , R ³ and R ⁵ are hydrogen atoms.

Preferred examples of combinations of l R ^1a and X ^1a in formula (2-1) are as follows.
U-1 X ^1a is a phenyl ring residue.
Wu-2 In Wu-1, l=0, there is no substituent R ^1a on X ^1a , and all moieties that can be substituted for R ^1a in X ^1a are hydrogen atoms.
U-3 In U-1, each R ^1a is independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. and l=1 to 5.
Wu-4 In Wu-3, l=1 to 3.
Wu-5 In Wu-4, R ^1a is each independently at least one branched alkyl group having 3 to 8 carbon atoms.
Wu-6 In Wu-4, l=1 and R ^1a are each independently a straight chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
U-7 In U-6, l=1, R ^1a is each independently a straight chain or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group preferably has 1 to 8 carbon atoms, and more preferably It preferably has 2 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and even more preferably 4 carbon atoms.
Wu-8 In any one of Wu-3 to Wu-7, at least one R ^1a is at the para position with respect to PhBzT ^1a -S-.
Wu-9 In Wu-4, l=2 and R ^1a are each independently a straight chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
U-10 In U-9, l=2, R ^1a is each independently a straight chain or branched alkyl group having 1 to 10 carbon atoms, and each alkyl group preferably has 1 to 5 carbon atoms. , more preferably 1 to 4 carbon atoms, still more preferably 1 carbon number, and/or the total carbon number of the alkyl group is preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 5 carbon atoms, and particularly preferably is 2.
Wu-11 In either Wu-9 or Wu-10, each R ^1a of PhBzT ^1a -S- has l=2 at the ortho or para position or the ortho or meta position.
U-12 In any of U-3 to U-11, R ^1a is each independently a hydrocarbon group having a tertiary carbon and/or a quaternary carbon, preferably an alkyl group.
U-13 In U-1, l R ^1a are each independently an alkoxy group having a straight chain or branched alkyl group having 1 to 18 carbon atoms, preferably a straight chain alkyl group having 1 to 8 carbon atoms. It is an alkoxy group having a group, more preferably an alkoxy group having a straight chain alkyl group having 1 to 4 carbon atoms. Further, preferably l=1 to 3, more preferably l=1 to 2, particularly preferably l=1.
Wu-14 In Wu-13, l=1 and the alkoxy group is in the meta position relative to PhBzT ^1a -S-.
U-15 In U-1, l R ^1a are hydroxy groups, preferably l=1 to 3, more preferably l=1 to 2, particularly preferably l=1.
Wu-16 In Wu-15, l=1 and the hydroxy group is in the para position to PhBzT ^1a -S-.
Wu-17 X ^1a is a residue of a naphthyl ring, preferably l=0.

The 2-phenylbenzotriazole derivative represented by formula (2-1) is not particularly limited, but for example, 5-phenylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H -benzotriazole, 5-(4-tert-butyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(2,4-dimethyl-phenylthio) )-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(3-methoxy-phenylthio)-2-(2-hydroxy-3-tert-butyl-5 -methylphenyl)-2H-benzotriazole, 5-(4-(1,1-dimethyl-propyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzo Triazole, 5-(4-isopropyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-(1,1,3,3- Tetramethyl-butyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(2-methyl-5-tert-butyl-phenylthio)-2 -(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-(4-methyl-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl )-2H-benzotriazole, 5-(2,4-di(1,1-dimethylpropyl)-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole , 5-(4-hydroxy-phenylthio)-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 5-naphthylthio-2-(2-hydroxy-3-tert- Examples include butyl-5-methylphenyl)-2H-benzotriazole, 5-phenylthio-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, and the like.

Preferred examples of combinations of m R ^1b in formula (2-2) are as follows.
A-1 m=0, Cy has no substituent R ^1b , and all moieties that can be substituted for R ^1b in Cy are hydrogen atoms.
A-2 m R ^1b 's are each independently a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and m= 1 to 5.
A-3 In A-2, m=1 to 3.
A-4 In A-3, R ^1b is each independently at least one branched alkyl group having 3 to 8 carbon atoms.
A-5 In A-3, m=1 and R ^1b is a straight chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
A-6 In A-5, when m=1, R ^1b is a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group preferably has 1 to 8 carbon atoms, more preferably carbon atoms. It has 2 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and even more preferably 4 carbon atoms.
A-7 In any one of A-2 to A-6, at least one R ^1b is at the para position with respect to PhBzT ^1b -S-.
A-8 In A-3, m=2, and R ^1b is each independently a straight-chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
A-9 In A-8, m=2, R ^1b is each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and each alkyl group preferably has 1 to 5 carbon atoms. , more preferably 1 to 4 carbon atoms, still more preferably 1 carbon number, and/or the total carbon number of the alkyl group is preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 5 carbon atoms, and particularly preferably is 2.
A-10 In either A-8 or 9, R ^1b with m=2 is at the ortho or para position or the ortho or meta position with respect to PhBzT ^1b -S-.
A-11 In any of A-2 to A-10, R ^1b is a hydrocarbon group having a tertiary carbon and/or a quaternary carbon, preferably a branched alkyl group.
A-12 In A-1, m R ^1b are each independently an alkoxy group having a straight chain or branched alkyl group having 1 to 18 carbon atoms, preferably a straight chain alkyl group having 1 to 8 carbon atoms. It is an alkoxy group having a group, more preferably an alkoxy group having a straight chain alkyl group having 1 to 4 carbon atoms. Further, preferably m=1 to 3, more preferably m=1 to 2, particularly preferably m=1.
A-13 In U-12, m = 1, and the alkoxy group is at the meta position with respect to PhBzT ^1b -S-. A-14 In A-1, m R ^1b are hydroxy groups, preferably m=1 to 3, more preferably m=1 to 2, particularly preferably m=1.
A-15 In A-14, m=1 and the hydroxy group is in the para position to PhBzT ^1b -S-.

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

In formula (2-3), A ^2c is a monovalent or divalent group selected from aromatic groups, unsaturated groups, nitrogen-containing groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and halogen atoms. A divalent hydrocarbon group having 1 to 20 carbon atoms, in which a hydrogen atom is substituted, at least one of both ends is interrupted, or a carbon-carbon bond is interrupted, 2 represents a valent aromatic group or a sulfide group -S-.

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

When the divalent hydrocarbon group is the monovalent or divalent group, a hydrogen atom is substituted, at least one of both ends is interrupted, or a carbon-carbon bond is interrupted, The number of valent or divalent groups is not particularly limited, but examples thereof include 2 or less, or 1 or less. Specific examples of the aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom of the monovalent or divalent group include 2- As substituents for R ¹ to R ⁹ of the phenylbenzotriazole skeleton, the same monovalent or divalent groups as described above may be mentioned, and the description thereof is referred to.

The divalent aromatic group in A ^2c includes an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, etc., and preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. The divalent aromatic group is not particularly limited, but includes, for example, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,8-naphthylene group, 2,7-naphthylene group. , 2,6-naphthylene group, 1,4-naphthylene group, 1,3-naphthylene group, 9,10-anthracenylene group, 1,8-anthracenylene group, 2,7-anthracenylene group, 2,6-anthracenylene group, Examples include 1,4-anthracenylene group and 1,3-anthracenylene group.

Preferred examples of combinations of n R ^1c and X ^1c , p R ^2c and X ^2c , and q A ^2c in formula (2-3) are as follows.
O-1 X ^1c and X ^2c are phenyl ring residues.
O-2 In O-1, n and p=0, there are no substituents R ^1c and R 2c in X ^1c and X ^2c , and all moieties that can be substituted for R 1c ^{and R 2c in} X ^1c and ^{X 2c are} hydrogen. It is an atom.
O-3 In O-1, n and p R ^1c and R ^2c are each independently a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably a linear chain having 1 to 18 carbon atoms. or a branched alkyl group, where n and p=1 to 5.
O-4 In O-3, n and p=1 to 3.
O-5 In O-4, R ^1c and R ^2c each independently represent at least one branched alkyl group having 3 to 8 carbon atoms.
O-6 In O-4, n and p=1, and R ^1c and R ^2c are each independently a straight chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
O-7 In O-6, n and p=1, R ^1c and R ^2c are each independently a straight chain or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group preferably has a carbon number of It has 1 to 8 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and even more preferably 4 carbon atoms.
O-8 In O-4, n and p=2, and R ^1c and R ^2c are each independently a straight chain or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
O-9 In O-8, n and p=2, R ^1c and R ^2c are each independently a straight chain or branched alkyl group having 1 to 10 carbon atoms, and each carbon number of the alkyl group is: The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1, and/or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, and even more preferably 2. -5, particularly preferably 2.
O-10 In any one of O-3 to O-9, R ^1c and R ^2c are each independently a hydrocarbon group having a tertiary carbon and/or a quaternary carbon, preferably an alkyl group.
O-11 In O-1, n and p R ^1c and R ^2c are each independently an alkoxy group having a straight chain or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. An alkoxy group having a straight chain alkyl group, more preferably an alkoxy group having a straight chain alkyl group having 1 to 4 carbon atoms. Further, preferably n and p=1 to 3, more preferably n and p=1 to 2, particularly preferably n and p=1.
O-12 In O-1, n and p R ^1c and R ^2c are hydroxy groups, preferably n and p = 1 to 3, more preferably n and p = 1 to 2, particularly preferably n, p=1.
O-13 X ^1c and X ^2c are naphthyl ring residues, preferably n and p=0.
O-14 In any one of O-1 to O-13, q=1 and A ^2c is a sulfide group. Preferably, n, p=0, X ^1c and X ^2c do not have substituents R ^1c and R ^2c , and all moieties that can be substituted for R 1c and R ^2c in X ^1c and ^{X 2c are} hydrogen atoms.
O-15 In any one of O-1 to O-13, q=1 and A ^2c is a hydrocarbon group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) (preferably a linear or branched alkylene group). basis). Preferably, n, p=0, X ^1c and X ^2c do not have substituents R ^1c and R ^2c , and all moieties that can be substituted for R 1c and R ^2c in X ^1c and ^{X 2c are} hydrogen atoms.
O-16 In any one of O-1 to O-13, q=0. Preferably, n, p=0, X ^1c and X ^2c do not have substituents R ^1c and R ^2c , and all moieties that can be substituted for R 1c and R ^2c in X ^1c and ^{X 2c are} hydrogen atoms.
O-17 In any of O-1 to O-16, -(A ^1c ) _q - is at the para position with respect to PhBzT ^1c -S- and PhBzT ^2c -S-.

The 2-phenylbenzotriazole derivative represented by formula (2-3) is not particularly limited, but for example, 4,4'-thiobis[(2-hydroxy-3-tert-butyl-5-methylphenyl)- 2H-benzotriazol-5-yl-thiobenzene], 4,4'-propane-2,2-diyl-bis[(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5 -yl-thiobenzene], 4,4'-biphenyl-bis[(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazol-5-yl-thio], and the like.

Further preferred embodiments of the organic compound A are as follows.
・The 2-phenylbenzotriazole derivative is represented by the formula (2-1) or (2-3), and in the formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c are It represents a phenyl ring residue, and l, n, and p are 0.
In particular, the 2-phenylbenzotriazole derivative is represented by either formula (2-1) or (2-3), and in formula (2-1) or (2-3), X ^1a , X ^1c , X ^2c represents a phenyl ring residue, l, n, and p are 0, and R ¹ of the 2-phenylbenzotriazole skeleton has a hydroxy group and R ⁴ has a methyl group.

・The 2-phenylbenzotriazole derivative is represented by the formula (2-1) or (2-3), and in the formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c are Represents a phenyl ring residue, l, n, and p R ^1a , R ^1c , and R ^2c each independently represent a straight-chain or branched hydrocarbon group having 1 to 18 carbon atoms, and l, n, and p are Indicates an integer from 1 to 5.
In particular, in formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c represent phenyl ring residues, and l, n, and p R ^1a , R ^1c , and R ^2c are each independently At least one of them represents a branched alkyl group having 3 to 8 carbon atoms, and l, n, and p represent integers of 1 to 3.
Alternatively, in formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c represent phenyl ring residues, and l, n, and p R ^1a , R ^1c , and R ^2c are each independently represents a straight chain or branched alkyl group having 1 to 18 carbon atoms, and l, n, and p represent an integer of 1.
Alternatively, in formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c represent phenyl ring residues, and l, n, and p R ^1a , R ^1c , and R ^2c are each independently represents a straight chain or branched alkyl group having 1 to 18 carbon atoms, and l, n, and p represent an integer of 2.
Alternatively, in formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c represent phenyl ring residues, and l, n, and p R ^1a , R ^1c , and R ^2c are each independently represents a hydrocarbon group having tertiary carbon and/or quaternary carbon having 1 to 18 carbon atoms, and l, n, and p represent integers of 1 to 5.

- The 2-phenylbenzotriazole derivative is represented by either formula (2-1) or (2-3), and in formula (2-1) or (2-3), X ^1a , X ^1c , X ^2c represents a phenyl ring residue, and l, n, and p R ^1a , R ^1c , and R ^2c each independently represent an alkoxy group having a linear or branched alkyl group having 1 to 18 carbon atoms.

・The 2-phenylbenzotriazole derivative is represented by the formula (2-1) or (2-3), and in the formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c are It represents a phenyl ring residue, and l, n, and p R ^1a , R ^1c , and R ^2c represent a hydroxyl group.

・The 2-phenylbenzotriazole derivative is represented by the formula (2-1) or (2-3), and in the formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c are Residues of the naphthyl ring are shown.

- The 2-phenylbenzotriazole derivative is represented by formula (2-2), and in formula (2-2), m is 0.

- The 2-phenylbenzotriazole derivative is represented by formula (2-2), and in formula (2-2), R ^1b each independently represents a hydrocarbon group having 1 to 18 carbon atoms.

- The 2-phenylbenzotriazole derivative is represented by the formula (2-3), in which X ^1c and X ^2c represent phenyl ring residues, q is 1, and A ^2c represents a sulfide group -S-.

- The 2-phenylbenzotriazole derivative is represented by the formula (2-3), in which X ^1c and X ^2c represent phenyl ring residues, q is 1, and A ^2c represents a hydrocarbon group having 1 to 8 carbon atoms.

- The 2-phenylbenzotriazole derivative is represented by formula (2-3), where X ^1c and X ^2c represent phenyl ring residues, and q is 0.

It is preferable that the organic compound A maintains a crystalline state in the coating film forming composition and the coating film. It can be confirmed by X-ray diffraction that the organic compound maintains a crystalline state.

The organic compound A is preferably crushed using a known dry or wet crushing device to a predetermined average particle size, and then blended into the composition for forming a coating film. The time required for the organic compound A to reach a predetermined average particle size after being pulverized depends on the pulverizing conditions such as the type of pulverizer, the input amount, and the number of rotations. For this reason, when mass producing, it is recommended to stop the grinding by the grinding device as appropriate and check the average particle size of the sampled crushed material in advance, and determine the time required to obtain the desired average particle size. good. In addition, at the time of pulverization, a surfactant, a water-soluble resin, etc. may be appropriately added to the organic compound A to be pulverized.

The organic compound A is preferably dispersed in the film as fine particles having an average particle size of 150 nm or less, preferably 10 to 150 nm, more preferably 50 to 140 nm, particularly preferably 70 to 140 nm. If the average particle diameter of the fine particles is too large, the transparency of the film will be reduced, but if it is too small, the ultraviolet absorbing ability may deteriorate or its sustainability may decrease. The above "average particle size" is a value based on the measured value by dynamic light scattering, which is a type of photon correlation method, including the measured value in the Examples section described later. This is the particle diameter at which the cumulative frequency is 50% in the volume-based diameter distribution. The "average particle size" can be measured using, for example, "Microtrac Ultrafine Particle Size Distribution Meter 9340-UPA150" manufactured by Nikkiso Co., Ltd.

The presence of the organic compound A fine particles dispersed in the film can be confirmed by observing them using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The average value A of the top 10% of the maximum length of each fine particle present in the membrane cross section observed using SEM or TEM does not fall below the value of the "average particle size" as defined above. Therefore, if the average value A is 150 nm or less, the "average particle size" can be considered to be 150 nm or less. In addition, the average value B of the lowest 10% of the lengths in the direction orthogonal to the direction that defines the maximum length of each fine particle existing in the membrane cross section must exceed the value of the "average particle diameter" as defined above. There isn't. Therefore, for example, if the average value B is 50 nm or more, the "average particle size" may be considered to be 50 nm or more.

The organic compound A can also be introduced into the membrane as a solute dissolved in an organic solvent that can dissolve it. Introduction as a solute is a method that is easier to implement and is also a desirable method for achieving a more uniform distribution of the organic compound A in the coating film. However, by introducing organic compound A into the film in the form of fine particles, the sustainability of the ultraviolet shielding ability of the film is improved. Furthermore, by adding organic compound A as fine particles, more preferable spectral absorption characteristics can be obtained than when adding organic compound A as a solute.

By adding it as fine particles, the absorption peak of organic compound A in the spectral absorbance curve may be shifted to a longer wavelength side than when it is added as a solute. This shift makes it possible to more effectively block light with a wavelength of around 400 nm. On the other hand, however, due to the shift of the absorption peak to the longer wavelength side, the yellowish coloring of the coating film becomes more intense. Organic compound A is suitable for sufficiently lowering the transmittance of light around a wavelength of 400 nm while suppressing strong yellowish coloring of the coating film.

The composition for forming a coating film may be a film forming solution containing a silicon oxide precursor and an organic compound A. Water and lower alcohols are suitable as the solvent constituting the film-forming solution, with water being the most suitable. As the lower alcohol, alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and isopropanol are suitable. The composition for forming a coating film may contain components that may be blended into the coating film, such as organic compound B and a silane coupling agent. The composition for forming a coating film may contain additives such as a wetting agent, a preservative, a fungicide, an antifoaming agent, and a stabilizer, as required.

The type of silicon oxide precursor is not limited as long as it can supply silicon oxide to the coating film. When forming a coating film by the sol-gel method described below, a preferred silicon oxide precursor is a silicon compound having a hydrolyzable functional group, typically silicon tetraalkoxide. Note that silicon oxide is also supplied from silicon atoms contained in the silane coupling agent. Therefore, the silane coupling agent also functions as a silicon oxide precursor.

Silicon oxide in the coating film may account for 40% by mass or more, 50% by mass or more of the entire film (in this case, silicon oxide is the main component of the film), and in some cases 70% by mass or more. The coating film preferably contains silicon oxide as a main component, and has a form in which fine particles of organic compound A and other components are dispersed in a network of Si--O bonds. A film having such a configuration is suitable for outdoor use as window glass or the like. The composition for forming a coating film preferably contains a silicon oxide precursor so that the silicon oxide content of the coating film formed from the composition is within the above range.

The organic compound A is contained in a range of 1 to 80%, further 5 to 60%, particularly 5 to 50%, particularly 7 to 30%, based on the silicon oxide in the coating film. Preferably. Considering this, the organic compound A should be added in an amount of 0.5 to 25%, more preferably 0.5 to 15%, based on the amount of the film forming solution, expressed in mass%. It is preferable to do so.

Organic compound B is an ultraviolet shielding component that does not correspond to organic compound A. The organic compound B preferably has a molecular structure that includes a 2-phenylbenzotriazole skeleton and has no sulfur atom-containing group connected to the 2-phenylbenzotriazole skeleton. The organic compound B may also be blended into the coating film or the composition for forming a coating film so that it has the form of fine particles with an average particle size of 150 nm or less.

Organic compound B is represented by the following formula (3), for example.

B ¹ to B ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group other than a thioorganic group. An atom or group that corresponds to at least one of the following. To be more precise, B ¹ to B ⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a thioorganic group. The group corresponds to at least one sulfur atom-containing group other than sulfur atom-containing groups. B ¹ to B ⁹ may correspond to two or more of the above groups. Specific examples of the halogen atom and each functional group are as described above for organic compound A.

Similar to organic compound A, at least one of B ¹ to B ⁵ of organic compound B is preferably an oxygen atom-containing group. In particular, at least B ¹ or B ⁵ is preferably an oxygen atom-containing group. A preferred oxygen atom-containing group is a hydroxy group. At least two of B ¹ to B ⁵ of organic compound B are preferably alkyl groups having 1 to 4 carbon atoms. B ² and B ⁴ may be a combination of a methyl group and a tert-butyl group.

Like organic compound A, organic compound B preferably maintains a crystalline state in the coating film forming composition and coating film. The organic compound B is preferably crushed using a known dry or wet crushing device so as to have a predetermined average particle size, and then blended into the composition for forming a coating film. The preferred average particle size of organic compound B is as described above for organic compound A. It is preferable that the organic compound B is blended in such a manner that the total amount of the organic compound B and the organic compound A is in the ratio described above for the organic compound A to silicon oxide in the coating film. Organic compound B is preferably added in an amount that is less than organic compound A, preferably less than 50% of organic compound A, on a mass basis.

Organic compound B may have two or more 2-phenylbenzotriazole skeletons. Two or more 2-phenylbenzotriazole skeletons are preferably connected by the above-mentioned groups.

A preferred example of the organic compound B having two 2-phenylbenzotriazole skeletons has a form in which they are bonded to each other through methylene groups bonded to B ² of each skeleton. In this form, B ¹ of each skeleton may be a hydroxy group, B ⁴ may be a tert-butyl group, and B ³ and B ⁵ may be hydrogen atoms.

Another example of organic compound B is a benzophenone compound. The benzophenone compound has the following formula (4) as its basic skeleton. However, the hydrogen atom of the benzene ring may be substituted with a substituent. The substituents may be the groups listed for B ¹ to B ⁹ . Organic compound B, which is a benzophenone compound, includes 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, An example is 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone).

The organic compound C is a hydrophilic organic compound and may be a polymer. The organic compound C contributes to improving the dispersibility of the benzotriazole-based UV-shielding component, which is the organic compound A or organic compounds A and B, in the coating film, increases the light-shielding ability of the benzotriazole-based UV-shielding component, and further This component suppresses the deterioration of this component. When forming a relatively thick coating film (for example, over 300 nm, or even over 500 nm) by liquid-phase film formation such as a sol-gel method, as the liquid component contained in the film forming solution evaporates, Cracks may occur. The organic compound C is also a component that enables the formation of a thick film while suppressing the occurrence of cracks.

The organic compound C preferably corresponds to at least one selected from polyether compounds, polyol compounds, polyvinylpyrrolidones, and polyvinylcaprolactams. A polyether compound is a compound containing two or more ether bonds. A polyol compound is a compound containing two or more hydroxy groups. Polyvinylpyrrolidones are polymers containing vinylpyrrolidone and its derivatives as monomers. Polyvinylcaprolactams are polymers containing vinylcaprolactam and derivatives thereof as monomers. Examples of the organic compound C include polyether type surfactants and polyol compounds produced by the reaction of epoxy groups of polyepoxy compounds. Organic compound C may be a polymer. Examples of organic compound C also include polycaprolactone polyol, bisphenol A polyol, polyethylene glycol, and polypropylene glycol.

The organic compound C is 0 to 75%, particularly 0.05 to 50%, particularly 0.1 to 40%, particularly 1 to 30%, in some cases, based on the silicon oxide in the film, expressed as mass %. is preferably added to the film in an amount of 10% or less, and if necessary, 7% or less.

The type of silane coupling agent is not particularly limited, but an organic compound represented by LSiM ₃ is preferable. Here, L is at least one selected from a vinyl group, a glycidoxy group, a methacryl group, an amino group, and a mercapto group, and M is a halogen element or an alkoxy group. In the silane coupling agent, the L group reacts with the organic substance in the coating film, and the M group hydrolyzes and reacts with the inorganic substance in the film. Through this reaction, the silane coupling agent contributes to improving the dispersibility of the ultraviolet shielding components, which are organic compound A or organic compounds A and B, in the film, making it possible to form a thick film while suppressing the occurrence of cracks. It has the effect of In the silane coupling agent, silicon oxide supplied from the silane coupling agent is expressed in mol% of 0 to 30%, preferably 0.1 to 20%, more preferably 0.1 to 20%, based on the total silicon oxide in the coating film. is preferably added to the film in an amount of 1 to 10%.

Note that the silicon oxide supplied from the silane coupling agent is calculated according to the number of oxygen atoms bonded to silicon atoms in the structural unit derived from the silane coupling agent in the coating film. For example, silicon oxide supplied from the silane coupling agent represented by LSiM ₃ above is expressed as SiO _1.5 because the silicon atom is bonded to three oxygen atoms.

Other components that the coating film may contain include indium tin oxide (ITO) fine particles. ITO fine particles are a preferred component for absorbing near-infrared rays. The ITO fine particles are preferably dispersed in the film as fine particles having an average particle size of 200 nm or less, preferably 5 to 150 nm. As with the fine particles of organic compound A, if the particle size is too large, the transparency of the film will be reduced, and if the particle size is too small, the effect of addition will not be sufficiently obtained. It is preferable to prepare a dispersion of ITO fine particles in advance and add this to the film forming solution. The coating film may contain inorganic components other than silicon oxide and ITO fine particles. Examples of such inorganic components include components derived from acid catalysts used in the sol-gel method.

The coating film 2 has silicon oxide as a main component. Preferably, the coating film 2 has a form in which the main component is silicon oxide, and fine particles of the organic compound A and other components are dispersed in a network constituted by Si--O bonds. A membrane having such a morphology is particularly suitable for outdoor use, such as as window glass.

A preferred method for forming a coating film by the sol-gel method will be described below. The organic solvent used in the sol-gel method is preferably a solvent that is highly compatible with silicon alkoxide or water, and lower alcohols having 1 to 3 carbon atoms are suitable. Examples of silicon alkoxides that are silicon oxide precursors include silicon tetraalkoxides such as silicon tetramethoxide, silicon tetraethoxide (TEOS), and silicon tetraisopropoxide. A hydrolyzate of silicon alkoxide may be used as the silicon oxide precursor. The concentration of silicon alkoxide in the solution formed by the sol-gel method is preferably 3 to 15% by mass, particularly 3 to 13% by mass, expressed as silicon oxide concentration when silicon alkoxide is converted to silicon oxide. If this concentration is too high, cracks may occur in the film.

The molar ratio of water to silicon alkoxide is preferably 4 times or more, specifically 4 to 40 times, preferably 4 to 35 times. As the hydrolysis catalyst, it is preferable to use an acid catalyst, particularly a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, and paratoluenesulfonic acid. Since organic substances derived from acid catalysts may reduce film hardness, inorganic acids are preferable as acid catalysts. Hydrochloric acid is the most preferred acid catalyst because it is highly volatile and does not easily remain in the membrane. The concentration of the acid catalyst is preferably in the range of 0.001 to 2 mol/kg expressed as the mass molar concentration of protons assuming that protons are completely dissociated from the acid.

By adding an excess of water to the above level and adding an acid catalyst to the above concentration, a relatively thick film can be easily formed by the sol-gel method in a temperature range where decomposition of organic matter can be prevented.

A coating film can be formed by mixing a solution containing the above-mentioned components that can be applied to the sol-gel method with a dispersion in which fine particles such as organic compound A are dispersed, and further adding organic compound C etc. as necessary. Can prepare solutions. However, the method for preparing the film forming solution is not limited to this, and components necessary for film formation by the sol-gel method may be sequentially added to the fine particle dispersion. The film-forming solution may be prepared to contain, together with fine particles such as organic compound A, components necessary for forming a film by a method other than the sol-gel method, such as polysilazane.

In the step of applying the film forming solution, the relative humidity of the atmosphere is preferably kept below 40%, more preferably below 30%. Keeping the relative humidity low prevents the membrane from absorbing too much moisture from the atmosphere. If a large amount of water is absorbed from the atmosphere, the remaining water that enters the membrane matrix may reduce the strength of the membrane.

The drying process of the film forming solution is preferably carried out to include an air drying process in a coating environment and a heat drying process involving heating. The air-drying step is preferably carried out by exposing the coated film of the forming solution to an atmosphere in which the relative humidity is maintained at less than 40%, preferably 30% or less. In the heat drying process, the condensation reaction of silanol groups generated by hydrolysis progresses, and the removal of liquid components remaining in the film, especially water, progresses, and the silicon oxide matrix (Si-O bond network) progresses. ) develops. The heat drying step is preferably carried out by exposing the coating film to an atmosphere of 300° C. or lower, for example 100 to 200° C. The heat drying step is preferably carried out by exposing and heating the coating film to an atmosphere of 300° C. or lower, for example 100 to 200° C., and in some cases 50 to 100° C. The heating temperature in the heat drying step is preferably lower than the melting point of organic compounds A and B added as fine particles, particularly organic compound A added as fine particles.

The heating temperature at which the film is heated in the heat drying step is preferably selected from a range lower than the melting point of the organic compound A added as fine particles. When adding organic compound B as fine particles, the heating temperature is preferably selected from a range lower than the melting point of organic compound A and the melting point of organic compound B. The melting points of organic compound A and organic compound B are preferably 65°C or higher, particularly 100°C or higher, for example 120 to 240°C, and may be 140 to 240°C.

The series of steps explained above, namely, a) step of preparing a film-forming solution for a coating film containing fine particles of organic compound A, etc., b) a step of applying the film-forming solution onto a glass plate, c) drying of the film-forming solution. By sequentially performing the steps, the glass plate of this embodiment can be obtained by a liquid phase film forming method. This manufacturing method uses a film forming solution for a coating film that contains a silicon-containing compound such as silicon alkoxide as a solute, and contains organic compound A, which is solid at room temperature and has an average molecular weight of 5,000 or less, as fine particles with an average particle size of 150 nm or less. A process of preparing a glass plate having a coating film, a process of applying the film-forming solution on a glass plate, and a process of drying the film-forming solution on the glass plate to form a coating film. This is the manufacturing method. This manufacturing method constitutes another aspect of the present invention.

The thickness of the coating film is preferably more than 300 nm and less than 15 μm, more preferably more than 500 nm and less than 10 μm, particularly more than 1000 nm and less than 5000 nm. If the film is too thin, sufficient ultraviolet shielding ability may not be obtained, and if the film is too thick, the transmittance of the film may decrease, impairing the transparency of the glass plate.

The glass plate is not particularly limited, and a soda lime silicate glass plate can be used. A typical composition example of this glass plate is shown. In the following, all "%" indicating the content of each component included in the glass plate is mass %. The alkali metal oxide (R ₂ O) is specifically the total amount of Na ₂ O and K ₂ O. T-Fe ₂ O ₃ is total iron oxide converted to Fe ₂ O ₃ . Moreover, each composition example may contain trace components that are not displayed.

(clear glass)
SiO ₂ :70-73%
Al ₂ O ₃ :0.6-2.4%
CaO: 7-12%
MgO: 1.0-4.5%
R ₂ O: 13-15%
T-Fe ₂ O ₃ :0.08-0.2%

As a soda lime silicate glass plate, a glass composition containing more than 0.2%, preferably 0.4% or more, more preferably 0.5% or more, for example 0.5 to 1.3% iron oxide A glass plate having a light transmittance of 70% or less at a wavelength of 380 nm, preferably 50% or less, and a light transmittance of 75% or more at a wavelength of 550 nm may be used. Some composition examples of such glass plates are illustrated below.

(green glass)
SiO ₂ :70-73%
Al ₂ O ₃ :0.6-2.4%
CaO: 7-12%
MgO: 1.0-4.5%
R ₂ O: 13-15%
T-Fe ₂ O ₃ :0.4-0.6%

(heat ray absorbing glass)
SiO ₂ :70-73%
Al ₂ O ₃ :0.6-2.4%
CaO: 7-12%
MgO: 1.0-4.5%
R ₂ O: 13-15%
T-Fe ₂ O ₃ :0.5-1.1%

(UV cut green glass)
SiO ₂ :70-73%
Al ₂ O ₃ :0.6-2.4%
CaO: 7-12%
MgO: 1.0-4.5%
R ₂ O: 13-15%
T-Fe ₂ O ₃ :0.7-1.3%
_CeO2 : 0-2%
_TiO2 : 0-0.5%

It is also possible to use a high transmittance glass plate with an iron oxide content of 0.1% or less, preferably 0.01% to 0.06%. An example is shown below.

(High transmittance glass)
SiO ₂ :70-73%
Al ₂ O ₃ :0.6-2.4%
CaO: 7-12%
MgO: 1.0-4.5%
R ₂ O: 13-15%
T-Fe ₂ O ₃ :0.01-0.06%.

The glass plate is not limited to the above, and may have a low light transmittance in the visible range. Examples of such glass plates include glass plates manufactured for vehicle window glasses that have a light transmittance of 20 to 60% at a wavelength of 550 nm. Since it is difficult to sufficiently block ultraviolet light, especially in the long wavelength range, with only the components constituting the glass plate, it is useful to apply the coating film 2 described above even to glass plates with low visible light transmittance. It is.

The glass plate of this embodiment may have an ultraviolet transmittance T _UV 380 based on ISO 9050 (1990 edition) of 2% or less, preferably 1% or less, and more preferably 0.5% or less. Further, the glass plate of this embodiment may have an ultraviolet transmittance T _UV 400 calculated according to ISO13837 (convention A) of 2% or less, preferably 1.5% or less, particularly preferably 1% or less. The glass plate of this embodiment may have a visible light transmittance YA of 70% or more when measured using a CIE standard A light source. The glass plate of this embodiment may have a T _UV 400 of 2% or less and a YA of 70% or more.

In the glass plate of this embodiment, the transmitted light ^{from the CIE standard C light source may have a* of -15 or more and 0 or less and b* of} 12 or less, as expressed by the L ^* a ^* b ^* color system. . a ^* may be -12 or more and -7 or less, for example -9 or more and -8 or less, and b ^* may be 10 or less, for example 5 to 10. Further, the glass plate of this embodiment may have a yellowness YI of 14 or less as defined in Japanese Industrial Standards (JIS) K7373:2006 of transmitted light for CIE standard C light source. The yellowness YI may be 10 or less, or even 8 or less. Further, in the glass plate of this embodiment, the dominant wavelength of transmitted light for the CIE standard C light source may be 560 nm or less. The dominant wavelength may be below 555 nm, for example in the range of 550-555 nm. The glass plate of this embodiment may have a blue light cut rate of 41% or less, preferably 37% or less, particularly preferably 36% or less based on the blue light obstruction function of JIS T7330.

The blue light cut rate is expressed as a percentage, which is the ratio of the effective radiant intensity reduced by passing through the glass plate to the effective radiant intensity related to retinal damage caused by blue light from sunlight (hereinafter referred to as the effective radiant intensity of sunlight). Specifically, it can be determined by the following method. The effective radiant intensity of sunlight is determined by integrating the wavelengths of 380 to 550 nm for the weighting function regarding the blue light disturbance function described in Appendix A of JIS T7330:2000. Next, the sum of the products of the spectral transmittance of the glass plate and the weighting function at each wavelength in the above wavelength range is taken to determine the effective radiant intensity of the light transmitted through the glass plate (hereinafter referred to as effective radiant intensity of transmitted light). The ratio of the effective radiant intensity of transmitted light to the effective radiant intensity of sunlight can be taken, and the value can be subtracted from 1 to convert it into a percentage.

The glass plate of this embodiment has a difference obtained by subtracting the ultraviolet transmittance T _UV 400 before irradiating the ultraviolet rays from the ultraviolet transmittance T _UV 400 after being irradiated with ultraviolet rays with a wavelength of 295 to 450 nm and an illuminance of 76 mW/cm ² for 100 hours. The ΔT _UV 400 may be 2% or less, even 1% or less, especially 0.5% or less. The glass plate of this embodiment has a difference ΔYA obtained by subtracting the visible light transmittance YA before irradiating the ultraviolet rays from the visible light transmittance YA after irradiating the ultraviolet rays with a wavelength of 295 to 450 nm and an illuminance of 76 mW/cm ² for 100 hours. It can be -0.5% or more, especially -0.2% or more. ΔYA may be -0.5% or more and 1% or less, or more preferably -0.2% or more and 0.5% or less.

The glass plate of this embodiment is suitable for use as window glass for buildings and transportation equipment, specifically for transportation equipment such as automobiles, railway vehicles, ships, and aircraft, and is particularly suitable for use as window glass for automobiles. There is. However, when used as a window glass that can be raised and lowered or opened and closed, as typified by automobile door glass, the peripheral surface of the glass plate repeatedly comes into contact with an end holding member called a run channel. It turns out. For this reason, there is a risk that the film may peel off during a long period of use, impairing the appearance of the window glass. Therefore, in such applications, as shown in FIGS. 2 and 3, it is preferable not to form the coating film 11 on the glass plates constituting the window glasses 10 and 20 in the peripheral area 12 that contacts the end holding member. preferable. In addition, if the presence of the coating film 11 makes it difficult to stably hold the door glass using the lifting member, as shown in FIG. Preferably, the coating film 11 is not formed. However, depending on the method of connection between the elevating member and the door glass or the type of membrane, the formation of the membrane in the bottom regions 13 and 14 may not interfere with the connection. Generally, a membrane having a contact angle with water of 50 degrees or less has little effect on connection. In such a case, it is not necessary to exclude the coating film 11 from the bottom regions 13, 14 (FIG. 3). As described above, the coating film 11 may not be formed on a portion of the surface of the glass plate, particularly on the peripheral edge that comes into contact with other members. However, in this case as well, a coating film 11 should be formed on the entire surface of the main area of the glass plate that separates the indoor and outdoor areas when the window is closed, in order to block ultraviolet rays.

When securing an area where no film is formed on a part of the surface of the glass plate, it is preferable to form the coating film so that the film thickness gradually decreases from the main area where the film is formed to the peripheral area where the film is not formed. . By forming in this manner, the boundary between the region where the film is formed and the region where the film is not formed is not noticeable, and deterioration in appearance can be prevented. FIG. 4 shows an example of a window glass (door glass) having a region where the film thickness is gradually reduced. In the form shown in FIG. 4, the window glasses 10 and 20 used as door glasses are closed, and the main area of the window glasses 10 and 20 (the outside including ultraviolet rays from the outside on the left side of the figure to the inside of the right side of the figure) is closed. A coating film 11 is formed on the indoor side surface of the glass plate 15 constituting the light-transmitting area) so as to have a predetermined thickness desirable for shielding ultraviolet rays. On the other hand, the coating film 11 is not formed on the surface of the glass plate 15 in the peripheral region from the glass plate tip A to the peripheral edge B where the glass plate 15 and the run channel 30 are in contact. The coating film 11 is formed so that its thickness gradually decreases from the periphery C toward the periphery B. FIG. 4 shows a configuration in which the tip of the run channel 30 and the periphery C coincide with each other (a configuration in which a coating film is formed with a constant thickness over the entire surface of the glass plate that is exposed and not covered by the run channel). ), but the tip of the run channel 30 and the periphery C do not need to coincide as long as the desired ultraviolet shielding ability can be obtained in the main areas of the window glasses 10 and 20. Further, as shown in the figure, the film thickness may gradually decrease to zero at a position slightly retreated from the periphery B toward the periphery C side, but the periphery B and the position where the film thickness becomes zero may coincide with each other. do not have. Although FIGS. 2 to 4 show a door glass in which no film is formed on the peripheral edge of the glass plate, it goes without saying that the glass plate according to the present invention is not limited to this form. Even when used as door glass, a coating film may be formed on the entire surface of the glass plate, or a film may be formed on the peripheral area 12 that contacts the end holding member, while a coating film may be formed on the bottom areas 13 and 14. It is also possible not to form a film.

Hereinafter, the present invention will be explained in more detail with reference to Examples. First, an ultraviolet shielding component to be used as organic compound A was synthesized.
<Synthesis Example 1> Synthesis of Compound 1

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), benzenethiol (17.4 g, 158.3 mmol), potassium carbonate (24 .1g, 174.2mmol) and potassium iodide (0.9g, 5.5mmol) were reacted in 62.5g of DMF (meaning N,N-dimethylformamide; the same applies hereinafter) at 125°C for 12 hours. did. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH (meaning methanol; the same applies hereinafter), washing with water, recrystallization, and column purification to obtain Compound 1.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1445, 1390cm ^-1 : Triazole ring stretching vibration 665cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.37 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 7.16 (s, 1H), 7.38 (d, 4H), 7.48 (s, 2H), 7.68 (s, 1H), 7.83 (d, 1H), 8.03 (d, 1H), (insg.10arom. C H ), 11.55 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 116.8, 118.0, 119.3, 128.3, 128.8, 129.6, 132.7 (CH _arom ), 125.5, 141.2, 143.2 (C _arom ), 129.8 ( C _arom -CH ₃ ), 139.2 ( C _arom -S), 139.2 (S- C _arom ), 139.2 ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH)

In the above, FT-IR (KBr) refers to the absorption wave number and the attribution of the absorption in the Fourier transform infrared spectra of a sample prepared by the KBr tablet method.
In addition, ¹ H-NMR (CDCl ₃ 400 MHz) and ¹³ C-NMR (CDCl ₃ 400 MHz) are nuclear magnetic resonance spectra of ¹ H and ¹³ C, respectively. In nuclear magnetic resonance, the nuclear magnetic resonance frequency of ¹ H is 400 MHz. The chemical shift δ and its attribution are shown for the sample prepared using deuterated trichloroform as the solvent under the following conditions. Note that the fact that some atoms are underlined in parentheses following the NMR chemical shift δ indicates that the atomic nucleus of that atom is the origin of the NMR signal. Furthermore, s, d, t, q, m in parentheses following the chemical shift δ in ¹ H-NMR indicates that the NMR signal is a singlet, doublet, triplet, quartet, multiplet, s, d, t, nH (n is a natural number) following q and m means that the integral value of the signal corresponds to n ¹ H , and “insg. This shows that the integral value of the NMR signal based on ¹ H bonded to carbon corresponds to X number of ¹ Hs. Further, _Carom in parentheses following the chemical shift δ in ¹³ C-NMR means carbon having aromaticity.

<Synthesis Example 2> Synthesis of Compound 2

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-tert-butylbenzenethiol (26.3 g, 158.3 mmol) , potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 2.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1444, 1390cm ^-1 : Triazole ring stretching vibration 668cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.36 (s, 9H, -S-Ph-C(C H ₃ ) ₃ ), 1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.37 (s, 3H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 7.16 (s, 1H), 7.35 (d, 1H), 7.44 (s, 4H), 7.59 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 31.3 (-S-Ph-C( CH ₃ ) ₃ ), 34.8 (-S-Ph- C (CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 115.4 , 117.8, 119.3, 126.8, 128.8, 129.2, 133.2 (CH _arom ), 125.4, 141.5, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.5 ( C _arom -S), 138.5 (S - C _arom ), 139.1, 152.0 ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH)

<Synthesis Example 3> Synthesis of Compound 3

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 2,4-dimethylbenzenethiol (21.9 g, 158.3 mmol) , potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 3.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1447, 1385cm ^-1 : Triazole ring stretching vibration 665cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.47 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.38 (s, 9H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ , -Ph-C H ₃ -C H ₃ ), 7.08 (d, 1H), 7.15 (d, 2H), 7.30 (m, 2H), 7.43 (d, 1H), 7.77 (d , 1H), 8.01 (d, 1H), (insg.8arom. C H ), 11.57 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.6 (-Ph- C H ₃ -CH ₃ ), 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 20.6 (-Ph-CH ₃ - C H ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 113.3, 117.7, 119.2, 128.0, 128.3, 128.6, 135.8 (CH _arom ), 125.4, 141.3, 143.4, 152.0 (C _arom ), 128.2, 132.0, 141.9 ( C _arom -CH ₃ ), 138.8 ( C _arom -C(CH ₃ ) ₃ ), 139.1 ( C _arom -S), 139.9 (S - C _arom ), 146.6 ( C _arom -OH)

<Synthesis Example 4> Synthesis of Compound 4

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 3-methoxybenzenethiol (22.2 g, 158.3 mmol), carbonic acid Potassium (24.1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 4.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.38 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 3.79 (s, 3H, C H ₃ O-Ph-S-), 6.90 (d, 1H), 7.00 (s, 1H), 7.06 (d, 1H), 7.17 (s, 1H), 7.30 (s, 1H), 7.40 (d, 1H), 7.74 (s, 1H), 7.84 (s, 1H), 8.04 (s, 1H), (insg.9arom. C H ), 11.56 (s , 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 55.4 (-S-Ph-O- C H ₃ ), 114.1, 117.3, 117.5, 118.0, 119.3, 124.6, 128.9, 130.0, 130.4 ( CH _arom ), 125.4, 141.5, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.5 ( C _arom -S), 138.5 (S - C _arom ), 139.1, ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH), 159.9 ( C _arom -OCH ₃ )

<Synthesis Example 5> Synthesis of Compound 5

4-tert-amylphenol (25.0 g, 152.2 mmol), dimethylcarbamoyl chloride (28.2 g, 228.3 mmol), sodium hydride (7.3 g, 167.4 mmol), and THF (tetrahydrofuran). The same applies hereinafter)) The reaction was carried out at 60° C. for 4 hours in 50 g of the mixture. After the reaction was completed, toluene and water were added, followed by acid treatment by adding hydrochloric acid, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was purified by column to obtain solid intermediate 5-1. The obtained intermediate 5-1 was reacted in 50 g of sulfolane at 240° C. for 4 hours. After the reaction was completed, toluene and water were added and washed with water, followed by distillation under reduced pressure to obtain a liquid intermediate 5-2. The obtained intermediate 5-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours, and after cooling, hydrochloric acid was added and stirred, followed by water washing, recrystallization, and column purification to obtain 4-tert- Amylthiophenol was obtained.
2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (3.8 g, 12.0 mmol), 4-tert-amylthiophenol (2.8 g, 15.5 mmol) , potassium carbonate (3.6 g, 26.4 mmol) and potassium iodide (0.1 g, 0.8 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 5.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ0.72 (t, 3H, -S-Ph-CCH ₂ C H ₃ ), 1.31 (s, 6H, -S-Ph-C(C H ₃ ) ₂ ), 1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 1.66 (q, 2H, -S-Ph-CC H ₂ CH ₃ ), 2.37 (s, 3H, -Ph- OH-C H ₃ -C(CH ₃ ) ₃ ), 7.16 (d, 1H), 7.36 (m, 3H), 7.44 (d, 2H), 7.60 (s, 1H), 7.81 (d, 1H), 8.02 (s, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ9.18 (-S-Ph-CCH ₂ C H ₃ ), 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 28.3 (-S- Ph-C( CH ₃ ) ₂ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 36.8 ( -S-Ph- C (CH ₃ ) ₂ ), 38.1 (-S-Ph-C C H ₂ CH ₃ ), 115.5, 117.8, 119.3, 127.4, 128.8, 129.3, 133.0 (CH _arom ), 125.4, 141.5, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.4 ( C _arom -S), 138.4 (S - C _arom ), 139.1 ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH ), 150.4 ( C _arom -C(CH ₃ ) ₂ )

<Synthesis Example 6> Synthesis of Compound 6

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4-isopropylbenzenethiol (24.1 g, 158.3 mmol), carbonic acid Potassium (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 6.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1446, 1389cm ^-1 : Triazole ring stretching vibration 666cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.30 (d, 6H, ( CH ₃ ) ₂ CH-Ph-S-), 1.48 (s, 9H, -Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 2.37 (s, 3H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 2.95 (m, 1H, (CH ₃ ) ₂ C H -Ph-S-), 7.16 ( s, 1H), 7.28 (s, 2H), 7.36 (d, 1H), 7.45 (s, 2H), 7.57 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg. 9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 23.9 (( C H ₃ ) ₂ CH-Ph-S-), 29.5 (- Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 33.9 ((CH ₃ ) ₂ C H-Ph-S-), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 115.3, 117.8, 119.3, 127.9, 128.7, 129.2, 129.6, 133.6 (CH _arom ), 125.4, 141.4, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.5 ( C _arom -S), 138. 5 (S - C _arom ), 139.1 ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH), 149.7 (C _arom - C H)

<Synthesis Example 7> Synthesis of Compound 7

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

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (5.5 g, 17.3 mmol), 4-(1,1,3,3-tetramethylbutyl)thio Phenol (5.0 g, 22.5 mmol), potassium carbonate (5.3 g, 38.1 mmol) and potassium iodide (0.2 g, 1.2 mmol) were reacted in 60 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 7.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ0.76 (s, 9H, -S-Ph-CCH ₂ C(C H ₃ ) ₃ ), 1.40 (s, 6H, -S-Ph-C(C H ₃ ) ₂ ), 1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 1.77 (s, 2H, -S-Ph-CC H ₂ ), 2.37 (s, 3H, - Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 7.16 (d, 1H), 7.34 (m, 1H), 7.42 (s, 4H), 7.59 (s, 1H), 7.80 (d, 1H) , 8.02 (s, 1H), (insg.9arom. C H ), 11.58 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 31.8 (-S-Ph-CCH ₂ C( C H ₃ ) ₃ ), 31.4 (-S-Ph-C( C H ₃ ) ₂ ), 32.5 (-S-Ph- C ), 35.4 (-Ph-OH -CH ₃ - C (CH ₃ ) ₃ ), 38.6 (-S-Ph-CCH ₂ C (CH ₃ ) ₃ ), 57.0 (-S-Ph-C C H ₂ ), 115.4, 117.8, 119.3, 127.6, 128.7, 129.2, 133.0 (CH _arom ), 125.4, 141.5, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.5 ( C _arom -S), 138.5 (S - C _arom ), 139.1 ( C _arom - C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH), 151.2 ( C _arom -C(CH ₂ ) ₂ )

<Synthesis Example 8> Synthesis of compound 8

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 5-tert-butyl-2-methylbenzenethiol (28.5 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 8.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1385cm ^-1 : Triazole ring stretching vibration 665cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.31 (s, 9H, -S-Ph-C(C H ₃ ) ₃ ), 1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.36 (s, 6H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ , -S-Ph-C H ₃ ), 7.15 (d, 1H), 7.34 (m, 4H) , 7.56 (d, 1H), 7.80 (d, 1H), 8.01 (d, 1H), (insg.8arom. C H ), 11.57 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.1 (-Ph- C H ₃ ), 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 31.3 (-Ph-CH ₃ -C( C H ₃ ) ₃ ), 34.5 (-Ph-CH ₃ - C (CH ₃ ) ₃ ), 35.4 (-Ph-OH- CH ₃ - C (CH ₃ ) ₃ ), 113.6, 117.7, 119.2, 126.7, 128.7, 130.4, 130.8, 132.5 (CH _arom ), 125.4, 141.3, 143.4, 152.0 (C _arom ), 128.3, 128.4 ( C _arom - CH ₃ ), 138.5 ( C _arom -S), 139.1 (S - C _arom ), 138.8, 150.4 ( C _arom -C(CH ₃ ) ₃ ), 146.6 ( C _arom -OH)

<Synthesis Example 9> Synthesis of Compound 9

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0g, 79.2mmol), p-toluenethiol (19.7g, 158.3mmol), potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 9.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1444, 1389cm ^-1 : Triazole ring stretching vibration 667cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.37 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ) , 2.40 (s, 3H, C H ₃ -Ph-S-) , 7.16 (s, 1H), 7.23 (s, 2H), 7.32 (d, 1H), 7.43 (s, 2H ), 7.56 (s, 1H), 7.81 (d, 1H), 8.02 (d, 1H), (insg.9arom. C H ), 11.56 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 21.2 ( C H ₃ -Ph-S-), 29.5 (-Ph-OH- CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 115.3, 117.8, 119.3, 128.7, 129.3 130.5, 133.7(CH _arom ), 125.4, 141.2 , 143.4 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.9( C _arom -S) , 138.7(S - C _arom ), 139.1( C _arom -C(CH ₃ ) ₃ ), 146.7( C _arom - OH)

<Synthesis Example 10> Synthesis of Compound 10

2,4-di-tert-amylphenol (25.0 g, 106.7 mmol), dimethylcarbamoyl chloride (19.8 g, 160.0 mmol), and sodium hydride (5.1 g, 117.4 mmol) in 50 g of THF. The reaction was carried out at 60°C for 4 hours. After the reaction was completed, toluene and water were added, followed by acid treatment by adding hydrochloric acid, and the organic layer washed with water was distilled off under reduced pressure. The resulting liquid was purified by column to obtain solid Intermediate 10-1. The obtained intermediate 10-1 was reacted in 50 g of sulfolane at 240° C. for 4 hours. After the reaction was completed, toluene and water were added and washed with water, followed by distillation under reduced pressure to obtain a liquid intermediate 10-2. The obtained intermediate 10-2 and potassium hydroxide were stirred in ethanol at 60°C for 3 hours, and after cooling, hydrochloric acid was added and stirred, followed by water washing, recrystallization, and column purification to obtain 2,4- Di-tert-amylthiophenol was obtained.

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (2.9 g, 9.2 mmol), 2,4-di-tert-amylthiophenol (3.0 g, 12.0 mmol), potassium carbonate (2.8 g, 20.3 mmol), and potassium iodide (0.1 g, 0.6 mmol) were reacted in 60 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 10.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ0.60 (m, 6H, -S-Ph-(CCH ₂ C H ₃ ) ₂ ), 1.23 (s, 6H, -S-Ph-C(C H ₃ ) ₂ ), 1.39 (m, 15H, -S-Ph-C(C H ₃ ) ₂ ,-Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 1.58 (q, 2H, -S-Ph- CC H ₂ CH ₃ ), 1.96 (q, 2H, -S-Ph-CC H ₂ CH ₃ ), 2.26 (s, 3H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 7.05 ( m, 2H), 7.20 (d, 1H), 7.27 (s, 1H), 7.30 (s, 1H), 7.35 (s, 1H), 7.68 (d, 1H), 7.92 (d, 1H), (insg. 8arom. C H ), 11.50 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ9.22 (-S-Ph-CCH ₂ C H ₃ ), 9.54 (-S-Ph-CCH ₂ C H ₃ ), 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 28.3 (-S-Ph-C( CH ₃ ) ₂ ), 28.8 (-S-Ph-C( CH ₃ ) ₂ ), 29.6 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 34.4 (-S-Ph- C ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 37.0 (-S-Ph- C ), 36.8 ( -S-Ph-C C H ₂ ), 40.5 (-S-Ph-C C H ₂ ), 114.0, 117.6, 119.3, 125.0, 126.6, 127.3, 128.6, 128.7, 140.9 (CH _arom ), 125.4, 141.2, 143.4 (C _arom ), 128.3 ( C _arom -CH ₃ ), 138.3 ( C _arom -S), 138.3 (S - C _arom ), 139.1 ( C _arom -C(CH ₃ ) ₃ ), 146.6 ( C _arom -OH ), 150.1 ( C _arom -C), 150.2 ( C _arom -C)

<Synthesis Example 11> Synthesis of Compound 11

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0g, 79.2mmol), 4-hydroxybenzenethiol (20.0g, 158.3mmol), carbonic acid Potassium (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 11.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1445, 1390cm ^-1 : Triazole ring stretching vibration 667cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.36 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 5.02 (s, 1H, -Ph-O H ), 6.90 (d, 2H), 7.15 (s, 1H), 7.29 (d, 1H), 7.46 (m, 3H), 7.80 (d, 1H), 8.01 (d, 1H), (insg.9 _arom . C H ), 11.57 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 114.0, 116.9, 117.7, 119.3, 128.3, 136.5 (CH _arom ), 125.4, 141.3, 143.3 (C _arom ), 128.7 ( C _arom -CH ₃ ), 139.1 ( C _arom -C(CH ₃ ) ₃ ), 139.8 ( C _arom -S), 139.8 (S - C _arom ), 146.7, 156.6 ( C _arom -OH)

<Synthesis Example 12> Synthesis of Compound 12

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0g, 79.2mmol), 2-naphthalenethiol (25.4g, 158.3mmol), potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 12.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1444, 1389cm ^-1 : Triazole ring stretching vibration 667cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.36 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 7.16 (s, 1H), 7.39 (d, 1H), 7.51 (m, 3H), 7.72-7.86 (m, 5H), 8.02 (d, 1H), (insg.12arom. C H ), 11.56 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 117.0, 118.0, 119.3, 126.8, 127.6, 127.8, 128.9, 129.4, 131.0, 131.9, 132.8, 133.9 (CH _arom ), 125.4, 131.0, 133.9, 141.7, 143.2 (C _arom ), 128.3 ( C _arom -CH ₃ ), 137.2 ( C _arom -S), 137.2 (S - C _arom ), 139.2 ( C _arom -C(CH ₃ ) ₃ ), 146.7 ( C _arom -OH)

<Synthesis Example 13> Synthesis of Compound 13

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (25.0 g, 79.2 mmol), 4,4'-thiobisbenzenethiol (9.0 g, 36. 0 mmol), potassium carbonate (10.9 g, 79.2 mmol), and potassium iodide (0.4 g, 2.5 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 13.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1444, 1389cm ^-1 : Triazole ring stretching vibration 667cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 18H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.37 (s, 6H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 7.17 (s, 2H), 7.32-7.39 (m, 10H), 7.77 (s, 2H), 7.83 (d, 2H), 8.03 (d, 2H), (insg.18arom. C H ), 11.53 (s, 2H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 118.0, 118.2, 119.4, 129.0, 130.2, 131.9, 132.6, 133.6 (CH _arom ), 125.3, 141.8, 143.2 (C _arom ), 128.4 ( C _arom -CH ₃ ), 135.3 ( C _arom -S), 136.0 (S - C _arom ), 139.2 ( C _arom -C(CH ₃ ) ₃ ), 146.8 ( C _arom -OH)

<Synthesis Example 14> Synthesis of Compound 14

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

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (8.0 g, 25.3 mmol), 2,2-bis(4-mercaptophenyl)propane (3.0 g , 11.5 mmol), potassium carbonate (7.0 g, 50.6 mmol), and potassium iodide (0.3 g, 1.8 mmol) were reacted in 60 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 14.
FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration

¹ H-NMR (CDCl ₃ 400MHz): δ1.49 (s, 18H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 1.73 (s, 6H, -S-Ph-C(C H ₃ ) ₂ ), 2.37 (s, 6H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 7.16 (d, 2H), 7.29 (m, 4H), 7.37 (m, 2H), 7.41 (m, 4H), 7.67 (s, 2H), 7.81 (d, 2H), 8.02 (s, 2H), (insg.18arom. C H ), 11.58 (s, 2H, -Ph-O H -CH ₃ -C( _CH3 ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 30.6 (-S-Ph-C( CH ₃ ) ₂ -Ph-S), 5.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 43.0 (-S-Ph- C (CH ₃ ) ₂ -Ph-S), 116.3, 117.9, 119.3, 128.1, 128.8, 129.6, 132.7 (CH _arom ), 125.4, 141.5, 143.3 (C _arom ), 128.3 ( C _arom -CH ₃ ), 137.6 ( C _arom -S ), 137.6 (S - C _arom ), 139.2 ( C _arom -C(CH ₃ ) ₂ ), 146.7 ( C _arom -OH)

<Synthesis Example 15> Synthesis of Compound 15

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

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (4.6g, 14.6mmol), biphenyl-4,4'-dithiol (1.5g, 6.9mmol) ), potassium carbonate (4.0 g, 28.9 mmol), and potassium iodide (0.2 g, 1.2 mmol) were reacted in 60 g of DMF at 125° C. for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 15.

FT-IR (KBr): 3000cm ^-1 : O-H stretching vibration 1450, 1380cm ^-1 : Triazole ring stretching vibration 660cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.48 (s, 18H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.38 (s, 6H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ), 7.17 (d, 2H), 7.41 (d, 2H), 7.55 (d, 4H), 7.41 (d, 4H), 7.77 (s, 2H), 7.85 (d, 2H), 8.04 (d, 2H), (insg.18arom. C H ), 11.56 (s, 2H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 118.1, 119.3, 128.1, 128.4, 128.9, 130.0, 132.8 (CH _arom ), 125.4, 141.7 143.2 (C _arom ), 128.4 ( C _arom - CH ₃ ), 136.9 ( C _arom -S), 136.9 (S - C _arom ), 139.2 ( C _arom -C(CH ₃ ) ₃ ), 146.8 ( C _arom -OH)

<Synthesis Example 16> Synthesis of compound 16

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (32.3g, 0.102mol), cyclohexanethiol (23.8g, 0.205mol), potassium carbonate (31 .1g, 0.225mol) and potassium iodide (1.2g, 0.007mol) were reacted in 100g of DMF at 125°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Compound 16.

FT-IR (KBr): 2930cm ^-1 : O-H stretching vibration 1450, 1391cm ^-1 : Triazole ring stretching vibration 667cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ 1.40 (m, 4H, CH ₂ (C H ₂ ) ₂ (CH ₂ ) ₂ CH-S), 1.49 (S, 9H, -Ph-OH-CH ₃ -C (C H ₃ ) ₃ ), 1.54 (m, 2H, C H ₂ (CH ₂ ) ₂ (CH ₂ ) ₂ CH-S), 1.83 (m, 2H, CH ₂ (CH ₂ ) ₂ CH ₂ C H ₂ CH-S), 2.06 (m, 2H, CH ₂ (CH ₂ ) ₂ CH 2 CH _{2 CH} -S), 2.38 (s, 3H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ) , 3.29 (m, 1H, CH ₂ CH ₂ CH ₂ C H -S), 7.17 (s, 1H), 7.43 (d, 1H), 7.80 (s, 1H), 7.84 (d, 1H), 8.06 (d , 1H), (insg.5arom. C H ), 11.62 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ 20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 25.7 (CH ₂ ( CH ₂ ) ₂ (CH ₂ ) ₂ CH-S), 26.0 ( CH ₂ (CH ₂ ) ₂ (CH ₂ ) ₂ CH-S), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 33.1 (CH ₂ (CH ₂ ) ₂ ( C H ₂ ) ₂ CH-S), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 46.3 (CH ₂ (CH ₂ ) ₂ (CH ₂ ) ₂ C H-S), 117.2, 117.5, 119.3 , 128.3, 128.8 ( C H _arom ), 141.5, 143.2 ( C _arom ), 125.4 ( C _arom -N), 131.2 ( C _arom -CH ₃ ), 136.1 ( C _arom -S), 139.1 ( C _arom -C( CH ₃ ) ₃ ), 146.7 ( C _arom -OH)

<Synthesis Example 17> Synthesis of Compound 17

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (59.2 g, 0.187 mol) was added to 500 mL of toluene and heated to 80°C. Next, aluminum trichloride (50.0 g, 0.375 mol) was added and stirred for 30 minutes, then cooled to room temperature, and 500 mL of ice-cooled ion exchange water was slowly added. Thereafter, the aqueous layer was removed, the organic layer was washed with water, evaporated under reduced pressure, and then recrystallized to obtain Intermediate 17-1. The obtained intermediate 17-1 (20.0 g, 0.077 mol), benzenethiol (11.0 g, 0.100 mol), potassium carbonate (23.4 g, 0.169 mol) and potassium iodide (0.9 g, 0.005 mol) was reacted in 80 g of DMF at 125°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 17.

FT-IR (KBr): 2950cm ^-1 : O-H stretching vibration 1459, 1388cm ^-1 : Triazole ring stretching vibration 670cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ2.38 (s, 3H, -Ph-OH-C H ₃ ), 7.09 (d, 1H), 7.14 (d, 1H), 7.38 (d, 4H), 7.48 (d, 2H), 7.69 (s, 1H), 7.83 (d, 1H), 8.14 (d, 1H), (insg.11arom. C H ), 10.94 (s, 1H, -Ph-O H -CH ₃ )
^13C -NMR (CDCl ₃ 400MHz): δ20.5 (-Ph-OH- C H ₃ ), 116.8, 118.1, 118.8, 121.0, 128.3, 129.6, 131.3, 132.8 (CH _arom ), 124.8, 141.8, 143.4 ( C _arom ), 129.9 ( C _arom -CH ₃ ), 137.6 ( C _arom -S), 139.2 (S- C _arom ), 147.5 ( C _arom -OH)

<Synthesis Example 18> Synthesis of compound 18

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

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

Intermediate 18-2 (75.0 g, 0.192 mol), 2M NaOH aqueous solution (288.5 g), and zinc powder (150.99 g) were added to 400 mL of toluene and stirred at 85° C. for 2 hours. After the reaction was completed, intermediate 18-3 was obtained by filtration, washing, and recrystallization.

Intermediate 18-3 (5.0 g, 0.014 mol), 4-tert-butylbenzenethiol (3.5 g, 0.021 mol), potassium carbonate (4.3 g, 0.031 mol) and potassium iodide (0.0 g, 0.021 mol). 2g, 0.001mol) was reacted in 50g of DMF at 125°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, recrystallization, and column purification to obtain Intermediate 18-4.

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

Intermediate 18-4 (1.00 g, 2.052 mmol), Intermediate 18-5 (1.34 g, 2.341 mmol), and 28% sodium methylate MeOH solution (1.33 g) were added to 25 mL of xylene and autoclaved. The reaction was carried out at 175°C for 15 hours. After the reaction was completed, compound 18 was obtained by column purification.

FT-IR (KBr): 2953cm ^-1 : O-H stretching vibration 1460, 1389cm ^-1 : Triazole ring stretching vibration 670cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ0.68 (s, 18H, -Ph-OH-CCH ₂ C(C H ₃ ) ₃ ), 1.35 (s, 18H, -S-Ph-C(C H _{3 )} ) ₃ ), 1.36 (s, 12H, -Ph-OH-C(C H ₃ ) ₂ CH ₂ C(CH ₃ ) ₃ ), 1.70 (s, 4H, -Ph-CC H ₂ C), 4.26 (s , 2H, -Ph-OH-C H ₂ -OH-Ph-), 7.34 (m, 2H), 7.37 (m, 2H), 7.43 (d, 8H), 7.63 (s, 2H), 7.80 (d, 2H), 8.02 (d, 2H), (insg.18arom. C H ), 11.36 (s, 2H, -Ph-O H )
¹³ C-NMR (CDCl ₃ 400MHz): δ30.9 (-Ph-OH- C H ₂ -OH-Ph-), 31.3 (-S-Ph-C( C H ₃ ) ₃ ), 31.7 (-Ph- OH-C( CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₃ ), 31.8 (-Ph-OH-C(CH ₃ ) ₂ CH ₂ C( CH ₃ ) ₃ ), 32.3 (-Ph-OH- C(CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₃ ), 34.7 (-S-Ph- C (CH ₃ ) ₃ ), 38.2 (-Ph-OH- C (CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₃ ), 56.6 (-Ph-OH-C(CH ₃ ) ₂ C H ₂ C(CH ₃ ) ₃ ), 115.9, 116.5, 117.9, 126.7, 129.4, 129.6, 133.0 (CH _arom ), 124.4, 141.6, 143.4 (C _arom ), 129.3 ( C _arom -CH ₂ ), 129.9 ( C _arom -S), 138.1 (S - C _arom ), 141.4 ( C _arom -C(CH ₃ ) ₃ ), 145.6 ( C _arom -OH ), 151.8 ( C _arom -C(CH ₃ ) ₂ )

<Synthesis Example 19> Synthesis of Compound 19

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (50.0 g, 0.158 mol), octanethiol (46.3 g, 0.316 mol), potassium carbonate (48 .1g, 0.348mol) and potassium iodide (1.8g, 0.011mol) were reacted in 125g of DMF at 125°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, and recrystallization to obtain Compound 19.

FT-IR (KBr): 2956cm ^-1 : O-H stretching vibration 1445, 1392cm ^-1 : Triazole ring stretching vibration 662cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ 0.89 (t, 3H _{, CH 3} ( CH ₂ ) ₇ -S), 1.33 (m, 8H, CH ₃ ( CH ₂ ) ₄ (CH ₂ ) ₃ -S ), 1.49 (m, 11H, -Ph-OH-CH ₃ -C(C H _{3 ) 3} , CH ₃ (CH ₂ ) ₄ CH 2 (CH ₂ ) ₂ -S), 1.73 (quin, 2H, CH ₃ (CH ₂ ) ₅ C H ₂ CH ₂ -S), 2.38 (s, 3H, -Ph-OH-C H ₃ -C(CH ₃ ) ₃ ), 3.02 (t, 2H, CH ₃ (CH ₂ ) ₅ CH ₂ C H ₂ -S), 7.16 (s, 1H), 7.36 (d, 1H), 7.69 (s, 1H), 7.78 (d, 1H), 8.04 (s, 1H), (insg.5arom. C H ), 11.62 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ 14.0 ( CH ₃ (CH ₂ ) ₇ -S), 20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 22.6 (CH ₃ C H ₂ (CH ₂ ) ₅ CH ₂ -S), 28.7 (CH ₃ CH ₂ ( CH ₂ ) ₄ CH ₂ CH ₂ -S), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ) , 31.8 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ) , 33.8 (CH ₃ (CH ₂ ) ₅ C H ₂ CH ₂ -S), 35.4 (CH ₃ (CH ₂ ) ₅ CH ₂ C H ₂ -S), 113.6, 117.5, 119.3, 128.7, 129.2 ( C H _arom ), 125.4, 141.2, 143.4 ( C _arom ), 128.3 ( C _arom -CH ₃ ), 138.0( C _arom -S), 139.1( C _arom -C(CH ₃ ) ₃ ), 146.7( C _arom -OH)

<Synthesis Example 20> Synthesis of compound 20

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (20.0 g, 63.3 mmol), benzyl mercaptan (15.7 g, 126.6 mmol), potassium carbonate (19 .3g, 139.4mmol) and potassium iodide (0.74g, 4.5mmol) were reacted in 50.0g of DMF at 125°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, washing with MeOH, washing with water, and recrystallization to obtain Compound 20.

FT-IR (KBr): 2960cm ^-1 : O-H stretching vibration 1441, 1392cm ^-1 : Triazole ring stretching vibration 664cm ^-1 : CS stretching vibration
¹ H-NMR (CDCl ₃ 400MHz): δ1.49 (s, 9H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 2.38 (s, 3H, -Ph-OH-C H ₃ - C(CH ₃ ) ₃ ) , 4.24 (s, 2H, Ph-C H ₂ -S-) , 7.16 (s, 1H), 7.26~7.38 (m, 6H), 7.72 (s, 1H), 7.80 (d , 1H), 8.04 (d, 1H), (insg.10 _arom . CH), 11.58 (s, 1H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
¹³ C-NMR (CDCl ₃ 400MHz): δ20.9 (-Ph-OH- CH ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( CH ₃ ) ₃ ), 35.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 38.6 (Ph- C H ₂ -S-), 115.4, 117.6, 119.3, 128.7, 128.8, 128.8, 129.7, 137.0( C H _arom ) , 125.4, 141.4, 143.4 ( C _arom ), 128.3 ( C _arom -CH ₃ ), 136.5( C _arom CH ₂ -S-) , 138.7(S - C _arom ), 139.1( C _arom -C(CH ₃ ) ₃ ), 146.7( C _arom -OH)

<Synthesis Example 21> Synthesis of Compound 21

2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole (10.0 g, 31.7 mmol), hexanedithiol (4.76 g, 31.7 mmol), potassium carbonate (8 .75g, 63.3mmol) and potassium iodide (0.37g, 2.2mmol) were reacted in 50g of DMF at 130°C for 12 hours. After the reaction was completed, the pH was adjusted, followed by filtration, MeOH washing, water washing, recrystallization, and column purification to obtain Compound 21.

FT-IR (KBr): 3009cm ^-1 : O-H stretching vibration 1431, 1391cm ^-1 : Triazole ring stretching vibration 656cm ^-1 : CS stretching vibration
1H-NMR (CDCl3 400MHz): δ1.49 (s, 18H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ ), 1.55 (m, 4H, -S-CH ₂ CH ₂ C H ₂ C H ₂ CH ₂ CH ₂ -S-), 1.77 (m, 4H, -S _- CH ₂ C H 2 CH ₂ CH ₂ C H ₂ CH ₂ -S-), 2.38(s, 6H, (-Ph-OH -C H ₃ -C(CH ₃ ) ₃ ) , 3.04 (t, 4H, -SC H ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -S-), 7.16 (s, 2H), 7.37 (d, 2H), 7.70 (s, 2H), 7.81 (d, 2H), 8.05 (s, 2H) (insg.10arom. CH), 11.60 (s, 2H, -Ph-O H -CH ₃ -C(CH ₃ ) ₃ )
13C-NMR (CDCl3 400MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 28.4 (-Ph-OH-CH ₃ - C (CH ₃ ) ₃ ), 28.6 -S -CH ₂ CH ₂ C H ₂ C H ₂ CH ₂ CH ₂ -S-, 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 33.1 -S-CH ₂ C H ₂ CH ₂ CH ₂ C H ₂ CH ₂ -S-, 35.4 -S- C H ₂ CH ₂ CH ₂ CH ₂ CH ₂ C H ₂ -S-, 113.7, 117.6, 119.3, 128.3, 129.3 ( C H _arom ), 141.2, 143.4 ( C _arom ), 125.4( C _arom -N), 128.3 ( C _arom -CH3), 137.7( C _arom -S), 139.1( C _arom -C(CH ₃ ) ₃ , 146.7( C _arom -OH)

Next, the characteristics of each compound synthesized as organic compound A were evaluated.

1. Light resistance evaluation Compounds 1 to 16 and 19 to 21 were dissolved in a toluene solution of 20 wt% acrylic resin (Paraloid B72) at the following mass ratio while taking into account the solubility of the compounds, and then coated on a soda glass plate and heated at 80°C. , and dried for 10 minutes to obtain an evaluation sample.

・Compounds 1-6, 8-11, 16, 19, 20
Mixing ratio (mass ratio)
20wt% acrylic resin toluene solution: compound = 3.0:0.1
(Acrylic resin: compound = 0.6:0.1)
Dry film thickness: 2~3μm
・Compound 7,12
Blending ratio 20wt% acrylic resin toluene solution: compound = 6.0:0.1
(Acrylic resin: compound = 1.2:0.1)
Dry film thickness: 4-6μm
・Compound 13
Mixing ratio (mass ratio)
20wt% acrylic resin toluene solution: compound = 12.0:0.1
(Acrylic resin: compound = 2.4:0.1)
Dry film thickness: 7-9μm
・Compounds 14, 15, 21
Mixing ratio (mass ratio)
20wt% acrylic resin toluene solution: compound = 17.0:0.1
(Acrylic resin: compound = 3.4:0.1)
Dry film thickness: 50μm

The UV-visible transmission spectrum of the obtained evaluation sample was measured using a UV-visible spectrophotometer (Spectrophotometer U-3310 manufactured by Hitachi, Ltd.), and the initial (before irradiation) UV transmittance at a wavelength of 400 nm (%T _{(1 )400} :%), irradiate the surface with ultraviolet light using an ultraviolet irradiation device ( ^Suga Test Instruments Xenon Weather Meter After 140 hours of irradiation time, measure the ultraviolet-visible transmission spectrum, read the transmittance at a wavelength of 400 nm (%T ₍₂₎₄₀₀ :%), and calculate the difference in transmittance Δ%T ₄₀₀ (%) using the following formula. (Tables 1A and 1B).

Difference in transmittance (Δ%T ₄₀₀ ) = %T ₍₂₎₄₀₀ - %T ₍₁₎₄₀₀ (%)

2. Evaluation of Melting Point The melting points of Compounds 1 to 21 were measured using a differential scanning calorimeter (DSC6220 manufactured by SII), and the DSC peak top temperature was taken as the melting point (Tables 1A and 1B). Further, the melting point of Compound 17 was 114°C, and the melting point of Compound 18 was 176°C.

Compounds 1 to 18 all have a melting point of 100°C or higher, compounds 1 to 3, 5 to 12, 14 to 16, 18 have a melting point of 130°C or higher, compounds 2,5 to 9, 11, 12, 14 to 16, Compounds 18 had a melting point of 140°C or higher, and compounds 2,6 to 8, 11, 12, 14, 15, and 18 had a melting point of 145°C or higher. In particular, it was confirmed that Compounds 2, 11, 12, 14, 15, and 18 have melting points of 150° C. or higher, and are excellent in suppressing bleed-out and blocking, dispersion, and heat processability.

Compounds ^2,5,6,7,9 (melting point 140 to 155°C) has a higher melting point than Compound 1 where all R ^1a are hydrogen atoms (melting point 136°C) and Compound 4 where R ^1a is an alkoxy group (melting point 115°C). Compounds 2,5,6,7 (melting point 141-155°C) of ~8 are higher than compound 9 (melting point 140°C), which has 1 carbon number, and are furthermore compound 2,6 (melting point 140°C), which has 3-4 carbon atoms in the alkyl group. It was confirmed that the melting point (melting point 148 to 155°C) was higher than that of Compounds 5, 7, 9 (melting points 141, 146, 140°C) having 1, 5, and 8 carbon atoms, and in particular Compound 2 having 4 carbon atoms had a tendency to have a high melting point.

Compounds 1 to 12 in which the thioaryl ring group of formula (2-1) has been introduced have A ^1c of formula (2-3) introduced, and q=0 and q=1, compared to compound 19 having a thioalkyl group. Compounds 14 and 15, in which A ^2c is a hydrocarbon group, tended to have higher melting points than Compound 21, in which A ^1c was an alkylene group.

In addition, compounds 2, 3, 5 to 10 (melting point 131 to 155°C) where l=1 or 2 and R ^1a is a hydrocarbon group, compound 1 where all R ^1a are hydrogen atoms (melting point 136°C), and R ^1a are Compared to Compound 4 (melting point 115°C), which has an alkoxy group, Compound 11 (melting point 208°C), Compound 14 (melting point 196°C), Compound 15 (melting point 236°C), in which R ^1a is a hydroxy group, and Compound 15 (melting point 236°C), and X ^1a is a naphthyl group. The melting points of Compound 12 (melting point: 161°C) and Compound 18 (melting point: 176°C) are high, and they are particularly useful in terms of bleed-out and processability.

Next, a glass plate with a coating film was prepared using the compound obtained above as organic compound A, and evaluated. The evaluation items were as follows.
<Optical properties>
The optical properties were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100PC). The measured characteristics are visible light transmittance YA according to JIS R3212 measured using CIE standard A light source, ultraviolet transmittance T _UV 380 calculated according to ISO9050 (1990 edition), and ultraviolet transmittance calculated according to ISO13837 (convention A). rate T _UV 400, blue light cut rate BLcut calculated based on the blue light disturbance function of JIS T7330 mentioned above, L ^* a ^* b ^* color system according to JIS Z8729 of transmitted light measured using CIE standard C light source, Yellowness YI according to JIS K7373 (2006) of transmitted light measured using CIE standard C light source, dominant wavelength and stimulus purity according to JIS Z8701 (1999) of transmitted light measured using CIE standard C light source, wavelength 1500 nm The light transmittance is T1500 at . Note that T _UV 380 is based on the transmittance of light in the wavelength range of 280 to 380 nm, T _UV 400 is based on the transmittance of light in the wavelength of 300 to 400 nm, and blue light cut rate is the transmittance of light in the wavelength of 380 to 500 nm. These are the values calculated based on the respective values.

<Light resistance (UV resistance)>
Light resistance (ultraviolet ray resistance) was measured using an ultraviolet irradiation device (EYE SUPER UV TESTER SUV-W13) manufactured by Iwasaki Electric Co., Ltd., at a wavelength of 295 to 450 nm, an illumination intensity of 76 mW/cm ² , a black panel temperature of 83°C, and a humidity of 50% RH. The test was carried out by applying ultraviolet rays to the coated glass plate from the surface of the glass plate on which the film was not formed for a predetermined period of time (100 hours). The optical properties (YA, T _UV 400) before and after the same test were measured, and the changes (ΔYA, ΔT _UV 400) were calculated.

(Example 1)
In Example 1, Compound 16 was used as the organic compound A. Specifically, a dispersion containing an ultraviolet shielding component, which is organic compound A, as a dispersoid and using water as a dispersion medium (ultraviolet shielding component content: 10% by weight, average particle size: 100 nm) was prepared. The organic compound A was mixed with zirconia beads using a paint conditioner and pulverized in advance so as to have the above-mentioned average particle size. Along with this dispersion, pure water, ethyl alcohol, tetraethoxysilane (TEOS), a silane coupling agent glycidoxypropyltrimethoxysilane (GPTMS; 3-glycidyloxypropyltrimethoxysilane), and a polyol compound triethylene Glycol (TEG), polyether phosphate ester polymer (Solsperse 41000 manufactured by Nippon Lubrizol), ITO fine particle dispersion (ethyl alcohol solution containing 40% by mass of ITO fine particles; manufactured by Mitsubishi Materials; average particle size ( (nominal) 100 nm or less) and concentrated hydrochloric acid (35% by mass) were mixed and stirred to obtain a film-forming solution for a coating film. TEG and Solsperse correspond to organic compound C. The film-forming solution was prepared so that the concentration (content) of each component was as shown in Table 2. Table 2 also shows the concentrations of each component in the film forming solutions prepared in Examples and Comparative Examples described below.

Next, this forming solution was applied onto a washed soda lime silicate glass substrate (commercially available UV cut green glass 100 x 100 mm, thickness 3.1 mm) at 30% humidity and room temperature using a flow coating method. After drying as it was at room temperature for about 5 minutes, it was placed in an oven preheated to 65° C., heated for 15 minutes, and then cooled to form a coating film. During this heating, the temperature of the glass plate with the film did not exceed the melting point of the organic compound.

The UV cut green glass used has a light transmittance (T380) of 40% at a wavelength of 380 nm and a light transmittance (T550) of 77% at a wavelength of 550 nm. This UV-cut green glass plate contains about 0.9% by mass of total iron oxide converted to Fe ₂ O ₃ .

The above measurements were carried out on the glass plate with the coating film thus obtained. The results are shown in Table 2. Table 2 also shows measurement results for glass plates with coating films produced in Examples and Comparative Examples described below.

(Examples 2 to 16)
A glass plate with a coating film was obtained in the same manner as in Example 1, except that the type and amount of the ultraviolet shielding component were adjusted as shown in Table 2.

However, in Example 5, organic compound B was used together with organic compound A (compound 19) as the ultraviolet shielding component. As the organic compound B, TINUVIN360 (manufactured by Ciba Specialty Chemicals Co., Ltd.; melting point 195°C) was used. TINUVIN360 was also mixed with zirconia beads using a paint conditioner and pulverized in advance so as to have the above average particle size. In the above formula (3), TINUVIN360 has a form in which two 2-phenylbenzotriazole skeletons are bonded to each other through a methylene group bonded to B ² , and the two 2-phenylbenzotriazole skeletons have hydroxyl as B ¹ . A 1,1,3,3-tetramethylbutyl group is connected as the group B ⁴ , and a hydrogen atom is connected as B ³ , B ⁵ , B ⁶ to B ⁹ .

In some examples, sorbitol polyglycidyl ether (DEN; Denacol EX-614 manufactured by Nagase ChemteX Co., Ltd.) was used as the organic compound C in place of TEG. Sorbitol polyglycidyl ether is a polyepoxy compound, and in the membrane becomes a polyol compound having a hydroxyl group produced by reaction of glycidyl groups.

Further, in Examples 12 to 14, the temperature of the oven in the heat drying step was set to 180° C., which was higher than the melting point of organic compound A. Therefore, in Examples 12 to 14, organic compound A was dissolved and added to the film.

(Comparative example 1)
A glass plate with a coating film was obtained in the same manner as in Example 1, except that the type and amount of the ultraviolet shielding component were adjusted as shown in Table 2. In Comparative Example 1, only organic compound B was added as an ultraviolet shielding component.

(Comparative example 2)
A glass plate with a coating film was obtained in the same manner as in Example 1, except that the type and amount of the ultraviolet shielding component were adjusted as shown in Table 2. In Comparative Example 2, instead of organic compound A, Uvinul 3050 (manufactured by BASF Japan Co., Ltd.), which is an ultraviolet shielding component having a benzophenone skeleton, was used. Uvinul3050 was dissolved in ethyl alcohol in advance and added to the film forming solution. Furthermore, as the organic compound C, Solsperse (polyether-modified silicone, manufactured by Dow Corning Toray Co., Ltd.) was used.

A low T _UV 400 was not obtained from Comparative Example 1, and a low T _UV 400 was obtained from Comparative Example 2, but the yellowness index YI was high. On the other hand, in each of the Examples, T _UV 400 was able to be lowered while suppressing noticeable yellow coloration. Further, from a comparison between Examples 1 and 2 and Examples 12 and 13, it was confirmed that the addition of organic compound A as fine particles improved the light resistance of the film. In addition, as in Compounds 2, 6, and 7 (Examples 3 to 11, and 16), an organic compound A in which the thioorganic group has a thioaryl ring group to which a branched chain alkyl group is connected as a substituent for the hydrogen atom When using these compounds, the ΔT _UV 400 of the film could be sufficiently suppressed, although these compounds alone do not necessarily have excellent long-wavelength ultraviolet shielding properties or light resistance (Table 3: 0.1 to 1). .4). These compounds are particularly suitable for addition to coating films on glass plates.

Comparing the irradiation intensity of ultraviolet rays, the irradiation of the film (760 J/m ² ) is orders of magnitude stronger than that of the compound itself (42 J/m ² ) (taking into account that the T _UV 400 of the glass plate is 24.6%) This means that about 1/4 of the ultraviolet light reaches the film, but even taking this into account, the film is still irradiated with stronger ultraviolet light). Comparing the temperature during ultraviolet irradiation, the film (83°C) is higher than the compound alone (63°C) (generally, the deterioration of organic materials accelerates about twice as much for every 10°C, so the film has (Conditions are applied where the deterioration progresses approximately four times as much.) Considering the above, it can be understood that deterioration of the organic compound A is sufficiently suppressed, especially when the organic compound A is kept in the form of fine particles in the coating film. In particular, for Compounds 2, 6, and 7 (Examples 3 to 11, and 16), the ΔT _UV 400 was suppressed to an extremely low level that could not be expected from the characteristics of the compounds alone.

In addition, when the X-ray diffraction pattern was observed using a RAD-RC device manufactured by Rigaku Denki Co., Ltd. for the glass plate with the coating film obtained from each example, it was found that from the examples containing ITO and fine particles of an organic compound, the fine particles and A sharp diffraction peak attributed to , and a halo pattern over a wide range were observed. From this result, it was confirmed that each coating film was glassy.

1 Glass plate 2 Coating film

Claims (13)

A glass plate for transportation equipment with a vitreous coating film containing an additive that imparts ultraviolet absorption ability,
comprising a glass plate and a coating film in contact with the main surface of the glass plate,
The coating film contains silicon oxide as a main component and the additive,
A glass plate, wherein the additive includes an organic compound A represented by formula (2-1), which is a 2-phenylbenzotriazole derivative having a thioaryl ring group that may have a substituent for a hydrogen atom.
PhBzT ^1a -S-X ^1a -(R ^1a ) _l (2-1)
(In the formula, PhBzT ^1a represents a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-X ^1a -...), which may have the above-mentioned substituents, is bonded, and X ^1a represents the remainder of the phenyl ring. R ^1a each independently represents a branched hydrocarbon group having 4 to 9 carbon atoms containing a quaternary carbon, and 1 represents an integer of 1 to 5.) The difference ΔT UV 400 obtained by subtracting the ultraviolet transmittance T _UV 400 before irradiating the ultraviolet rays from the ultraviolet transmittance T _UV 400 after irradiating ultraviolet rays with a wavelength of 295 _to 450 nm and an illuminance of 76 mW/cm ² for 100 hours is 2% or less. The glass plate according to claim 1 . The glass plate according to claim 1 or 2 , wherein the organic compound A has the form of fine particles with an average particle size of 150 nm or less. Any one of claims 1 to 3 , wherein the T _UV 400 calculated according to ISO 13837 (convention A) is 2% or less, and the visible light transmittance YA measured using a CIE standard A light source is 70% or more. The glass plate described in. Any one of claims 1 to 4, wherein the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton has a hydroxy group at the 2-position and an alkyl group having 1 to 6 carbon atoms at the 5 -position, respectively. The glass plate described in section. The glass plate according to claim 5 , wherein the phenyl group of the 2-phenylbenzotriazole skeleton has a hydroxy group at the 2-position and a methyl group at the 5-position. The coating film further includes an organic compound B,
The glass plate according to any one of claims 1 to 6 , wherein the organic compound B has a molecular structure that includes a 2-phenylbenzotriazole skeleton and has no thioorganic group connected to the 2-phenylbenzotriazole skeleton. . The glass plate according to claim 7 , wherein the organic compound B has the form of fine particles with an average particle size of 150 nm or less. Any one of claims 1 to 8 , wherein the transmitted light from the CIE standard C light source has a* of -15 or more and 0 or less and ^{b* of} 12 or less as expressed by the L ^* a ^* b ^* color system. The glass plate according to item 1. The glass plate according to any one of claims 1 to 9 , wherein the yellowness YI defined in JIS K7373:2006 of transmitted light from a CIE standard C light source is 14 or less. A composition for forming a coating film for a glass plate for transportation equipment with a vitreous coating film containing an additive that imparts ultraviolet absorption ability,
containing a silicon oxide precursor and the organic compound A as the additive,
The organic compound A has the form of fine particles,
A composition for forming a coating film, wherein the organic compound A is a 2-phenylbenzotriazole derivative having a thioaryl ring group optionally having a substituent for a hydrogen atom, represented by formula (2-1).
PhBzT ^1a -S-X ^1a -(R ^1a ) _l (2-1)
(In the formula, PhBzT ^1a represents a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-X ^1a -...), which may have the above-mentioned substituents, is bonded, and X ^1a represents the remainder of the phenyl ring. R ^1a each independently represents a branched hydrocarbon group having 4 to 9 carbon atoms containing a quaternary carbon, and 1 represents an integer of 1 to 5.) The composition for forming a coating film according to claim 11 , wherein the fine particles have an average particle size of 150 nm or less. A fine particle dispersion composition for use in a glass plate for transportation equipment with a vitreous coating film containing an additive that imparts ultraviolet absorption ability,
Containing the organic compound A as the additive,
The organic compound A has the form of fine particles with an average particle size of 150 nm or less,
A fine particle dispersion composition in which the organic compound A is a 2-phenylbenzotriazole derivative having a thioaryl ring group optionally having a substituent for a hydrogen atom, represented by formula (2-1).
PhBzT ^1a -S-X ^1a -(R ^1a ) _l (2-1)
(In the formula, PhBzT ^1a represents a 2-phenylbenzotriazole skeleton to which a thioaryl ring group (-S-X ^1a -...), which may have the above-mentioned substituents, is bonded, and X ^1a represents the remainder of the phenyl ring. R ^1a each independently represents a branched hydrocarbon group having 4 to 9 carbon atoms containing a quaternary carbon, and 1 represents an integer of 1 to 5.)

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