JP2020105022A - Glass plate with coating film and composition for forming the same - Google Patents

Abstract

To provide a glass plate having a coating film formed thereon, which can reduce a transmittance of light in a vicinity of a wavelength of 400 nm while suppressing yellowish coloration.SOLUTION: The glass plate is provided with the coating film. The coating film 2 formed on the main surface of the glass plate 1 includes: silicon oxide as a main component; and an organic compound A as an additive that imparts ultraviolet absorbing capability to the coating film. The organic compound A has a molecular structure that includes a 2-phenylbenzotriazole skeleton and at least one organic thio group which is connected to the skeleton. The organic thio group is a group represented by -S-R when the organic group is represented by R. The organic thio group is, for example, a thioalkyl group that may have a substituent of a hydrogen atom, or a thioaryl ring group that may have a substituent of a hydrogen atom.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a glass plate with a coating film, and more particularly to a glass plate for a transportation equipment with a glassy coating film. The present invention also relates to a coating film forming composition for forming this glass plate.

A glass plate is required to block visible light while transmitting visible light. Especially for window glass of transportation equipment, there is a high demand for a glass plate provided with an ultraviolet shielding property against the background of the demand for preventing sunburn. By increasing the ratio of iron oxide in the glass composition constituting the glass plate, the ultraviolet shielding property of the glass plate is improved. However, there is a limit to the improvement of the ultraviolet shielding property by adding an inorganic ultraviolet shielding component such as iron oxide, and it is not possible to sufficiently shield UVA which is an ultraviolet ray in a long wavelength range. For this reason, there has been proposed a glass plate having an improved ultraviolet shielding property by forming a coating film containing an organic ultraviolet shielding component composed of an organic substance on the glass plate.

For example, in International Publication No. 2006/137454 pamphlet (Patent Document 1), a glass plate having a coating film containing silicon oxide as a main component and 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 that is a polar solvent is used as a solvent of a solution for forming the film. In Patent Document 1, an organic ultraviolet shielding component that is soluble in lower alcohol is used.

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

In order to uniformly add the ultraviolet shielding component to the film, it is advantageous to add the ultraviolet shielding component as a solute. For this reason, as disclosed in Patent Documents 1 and 2, the organic UV-screening agent is soluble in the film-forming solution, unlike the inorganic UV-screening agent, which is difficult to dissolve in the film-forming solution. And was added to the film. On the other hand, WO 2012/107968 pamphlet (Patent Document 3) discloses a glass plate having a coating film formed by adding an organic ultraviolet shielding component as fine particles. When added as fine particles, the sustainability of the ultraviolet ray shielding effect of the organic ultraviolet ray shielding component is significantly improved.

International Publication 2006/137454 Pamphlet JP, 2009-184882, A International Publication No. 2012/107968 pamphlet

Since the ultraviolet A wave (UVA) in the long wavelength range reaches the deep part of the skin and damages the skin, its effective shielding is desired. In particular, in recent years, the transmittance T _UV 380 in the ultraviolet region where the end on the long wavelength side is 380 nm and the transmittance T _UV 400 which is the transmittance in the wavelength region 300 nm to 400 nm where the end on the long wavelength side is 400 nm are sufficient. There is a need for glass plates 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, if T _UV 400 is added benzenethiol copper complex to the extent that sufficiently reduced, the coating film containing the ultraviolet shielding components, visible light transmittance while strongly colored yellow is a complementary color of the light in the visible short wavelength region YA decreases.

In general, and especially for glazing applications, strong tinting of the glass sheet to a yellowish color tends to be undesirable. Therefore, an object of the present invention is to provide a glass plate with a coating film containing an ultraviolet ray shielding component, which can reduce the transmittance of light near a wavelength of 400 nm while suppressing remarkable coloring to a yellowish color. .. Another object of the present invention is to provide a coating film-forming composition suitable for forming the coating film.

The present invention, from one aspect thereof,
A glass plate for transportation equipment having a glassy coating film containing an additive imparting ultraviolet absorption ability,
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 comprises an organic compound A,
There is provided a glass plate, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thio organic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR when the organic group is R.

The present invention, from another aspect thereof,
A composition for forming a coating film for a glass plate for transportation equipment with a glassy coating film, which contains an additive imparting ultraviolet absorbing ability,
Containing a silicon oxide precursor and an organic compound A which is an additive imparting ultraviolet absorbing ability,
The organic compound A has a 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 thio organic group connected to the 2-phenylbenzotriazole skeleton. ..
However, the thioorganic group is a group represented by -SR when the organic group is R.

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

ADVANTAGE OF THE INVENTION According to this invention, the glass plate with a coating film suitable for reducing the transmittance|permeability of the light of wavelength 400nm vicinity, suppressing the remarkable coloring to yellowish, and the composition suitable for formation of this coating film. , Can be provided.

It is sectional drawing which shows one form of the glass plate by this invention. It is a top view which shows the form when using the glass plate by this invention as a door glass. It is a top view which shows another form when using the glass plate by this invention as a door glass. It is a partial cross section top view which shows the form when using the glass plate by this invention as a door glass.

The preferred embodiments of the present invention will be described below, but the following description is not intended to limit the present invention to the particular embodiments.

One aspect of the present invention is as follows.
A glass plate with a coating film containing an additive that imparts ultraviolet absorbing ability,
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 comprises an organic compound A,
A glass plate in which the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thio organic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR when the organic group is R.

In one mode of the glass plate according to the present invention, the organic compound A includes a unit represented by the following formula (1). However, in the formula (1), A ^{1 to} A ⁹ are each independently 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 thio organic group is a group that contains a sulfur atom and is not connected to the 2-phenyl-benzotriazole skeleton by a sulfide bond (-S-).

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

In one mode of the glass plate according to the present invention, the thioorganic group is a thioalkyl group optionally having a hydrogen atom substituent or a thioaryl ring group optionally having a hydrogen atom substituent. Here, the thioalkyl group is a group represented by -S-Alk when an alkyl group which may have a substituent of a hydrogen atom is represented by Alk, and the thioaryl ring group has a substituent of a hydrogen atom. It is a group represented by -S-Ary when the aryl ring group which it may have is represented by Ary. However, the thio organic group may be other than the thioalkyl group and the thioaryl ring group.

In one mode of the glass plate according to the present invention, the alkyl group which may be substituted with a hydrogen atom contained in the thioalkyl group is an alkyl group having 1 to 18 carbon atoms, or a phenyl group as a hydrogen atom substituent. 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 linear 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 Each of the two 2-phenylbenzotriazole skeletons is connected via a sulfide bond.

The thioorganic group interposed between the two 2-phenylbenzotriazole skeletons is an alkylene group which may have a hydrogen atom substituent (Alk), and an arylene which may have a hydrogen atom substituent. When the ring group is represented by (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 present 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 of a hydrogen atom. The alkyl group may be a linear 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, as a substituent, a chain alkyl group containing a quaternary carbon atom and having a branch of 4 to 9 carbon atoms.

In one mode 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 mode 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 substituent of a hydrogen atom. 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 substituent of a hydrogen atom is represented by Cy.

In one mode of the glass plate according to the present invention, the number of carbon atoms of 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, a substituent of a hydrogen atom which may be contained in a thioalkyl group or a thioaryl ring group is a halogen atom, a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, It is 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 substituent of a hydrogen atom which may be contained in the thioalkylene group or the thioarylene ring group, and the substituent of a hydrogen atom described later.

The substituent of the hydrogen atom which may be contained in the cyclic thioorganic group, particularly the thioaryl ring group or the 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. May be The carbon number of the hydrocarbon group and the hydroxy group is preferably 2 or more, 3 or more, particularly 4 or more, and 12 or less, 9 or less, particularly 8 or less. The hydrocarbon group may be acyclic or cyclic, for example, a linear or branched chain alkyl group having 4 to 9, 3 to 8 or 4 to 8 carbon atoms, particularly a branched alkyl group. It is a chain alkyl group having. The number of hydrogen atom substituents which may be contained 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 a carbon atom. It is preferably a linear or branched chain alkylene group having a number of 3 to 12, and further preferably a branched alkylene group, and may be an alkylene group containing a quaternary carbon atom.

In one mode of the glass plate according to the present invention, the organic compound A is a thioaryl ring group optionally represented by any one of the following formulas (2-1) to (2-3) and having a hydrogen atom substituent. Alternatively, it is 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 -...) optionally having the substituent of a hydrogen atom is bonded, and X ^1a is phenyl. A residue of a ring or a naphthyl ring, and 1 R ^1a each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and l is 0 to 5 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-...) optionally having the above-mentioned substituent of a hydrogen atom is bonded, and Cy is a cyclohexyl ring. Represents a residue, and m R ^1b each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and m represents an integer of 0 to 5.)
^{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-), which may have the substituent, is bonded, A ^1c is the following formula:
-[ ^X1c- ( ^R1c ) _n ]-( ^A2c ) _q- [ ^X2c- ( ^R2c ) _p ]-
(In the formula, X ^1c and X ^2c each independently represent a residue of a phenyl ring or a naphthyl ring, and n R ^1c and p R ^2c are each independently a hydrocarbon group having 1 to 18 carbon atoms or a carbon atom. The number 1 to 18 represents an alkoxy group or a hydroxy group, n and p represent integers of 0 to 4, A ^2c represents an aromatic group, an unsaturated group, a nitrogen atom-containing group, a sulfur atom-containing group, an oxygen atom. A hydrogen atom is replaced by at least one of the both ends with a monovalent or divalent group selected from a containing group, a phosphorus atom-containing group, an alicyclic group, and a halogen atom, or a carbon- A divalent hydrocarbon group having 1 to 20 carbon atoms in which a carbon bond may be interrupted, a divalent aromatic group, or a sulfide bond, and q represents an integer of 0 or 1.). Is a group or represents a phenyl ring or naphthyl ring residue. )

In the 2-phenylbenzotriazole derivative represented by any of the formulas (2-1) to (2-3), the substituent of the hydrogen atom is, for example, a halogen atom, a hydrocarbon group, an aromatic group or an unsaturated group. , An atom or a group corresponding to at least one selected from an oxygen atom-containing group, a phosphorus atom-containing group, and a sulfur atom-containing group.

In one mode 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 residues of a phenyl ring. 1 and n and p are 0.

In one mode 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 the 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 a hydrogen atom at the 4- and 6-positions and an alkyl group having 1 to 6 carbon atoms at 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 the 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 atom of 1 ~6 alkyl group, especially a methyl group, A ⁵ is a hydrogen atom.

In one mode 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 residues of a phenyl ring. R ^{< 1a>} , R ^<1c> and R ^<2c > each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, and l, n and p each represent an integer of 1 to 5.

In one mode 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 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 each represent an integer of 1 to 3.

In one mode 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 residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, and l, n and p represent 1.

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

In one mode 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 residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, and l, n and p represent 2.

In one mode 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 residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having a carbon number of 1 to 18 containing a tertiary carbon and/or a quaternary carbon, and l, n and p shows the integer of 1-5.

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

In one mode 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 residues of a phenyl ring. R ^1a , R ^1c and R ^2c each independently represent an alkoxy group containing a linear or branched chain alkyl group having 1 to 18 carbon atoms.

In one mode 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 residues of a phenyl ring. Where R ^1a , R ^1c and R ^2c represent a hydroxy group.

In one mode 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 residues of a naphthyl ring. Show.

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

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

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

In one mode of the glass plate according to the present invention, the organic compound A is represented by the formula (2-3), 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 mode of the glass plate according to the present invention, the organic compound A is represented by the formula (2-3), X ^1c and X ^2c represent a residue of a phenyl group, 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), X ^1a represents a residue of a phenyl group, and R ^1a represents a straight 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. R ^1a may be a linear or branched chain alkyl group having 4 to 9 carbon atoms, and 1 may be 1 or 2. 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 a quaternary carbon.

In one mode of the glass plate according to the present invention, the organic compound A is represented by the 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 chain alkyl group having 1 to 18 carbon atoms, or a hydroxy group, and 1 is 1 or 2.

In one mode of the glass plate according to the present invention, the organic compound A is represented by the formula (2-1), and the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton has a hydroxy group and a The 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 be connected to this phenyl group, respectively. 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 mode 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 a thio organic group is not 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 a form of fine particles having an average particle size of 150 nm or less. In one form of the glass plate according to the present invention, the organic compound A has a form of fine particles having an average particle size of 150 nm or less.

In one form of the glass plate according to the present invention, T _UV 400 calculated according to ISO13837 (convention A) is 2% or less, and visible light transmittance YA measured using a CIE standard A light source is 70% or more. In one mode of the glass plate according to the present invention, the transmitted light from the CIE standard C light source is displayed by the L ^* a ^* b ^* color system, and a ^{* of} -15 or more and 0 or less and b ^{* of} 12 or less are displayed. Have. In one form of the glass plate according to the present invention, the yellowness YI defined by JIS K7373:2006 of the transmitted light from the CIE standard C light source is 14 or less. In one form of the glass plate according to the present invention, wavelength 295～450Nm, the ultraviolet transmittance T _UV 400 before irradiating the ultraviolet rays UV transmittance T _UV 400 after irradiation for 100 hours with ultraviolet rays at an illuminance 76mW / cm ² The subtracted difference ΔT _UV 400 is 2% or less.

Another aspect of the present invention is as follows.
A coating film-forming composition for a glass plate with a coating film, which contains an additive imparting an ultraviolet absorbing ability,
Containing a silicon oxide precursor and an organic compound A which is an additive imparting ultraviolet absorbing ability,
The organic compound A has a form of fine particles,
The composition for forming a coating film, wherein the organic compound A has a molecular structure containing a 2-phenylbenzotriazole skeleton and a thio organic group connected to the 2-phenylbenzotriazole skeleton through a sulfide bond.

In one mode of the coating film forming composition according to the present invention, the average particle diameter of the fine particles is 150 nm or less.

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

Hereinafter, one embodiment of the glass sheet according to the present invention will be described more specifically with reference to the drawings.

The glass plate of the present embodiment shown in FIG. 1 includes a glass plate 1 and a coating film 2 directly formed on the surface thereof and containing an ultraviolet ray shielding component. The coating film 2 contains silicon oxide and organic compound A. The coating film 2 preferably contains silicon oxide as a main component. In the present specification, the "main component" is a term meaning a component that occupies 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. The organic compound A functions as an ultraviolet shielding component. The organic compound A has a 2-phenylbenzotriazole skeleton, and has a molecular structure in which at least one thioorganic group is connected to this skeleton. The 2-phenylbenzotriazole skeleton is a portion excluding the functional groups A ^{1 to} A ⁹ of the formula (1).

The film quality of the coating film is arbitrary, but it is preferably glassy. As used herein, the film being "glassy" means that the main component of the film is glassy, that is, amorphous, and does not mean that the film does not contain crystals. Therefore, even a “glassy” film may contain a crystalline component derived from the organic compound A, the organic compound B described later, ITO fine particles, and the like.

The coating film 2 may contain components other than silicon oxide and the organic compound A. The optional components of the film 2 include an organic compound B which is a UV-shielding component that does not correspond to the organic compound A and an organic compound C which is a hydrophilic organic compound. The organic compound C may be a polymer. The coating film 2 may further contain other components such as a structural unit derived from a 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 substances and/or inorganic substances.

The organic compound A is preferably added as fine particles. The addition as fine particles improves the durability of the ultraviolet shielding effect as compared with the case where it is added as a solute. In order to suppress the haze ratio 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 the present specification, "normal temperature" is a term meaning 25°C.

A polymer obtained by polymerizing a polymerizable ultraviolet absorber is also known as an ultraviolet shielding component that is solid at room temperature. However, since such an ultraviolet shielding component is produced by polymerizing an ultraviolet absorber having a polymerizable functional group such as a (meth)acryl group introduced therein, the ultraviolet shielding effect is low in the molecular weight of ultraviolet rays when compared per unit mass. Inferior to absorbent.

The molecular weight of the organic compound A is preferably 5000 or less, more preferably 3000 or less, further preferably 2000 or less, particularly preferably 1500 or less, and in some cases 1300 or less, further 1200 or less, particularly 900 or less, and particularly 800 or less, Good. The molecular weight of the organic compound A is preferably 200 or more, more preferably 300 or more. The organic compound A preferably does not contain a polymerizable carbon-carbon double bond in the molecule. Examples of the polymerizable carbon-carbon double bond include a double bond contained in a polymerizable functional group such as a vinyl group, a vinylene group and a vinylidene group.

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

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. The corresponding atom or group. However, at least one of A ^{1 to} A ⁹ is a thio organic group. A ^{1 to} A ⁹ may include a sulfur atom-containing group that is not a thio organic group. A sulfur atom-containing group that does not correspond to a thio organic group is a group that contains a sulfur atom and is not connected to the 2-phenylbenzotriazole skeleton via a sulfide bond (-S-).

More specifically, A ^{1 to} A ⁹ are each independently a hydrogen atom or a halogen atom, or 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 A ^{1 to} A ⁹ may correspond to two or more of the above groups. For example, a phenyl group is an aromatic group with a hydrocarbon group, the formula: -S- (CH ₂₎ groups represented by ₂ -OH is a sulfur atom-containing group with an oxygen atom-containing group, thio organic Also applicable to the group. At least one of A ^{6 to} A ⁹ is preferably a thio organic group. However, A ^{6 to} A ⁹ does not include a thio organic group, and at least one of A ^{1 to} A ⁵ may be a thio organic group.

The organic compound A may be composed of one kind of compound or may contain plural kinds of compounds.

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

(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 described here. The aliphatic group may be acyclic or cyclic and is, for example, a linear or branched alkyl group, an alkenyl group or an alkynyl group, and for example, a hydrogen atom is substituted with an alkyl group. Optionally a cycloalkyl group or a cycloalkenyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The number of carbon atoms in the hydrocarbon group is preferably 1-20, more preferably 1-18, even more preferably 1-10, particularly preferably 4-9. Preferred examples of the hydrocarbon group include a straight-chain or branched alkyl group having 1 to 20, 1 to 9, and further 4 to 9 or 1 to 3 carbon atoms, and particularly a branched group having 4 to 9 carbon atoms. It includes an alkyl group and a cyclic alkyl group having 3 to 10 carbon atoms, and further 3 to 8 carbon atoms.

The linear or branched alkyl group is not particularly limited, and examples thereof include methyl group, benzyl group, α,α-dimethylbenzyl group, ethane-1-yl group, propan-1-yl group, 1-methylethane- 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, pentane-2- Yl group, hexane-1-yl group, heptan-1-yl group, octan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, nonan-1-yl group, decan- 1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1 -Yl group and octadecan-1-yl group. Examples of the linear or branched alkenyl group include vinyl group, prop-1-en-1-yl group, allyl group, isopropenyl group, but-1-en-1-yl group, but-2-ene- 1-yl group, but-3-en-1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, penta-1-en-1- Group, penta-2-en-1-yl group, penta-3-en-1-yl group, penta-4-en-1-yl group, 3-methylbut-2-en-1-yl group, 3 -Methylbut-3-en-1-yl group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, hexa-4-ene group -1-yl group, hexa-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group, hepta-1-ene-1 -Yl group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group, nona-1-en-1-yl group, nona- 8-en-1-yl group, deca-1-en-1-yl group, deca-9-en-1-yl group, undec-1-en-1-yl group, undec-10-en-1- Group, dodeca-1-en-1-yl group, dodeca-11-en-1-yl group, trideca-1-en-1-yl group, trideca-12-en-1-yl group, tetradeca-1 -En-1-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, hexadeca-15-en-1-yl group, heptadeca-1-en-1-yl group, heptadeca-16-en-1-yl group, octadeca-1-en-1-yl group, octadeca-9- Examples thereof include en-1-yl group and octadec-17-en-1-yl group. Examples of the linear or branched alkynyl group include ethynyl, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1-yn-1-yl group, buta-3. -In-1-yl group, 1-methylprop-2-yn-1-yl group, penta-1-in-1-yl group, penta-4-yn-1-yl group, hexa-1-yn-1 -Yl group, hexa-5-yn-1-yl group, hepta-1-in-1-yl group, hepta-6-in-1-yl group, octa-1-in-1-yl group, octa- 7-in-1-yl group, nona-1-in-1-yl group, nona-8-in-1-yl group, deca-1-in-1-yl group, deca-9-in-1- Group, undeca-1-yn-1-yl group, undeca-10-yn-1-yl group, dodeca-1-in-1-yl group, dodeca-11-in-1-yl group, trideca-1 -In-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, heptadeca-1-yn-1-yl group, heptadeca-16- Examples thereof include in-1-yl group, octadec-1-yn-1-yl group and octadec-17-in-1-yl group.

Examples of the preferred cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

(Aromatic group)
The aromatic group is a group containing an aromatic ring such as a benzene ring, a naphthalene ring and an anthracene ring. The carbon number of the aromatic group is preferably 6-18, more preferably 6-14. Examples of aromatic groups include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 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 Groups, 2-fluorophenyl groups and 4-fluorophenyl groups.

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

(Oxygen atom-containing group)
The oxygen atom-containing group is a group containing an oxygen atom. The oxygen atom-containing group usually contains carbon atoms and/or hydrogen atoms together with oxygen atoms. The number of carbon atoms contained in the oxygen atom-containing group is 6 to 20, particularly 6 to 12 when the aromatic ring group and/or the alicyclic group is contained, and when the aromatic ring group and the alicyclic group are not contained. 0-20, more preferably 0-12, especially 0-6 is preferred. Examples of the oxygen atom-containing group include hydroxy group, alkoxy group, acetoxy group, acetyl group, aldehyde group, carboxy group, carbamoyl group, urethane group, amide group, imide group, urea group, ether group, carbonyl group, ester group. , Oxazole groups and morpholine groups. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, methylphenoxy group, dimethylphenoxy group, naphthoxy group, phenylmethoxy group and phenylethoxy group. Examples of preferable 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)
The phosphorus atom-containing group is a group containing a phosphorus atom. The phosphorus atom-containing group usually contains a carbon atom and/or a hydrogen atom together with the phosphorus atom. The number of carbon atoms contained in the phosphorus atom-containing group is 6 to 20, particularly 6 to 12 when the aromatic ring group and/or the alicyclic group are contained, and when the aromatic ring group and the alicyclic group are not contained. 0 to 20, more preferably 0 to 12, and most preferably 0 to 6 is preferred. Examples of the phosphorus atom-containing group include phosphine group, phosphite group, phosphonic acid group, phosphinic acid group, trimethylphosphine group, tributylphosphine group, tricyclohexylphosphine group, triphenylphosphine group, tritolylphosphine group, and methylphosphite. Groups, ethyl phosphite groups, phenyl phosphite groups, phosphonic acid groups, phosphinic acid groups, phosphoric acid groups and phosphoric acid ester groups.

(Sulfur atom-containing group)
The sulfur atom-containing group is a group containing a sulfur atom. The sulfur atom-containing group usually contains a carbon atom and/or a hydrogen atom together with a sulfur atom. The number of carbon atoms contained in the sulfur atom-containing group is 6 to 20, further 6 to 12, particularly 6 to 10 when the aromatic ring group and/or the alicyclic group are contained, and the aromatic ring group and/or the alicyclic group. When it does not contain a group, it is preferably 0 to 20, more preferably 0 to 12, particularly 0 to 10, and especially 0 to 6. Examples of the sulfur atom-containing group include a thiol group, a sulfide group, a disulfide group, a sulfonyl group, and a sulfo group. Group, thiocarbonyl group, thiocarbamoyl group, thiourea group, thioalkoxy group, thiocarboxy group, thiophene group and thiazole group.

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 optionally having a hydrogen atom substituent (-S-Alk), or a thioaryl ring group optionally having a hydrogen atom substituent (-S-Ary). 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 of the hydrogen atom in the thio organic 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. Alternatively, it may be a group. Examples of these substituents are as described above.

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

The thioorganic group interposed between the two 2-phenylbenzotriazole skeletons is also preferably a group containing a unit represented by -S-(Ary)-(Alk)- 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. Also in this case, (Alk) is preferably a branched chain alkyl group, and particularly preferably a branched chain alkyl group having 4 to 9 carbon atoms.

Explaining from another aspect, the organic compound A is represented by any of the formulas (2-1) to (2-3), and is a thioaryl ring group or thiohexyl ring group which may have a substituent of a hydrogen atom. It may be a 2-phenylbenzotriazole derivative having The preferred substituents of the 2-phenylbenzotriazole skeleton (see formula (2-1)) possessed by this derivative will be described.

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 the thiocyclohexyl ring group is not particularly limited and may be any of R ^{1 to} R ⁹ , but R ^{6 to} R ⁹ are preferable, and R ⁷ and R ⁸ are more preferable. The number of substitutions of the thioaryl ring group or the thiocyclohexyl ring group is not particularly limited, but is preferably 1 or 2, and particularly preferably 1.

At least one of A ^{1 to} A ⁵ of the organic compound A is preferably an oxygen atom-containing group. Particularly, 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 the organic compound A are preferably alkyl groups having 1 to 4 carbon atoms. Particularly, at least A ² and A ⁴ are preferably an alkyl group 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 enhancing light resistance, the following combinations of substituents are preferable. Preferred examples of the combination of R ⁶ , R ⁷ , R ⁸ and R ⁹ in formula (2-1) are as follows.
A -1 Equation (2-1), at least one of ^{R 6, R 7, R 8} , R 9 of the (2-3), a thioaryl ring group. Further, 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 residues of a phenyl ring or a naphthyl ring.
In A-3A- ¹ , 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 .
In any of A -5 A -1 Karaa -4, R ⁶ ~R ⁹ except thioaryl ring group or thio cyclohexyl ring groups 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 residues of a phenyl ring.
In any of the A -7 A -1 Karaa -5, X ^1a, X ^1c of thioaryl ring group, the X ^2c is a residue of a naphthyl ring.

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 the formula (2-3) may be different from each other or the same.
B-1 hydrocarbon group having 1 to 18 carbon atoms (including alkenyl group and hydrocarbon group having 2 to 18 carbon atoms including alkynyl group), hydroxy group, aromatic group having 6 to 18 carbon atoms, and carbon number 1 To an ether group having 18 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an ester group having 1 to 18 carbon atoms, a (meth)acryloyloxy group and/or a polyoxyethylene group having 1 to 20 carbon atoms, or a substituent thereof. It contains at least one substituent selected from a hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with hydrogen atom, interrupted at the terminal end, or interrupted with carbon-carbon bond.
A-2 In a-1, the substituent is at least one selected from a hydrocarbon group having 1 to 10 carbon atoms and a hydroxy group.
A-3 In a-2, the substituent is at least one selected from a hydrocarbon group having 1 to 8 carbon atoms and a hydroxy group.
B-4 In any one of B-1 to B-3, the hydrocarbon group as the substituent is a linear or branched alkyl group.
A-5 in a-4, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group.
A-6 In a-5, the substituent is at least one selected from a methyl group, a t-butyl group, and a hydroxy group, and the number of the hydroxy groups is 1 or less.
B-7, in any one of B-1 to B-6, the number of substituents is 1 to 4.
B-8, in any one of B- ^{1 to B-} 7, it has a substituent at any position of R ^{1 to} R ⁴ , and the other R ^{1 to} R ⁵ are hydrogen atoms.
B-9, in any one of B- ¹ to B-8, it has a substituent at any position of R ¹ , R ² and R ⁴ , and the other R ^{1 to} R ⁵ are hydrogen atoms.
A-10 In a-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.
A-11 In any one of A-1 to A-9, it has a substituent at any position of R ¹ and R ⁴ , and R ^{1 to} R ⁵ other than it have a hydrogen atom.
A-12 In a-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 the combinations of ¹ R ^1a and X ^1a in the formula (2-1) are as follows.
C-1 X ^1a is a residue of a phenyl ring.
In c -2 c -1, with l = 0, no substituent R ^1a to X ^1a, a portion may be substituted in R ^1a in the X ^1a are all 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=1-5.
C-4 In C-3, l=1 to 3.
U-5 In U-4, at least one R ^1a is independently a branched alkyl group having 3 to 8 carbon atoms.
U-6 In U-4, l=1 and R ^1a's each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
U-7 In U-6, l=1 and R ^1a's each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group is preferably 1 to 8 carbon atoms; It preferably has 2 to 8 carbon atoms, more preferably 3 to 8 carbon atoms, still more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and most preferably 4 carbon atoms.
C-8 In any one of C-3 to C-7, at least one R ^1a is in the para position with respect to PhBzT ^1a -S-.
U-9 In U-4, when 1=2, R ^1a's each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
U-10 In U-9, when 1=2, R ^1a's each independently represent 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, more preferably 1 carbon atom, and/or the total number of carbon atoms of the alkyl group is preferably 2 to 12, more preferably 2 to 10, still more preferably 2 to 5, particularly preferably. Is 2.
U-11 In any of U-9 and 10, each R ^1a of 1=2 with respect to PhBzT ^1a -S- is in the ortho, para or ortho or meta position.
In any of U-12, U-3 to U-11, R ^1a is independently a hydrocarbon group having a tertiary carbon and/or a quaternary carbon, and preferably an alkyl group.
U-13 In U-1, each of ¹ R ^1a is independently an alkoxy group having a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear alkyl group having 1 to 8 carbon atoms. An alkoxy group having a group, more preferably an alkoxy group having a linear alkyl group having 1 to 4 carbon atoms. Further, preferably 1=1 to 3, more preferably 1=1 to 2, and particularly preferably 1=1.
U-14 In U-13, l=1 and the alkoxy group is in the meta position with respect to PhBzT ^1a —S—.
U-15 In U-1, one R ^1a is a hydroxy group, preferably 1=1 to 3, more preferably 1=1 to 2, and particularly preferably 1=1.
U-16 In U-15, 1=1 and the hydroxy group is in the para position with respect to PhBzT ^1a -S-.
U-17 X ^1a is a residue of a naphthyl ring, preferably 1=0.

The 2-phenylbenzotriazole derivative represented by the 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-). Butyl-5-methylphenyl)-2H-benzotriazole, 5-phenylthio-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole and the like can be mentioned.

Preferred examples of combinations of m R ^1b in formula (2-2) are as follows.
In d -1 m = 0, no substituent R ^1b to Cy, moiety capable of replacing the R ^1b in Cy are all hydrogen atoms.
D-2 m R ^1b 's each independently represent 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 m= 1 to 5.
D-3 In m-2, m=1 to 3.
D) In d-3, at least one R ^1b is independently a branched alkyl group having 3 to 8 carbon atoms.
D-5 In D-3, m 1 and R ^1b is a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
D-6 In d-5, m=1 and R ^1b is a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group is preferably 1 to 8 carbon atoms, more preferably carbon. It has 2 to 8 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and most preferably 4 carbon atoms.
D-7 In any one of D-2 to D-6, at least one R ^1b is in the para position with respect to PhBzT ^1b -S-.
D-8 In d-3, m 1 =2 and R ^1b's each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
E-9 In E-8, R ^1b is 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, more preferably 1 carbon atom, and/or the total number of carbon atoms of the alkyl group is preferably 2 to 12, more preferably 2 to 10, still more preferably 2 to 5, particularly preferably. Is 2.
D-10 In any one of d-8 and d-9, R ^{1b having} m=2 with respect to PhBzT ^1b -S- is in the ortho, para position or ortho, meta position.
In any one of d-11 to d-10, R ^1b is a hydrocarbon group having a tertiary carbon and/or a quaternary carbon, preferably a branched alkyl group.
D-12 In D-1, m R ^1b 's each independently represent an alkoxy group having a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear alkyl group having 1 to 8 carbon atoms. An alkoxy group having a group, more preferably an alkoxy group having a linear alkyl group having 1 to 4 carbon atoms. Further, preferably m=1 to 3, more preferably m=1 to 2, and particularly preferably m=1.
E-13 In U-12, m=1, and the alkoxy group is in the meta position relative to PhBzT ^1b -S-. E-14 In E-1, m R ^1b are hydroxy groups, preferably m=1 to 3, more preferably m=1 to 2, and particularly preferably m=1.
E-15 In E-14, m=1 and the hydroxy group is in the para position with respect to PhBzT ^1b —S—.

The 2-phenylbenzotriazole derivative represented by the 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 the formula (2-3), A ^2c is a monovalent or divalent selected from an aromatic group, an unsaturated group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom. 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, with a valent group, 2 A valent aromatic group or a sulfide group -S- is shown.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in A ^2c include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Of these, an aliphatic hydrocarbon group is preferable, and examples thereof include a linear or branched alkylene group, a linear or branched alkenylene group, and a linear or branched alkynylene group. Although not particularly limited, for example, methylene group, 1,1-dimethyl-methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group , 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group , Pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, Hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, eicosan-1,20-diyl group and the like can be mentioned. Among these, a linear or branched alkylene group is preferable, and a branched alkylene group is more preferable.

In the case where the divalent hydrocarbon group is a monovalent or divalent group, in which a hydrogen atom is replaced, at least one of both ends is interrupted, or a carbon-carbon bond is interrupted, the above-mentioned 1 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 monovalent or divalent aromatic group, unsaturated group, nitrogen-containing group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group and halogen atom are the above-mentioned 2- The same as the monovalent or divalent groups described as the substituents of R ^{1 to} R ⁹ of the phenylbenzotriazole skeleton are mentioned, and the description is referred to.

The divalent aromatic group for A ^2c includes an aromatic ring such as a benzene ring, a naphthalene ring and an anthracene ring, and preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. The divalent aromatic group is not particularly limited, and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,8-naphthylene group, and a 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.
In o -2 o -1, n, at ^{p = 0, X 1c, X} 2c substituent R ^1c, R ^2c instead, X ^1c, R ^1c in the X ^2c, all parts may be substituted with R ^2c is hydrogen Is an atom.
O-3 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 straight chain having 1 to 18 carbon atoms. Alternatively, it is a branched alkyl group, and n and p=1 to 5.
O-4 In o-3, n and p=1 to 3.
O-5 In O-4, at least one of R ^1c and R ^2c is independently a branched alkyl group having 3 to 8 carbon atoms.
O-6 In O-4, when n and p=1, R ^1c and R ^2c are each independently a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms).
O-7 In o-6, n, p=1, R ^1c and R ^2c are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group preferably has 1 to 10 carbon atoms. 1 to 8, more preferably 2 to 8 carbon atoms, still more preferably 3 to 8 carbon atoms, still more preferably 3 to 5 carbon atoms, particularly preferably 4 to 5 carbon atoms, and most preferably 4 carbon atoms.
O-8 In O-4, n 1 and p=2, R ^1c and R ^2c are each independently a linear 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 linear or branched alkyl group having 1 to 10 carbon atoms, and each carbon number of the alkyl group is Preferably, it has 1 to 5, more preferably 1 to 4, still more preferably 1 carbon atom, and/or the total number of carbon atoms in the alkyl group is preferably 2 to 12, more preferably 2 to 10, still more preferably 2 carbon atoms. -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 each independently represent an alkoxy group having a linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Is an alkoxy group having a linear alkyl group, and more preferably an alkoxy group having a linear alkyl group having 1 to 4 carbon atoms. Further, preferably n and p=1 to 3, more preferably n and p=1 to 2, and 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 and 2, particularly preferably n and p=1.
O-13 X ^1c and X ^2c are residues of a naphthyl ring, and 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, substituents R ^1c to X ^2c, R ^2c instead, X ^1c, R ^1c in the X ^2c, portion which substitutes the R ^2c are all 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 linear or branched alkylene). Group). Preferably, n, p = 0, X 1c, substituents R ^1c to X ^2c, R ^2c instead, X ^1c, R ^1c in the X ^2c, portion which substitutes the R ^2c are all hydrogen atoms.
O-16 In any of o-1 to o-13, q=0. Preferably, n, p = 0, X 1c, substituents R ^1c to X ^2c, R ^2c instead, X ^1c, R ^1c in the X ^2c, portion which substitutes the R ^2c are all hydrogen atoms.
In any of o -17 o -1 Calao _{^{-16, - (A 1c) q}} - is, PhBzT ^1c -S-, is in the para position relative PhBzT ^2c -S-.

The 2-phenylbenzotriazole derivative represented by the 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.

The preferred embodiment of the organic compound A is as follows.
The 2-phenylbenzotriazole derivative is represented by formula (2-1) or (2-3), and in formula (2-1) or (2-3), X ^1a , X ^1c , and X ^2c are It represents a residue of a phenyl ring, and l, n, and p are 0.
Particularly, the 2-phenylbenzotriazole derivative is represented by any one of formulas (2-1) and (2-3), and in formulas (2-1) and (2-3), X ^1a and X ^{1c are represented.} , X ^2c represents a residue of a phenyl ring, l, n and p are 0, and the 2-phenylbenzotriazole skeleton has a hydroxy group at R ¹ and a methyl group at R ⁴ .

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 residue of a phenyl ring, l, n and p R ^1a , R ^1c and R ^2c each independently represent a linear or branched hydrocarbon group having 1 to 18 carbon atoms, and l, n and p are Indicates an integer of 1 to 5.
Particularly, in the formula (2-1) or (2-3), X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and l, n and p R ^1a , R ^1c and R ^2c are each independently. At least one represents a branched alkyl group having 3 to 8 carbon atoms, and l, n, and p each represent an integer of 1 to 3.
Alternatively, in the formula (2-1) or (2-3), X ^1a , X ^1c and X ^2c represent a residue of a phenyl ring, and l, n and p R ^1a , R ^1c and R ^2c are each independently. Represents a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n, and p each represent an integer of 1.
Alternatively, in the formula (2-1) or (2-3), X ^1a , X ^1c and X ^2c represent a residue of a phenyl ring, and l, n and p R ^1a , R ^1c and R ^2c are each independently. Represents a linear or branched alkyl group having 1 to 18 carbon atoms, and l, n, and p each represent an integer of 2.
Alternatively, in the formula (2-1) or (2-3), X ^1a , X ^1c and X ^2c represent a residue of a phenyl ring, and l, n and p R ^1a , R ^1c and R ^2c are each independently. Shows a hydrocarbon group having a tertiary carbon and/or a quaternary carbon having 1 to 18 carbon atoms, and l, n and p each represent an integer 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 residue of a phenyl ring, 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 residue of a phenyl ring, 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 The residue of the naphthyl ring is shown.

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

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

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

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

The organic compound A preferably 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 retains the crystalline state.

The organic compound A may be blended into the coating film forming composition after being crushed by a known dry or wet pulverizing device so as to have a predetermined average particle size. The time required for the organic compound A to be crushed to reach a predetermined average particle diameter depends on the type of crushing device, the amount charged, and the crushing conditions such as the number of revolutions. Therefore, in mass production, the time until the predetermined average particle size is obtained can be determined in advance by repeatedly interrupting the crushing by the crushing device and checking the average particle size of the sampled crushed product. Good. At the time of crushing, a surfactant, a water-soluble resin, etc. may be added to the organic compound A to be crushed as appropriate.

The organic compound A may be 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, and particularly preferably 70 to 140 nm. If the average particle diameter of the fine particles is too large, the transparency of the film is lowered, but if it is too small, the ultraviolet absorbing ability may be deteriorated or the durability thereof may be lowered. The "average particle size" is a numerical value based on a measurement value by a dynamic light scattering method which is a kind of photon correlation method, including the measurement values in the section of Examples described later, and specifically, a sphere equivalent. It is the particle size at which the cumulative frequency is 50% in the distribution based on the volume of the size. 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 fine particles of the organic compound A dispersed in the film can be confirmed by observing the particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The average value A of the uppermost 10% of the maximum lengths of the respective fine particles present in the film cross section observed using SEM or TEM does not fall below the value of the “average particle diameter” defined above. Therefore, if the average value A is 150 nm or less, the “average particle size” can be regarded as 150 nm or less. In addition, the average value B of the lower 10% of the length in the direction orthogonal to the direction that defines the maximum length of each fine particle existing in the above-mentioned film cross section must exceed the value of the "average particle size" defined above. There is no. 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 film as a solute obtained by dissolving the organic compound A in an organic solvent capable of dissolving the organic compound A. The introduction as a solute is a method that can be more easily carried out, and is also a desirable method for achieving a more uniform distribution of the organic compound A in the coating film. However, by introducing the organic compound A as fine particles into the film, the durability of the ultraviolet shielding ability of the film is improved. Furthermore, by adding the organic compound A as fine particles, more preferable spectral absorption characteristics can be obtained as compared with addition as a solute.

When added as fine particles, the absorption peak of the organic compound A in the spectral absorbance curve may shift to a longer wavelength side than when added as a solute. Due to this shift, it becomes possible to more effectively shield the light near the wavelength of 400 nm. On the other hand, however, the yellowing of the coating film becomes stronger due to the shift of the absorption peak to the longer wavelength side. The organic compound A is suitable for sufficiently reducing the transmittance of light having a wavelength of about 400 nm while suppressing the strong coloring of the coating film in yellow.

The coating film forming composition 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, but water is most suitable. As the lower alcohol, alcohols having 1 to 3 carbon atoms such as methanol, ethanol and isopropanol are preferable. The coating film forming composition may contain components such as an organic compound B and a silane coupling agent, which may be added to the coating film. The coating film forming composition may optionally contain additives such as a wetting agent, a preservative, an antifungal agent, an antifoaming agent and a stabilizer.

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 later, a preferred silicon oxide precursor is a silicon compound having a hydrolyzable functional group, typically a silicon tetraalkoxide. 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.

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

The organic compound A is contained in the range of 1 to 80%, further 5 to 60%, especially 5 to 50%, and especially 7 to 30%, expressed by mass% with respect to the silicon oxide in the coating film. Is preferred. Taking this into consideration, the organic compound A is added so as to be 0.5 to 25%, more preferably 0.5 to 15%, also expressed by mass% with respect to the liquid amount of the film forming solution. Preferably.

The organic compound B is an ultraviolet shielding component that does not correspond to the organic compound A. The organic compound B preferably has a 2-phenylbenzotriazole skeleton and has a molecular structure in which a sulfur atom-containing group is not connected to the 2-phenylbenzotriazole skeleton. The organic compound B may also be added to the coating film or the coating film forming composition so as to have a form of fine particles having an average particle size of 150 nm or less.

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

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, or a sulfur atom-containing group other than a thioorganic group. An atom or group corresponding to at least one selected. More specifically, B ^{1 to} B ⁹ are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group, an aromatic group, an unsaturated group, an oxygen atom-containing group, a phosphorus atom-containing group, and a thioorganic group. Is a group corresponding to at least one selected from sulfur atom-containing groups other than. 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 the organic compound A.

Like the organic compound A, at least one of B ^{1 to} B ⁵ of the organic compound B is preferably an oxygen atom-containing group. Particularly, 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 the 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 the organic compound A, the organic compound B preferably maintains a crystalline state in the coating film forming composition and the coating film. The organic compound B may be crushed by a known dry or wet crushing device so as to have a predetermined average particle size and then added to the coating film forming composition. The preferable average particle size of the organic compound B is as described above for the organic compound A. The organic compound B is preferably blended such that the total amount of the organic compound A and the organic compound A is the above-described ratio of the organic compound A to the silicon oxide in the coating film. The organic compound B may be added so as to be less than the organic compound A on a mass basis, preferably less than 50% of the organic compound A.

The 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 preferable example of the organic compound B having two 2-phenylbenzotriazole skeletons has a form in which they are bonded to each other by a methylene group 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 the organic compound B is a benzophenone compound. The benzophenone compound has the following formula (4) as a basic skeleton. However, the hydrogen atom of the benzene ring may be substituted with a substituent. The substituent may be any of the groups listed for B ^{1 to} B ⁹ . Examples of the organic compound B which is a benzophenone compound include 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 the organic compounds A and B in the coating film, and enhances the light-shielding ability of the benzotriazole-based UV-shielding component. It is a component that suppresses deterioration of this component. When a coating film is formed to be relatively thick (for example, a thickness of more than 300 nm, or even a thickness of 500 nm or more) by a liquid phase film forming method such as a sol-gel method, the liquid component contained in the film forming solution is evaporated. Cracks may occur. The organic compound C is also a component that enables 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 its derivatives as monomers. Examples of the organic compound C include a polyether type surfactant and a polyol compound produced by reaction of an epoxy group of a polyepoxy compound. The organic compound C may be a polymer. Examples of the organic compound C also include polycaprolactone polyol, bisphenol A polyol, polyethylene glycol, and polypropylene glycol.

The organic compound C is 0 to 75%, more preferably 0.05 to 50%, particularly 0.1 to 40%, and particularly 1 to 30%, depending on the case, expressed as% by mass relative to the silicon oxide in the film. Is preferably 10% or less, and if necessary 7% or less, is preferably added to the film.

The type of the 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 an organic substance in the coating film, and the M group hydrolyzes to react with an inorganic substance in the film. Through this reaction, the silane coupling agent contributes to the improvement of the dispersibility of the organic compound A or the ultraviolet shielding components of the organic compounds A and B in the film, and enables the formation of a thick film while suppressing the occurrence of cracks. Produces the effect of The silane coupling agent is such that the silicon oxide supplied from the silane coupling agent is 0 to 30%, preferably 0.1 to 20%, more preferably, expressed as mol% with respect to the total silicon oxide in the coating film. Is preferably added to the film so as to be 1 to 10%.

The silicon oxide supplied from the silane coupling agent is calculated according to the number of oxygen atoms bonded to silicon atoms of 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 described above is represented as SiO _1.5 because the silicon atom is bonded to three oxygen atoms.

Other components that the coating film may include include indium tin oxide (ITO) fine particles. ITO fine particles are a preferable component for absorbing near infrared rays. The ITO fine particles may be dispersed in the film as fine particles having an average particle diameter of 200 nm or less, preferably 5 to 150 nm. Like the fine particles of the organic compound A, if the particle size is too large, the transparency of the film is lowered, and if it is too small, the effect due to the addition cannot be sufficiently obtained. A dispersion liquid of ITO fine particles may be prepared in advance and added to the film forming solution. The coating film may contain an inorganic component other than silicon oxide and ITO fine particles. Examples of such an inorganic component include components derived from the acid catalyst used in the sol-gel method.

The coating film 2 contains silicon oxide as a main component. The coating film 2 preferably has a form in which fine particles of the organic compound A and other components are dispersed in a network composed of Si—O bonds, containing silicon oxide as a main component. A film having such a form is particularly suitable for outdoor use such as a window glass.

The preferred method for forming the coating film by the sol-gel method will be described below. The organic solvent used in the sol-gel method is preferably a solvent having high compatibility with silicon alkoxide and water, and a lower alcohol having 1 to 3 carbon atoms is 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 a silicon oxide precursor. The concentration of silicon alkoxide in the formation solution by the sol-gel method is 3 to 15% by mass, and particularly preferably 3 to 13% by mass, which is represented by the silicon oxide concentration when silicon alkoxide is converted into silicon oxide. If this concentration is too high, cracks may occur in the film.

Water is preferably 4 times or more, specifically 4 to 40 times, and more preferably 4 to 35 times, in terms of molar ratio, with respect to silicon alkoxide. As the hydrolysis catalyst, it is preferable to use an acid catalyst, particularly a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid or paratoluenesulfonic acid. An inorganic acid is preferable as the acid catalyst because an organic substance derived from the acid catalyst may lower the film hardness. 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, which is represented by the molar mass concentration of protons on the assumption that the protons are completely dissociated from the acid.

When water is added to the above-mentioned level in excess and an acid catalyst is added so that the concentration becomes the above-mentioned level, a relatively thick film can be easily formed by a sol-gel method in a temperature range where decomposition of organic substances can be prevented.

A solution to which the sol-gel method including the above-mentioned components can be applied is mixed with a dispersion liquid in which fine particles such as an organic compound A are dispersed, and if necessary, an organic compound C is added to form a coating film. A solution can be prepared. 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 dispersion liquid of fine particles. The film-forming solution may be prepared so as to contain, together with fine particles such as the organic compound A, components necessary for forming a film by a method other than the sol-gel method, such as polysilazane.

In the film forming solution coating step, the relative humidity of the atmosphere is preferably maintained at less than 40%, and more preferably 30% or less. Keeping the relative humidity low prevents the membrane from absorbing too much moisture from the atmosphere. When a large amount of water is absorbed from the atmosphere, the water remaining in the matrix of the film may reduce the strength of the film.

The film forming solution drying step is preferably performed so as to include an air drying step under a coating environment and a heating and drying step accompanied by heating. The air-drying step may be carried out by exposing the coating film of the forming solution to an atmosphere in which the relative humidity is kept at less than 40%, further 30% or less. In the heating and drying step, the condensation polymerization reaction of the silanol groups produced by hydrolysis proceeds, and the removal of the liquid component remaining in the film, especially the removal of water, proceeds, and the silicon oxide matrix (Si-O bond network) is removed. ) Develops. In the heating and drying step, the coating film may be exposed to an atmosphere of 300°C or lower, for example, 100 to 200°C. In the heating and drying step, it is particularly preferable to expose 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. to heat it. The heating temperature in the heating and drying step is preferably not higher than the melting point of the organic compounds A and B added as fine particles, particularly the organic compound A added as fine particles.

The heating temperature for heating the film in the heating and drying step is preferably selected from the range lower than the melting point of the organic compound A added as fine particles. When the organic compound B is added as fine particles, the heating temperature is preferably selected from a range lower than the melting points of the organic compound A and the organic compound B. The melting point of the organic compound A and the melting point of the 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 described above, namely, a) a step of preparing a film forming solution of a coating film containing fine particles of the organic compound A, b) a step of applying the film forming solution onto a glass plate, and c) drying of the film forming solution. By sequentially performing the steps, the glass plate of the present embodiment can be obtained by the liquid phase film forming method. This manufacturing method provides a film-forming solution for a coating film, which contains a silicon-containing compound such as silicon alkoxide as a solute, and is an organic compound A which is solid at room temperature and has an average molecular weight of 5000 or less as fine particles having an average particle size of 150 nm or less. A glass plate having a coating film, which comprises a step of preparing, a step of applying the film forming solution on a glass plate, and a step of drying the film forming solution on the glass plate to form a coating film. It is a manufacturing method. This manufacturing method constitutes another aspect of the present invention.

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

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 "%" showing the content of each component contained in the glass plate are% by 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 the total iron oxide in terms of Fe ₂ O _3. Further, each composition example may contain a trace component that is not shown.

(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, preferably 50% or less at a wavelength of 380 nm, and a light transmittance of 75% or more at a wavelength of 550 nm may be used. Some composition examples of such a glass plate 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 absorption 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} %
CeO ₂ : 0 to 2%
TiO ₂ : 0-0.5%

It is also possible to use a high transmittance glass plate having 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 a glass plate include a glass plate having a light transmittance of 20 to 60% at a wavelength of 550 nm, which is manufactured for a window glass of a vehicle. Since it is difficult to sufficiently shield the ultraviolet region of the long wavelength region only with the components constituting the glass plate, the application of the coating film 2 described above is useful even for a glass plate having a low visible light transmittance. Is.

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

In the glass plate of the present embodiment, transmitted light from a CIE standard C light source may have an a ^{* of} -15 or more and 0 or less and a b ^{* of} 12 or less when displayed 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, 5-10. Further, the glass plate of the present embodiment may have a yellowness YI of 14 or less, which is defined in Japanese Industrial Standard (JIS) K7373:2006 of transmitted light with respect to the CIE standard C light source. The yellowness YI may be 10 or less, further 8 or less. Further, the glass plate of the present embodiment may have a dominant wavelength of transmitted light for a CIE standard C light source of 560 nm or less. The dominant wavelength may be 555 nm or less, for example in the range of 550 to 555 nm. The glass plate of this embodiment may have a blue light cut rate of 41% or less, preferably 37% or less, and 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 of the ratio of the effective radiant intensity reduced by passing through the glass plate to the effective radiant intensity related to retinal damage due to blue light of sunlight (hereinafter, the effective radiant intensity of sunlight). Is defined as a value obtained by the following method, and specifically, it can be obtained by the following method. The wavelength of 380 to 550 nm is summed with respect to the weighting function of the weighting function regarding the blue light interference function described in Appendix A of JIS T7330:2000, and the effective radiant intensity of sunlight is obtained. 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 summed up to obtain the effective radiant intensity of the light transmitted through the glass plate (hereinafter, the effective radiant intensity of the transmitted light). The ratio of the effective radiant intensity of transmitted light to the effective radiant intensity of sunlight can be obtained, and the value can be subtracted from 1 to be converted into a percentage.

The glass plate of the present embodiment has a difference obtained by subtracting the _UV transmittance T _UV 400 before the UV irradiation from the _UV transmittance T _UV 400 after the UV irradiation having the wavelength of 295 to 450 nm and the illuminance of 76 mW/cm ² for 100 hours. ΔT _UV 400 can 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 irradiation of the above-mentioned ultraviolet rays from the visible light transmittance YA after irradiation of ultraviolet rays having 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, and further −0.2% or more and 0.5% or less.

The glass sheet of the present embodiment is suitable for use as a window glass for buildings and transportation equipment, specifically, transportation equipment such as automobiles, railway vehicles, ships, and aircraft, and is particularly suitable for use as a window glass for automobiles. There is. However, when it is used as a window glass that can be raised or lowered or opened/closed as represented by a door glass of an automobile, the surface of the peripheral edge of the glass plate repeatedly contacts an end holding member called a run channel. It will be. For this reason, the film may peel off during a long period of use, and the appearance of the window glass may be impaired. Therefore, in such an application, as shown in FIGS. 2 and 3, the coating film 11 may not be formed on the glass plates forming the window glasses 10 and 20 in the peripheral region 12 that abuts against the end holding member. preferable. Further, when it is difficult to stably hold the door glass using the elevating member due to the presence of the coating film 11, as shown in FIG. 2, also in the bottom regions 13 and 14 for connecting to the elevating member, It is preferable not to form the coating film 11. However, depending on the method of connecting the elevating member and the door glass or the type of the film, the film formation in the bottom regions 13 and 14 may not hinder the connection. Generally, a film having a contact angle with water of 50 degrees or less has a small effect on connection. In such a case, it is not necessary to exclude the coating film 11 from the bottom regions 13 and 14 (FIG. 3). As described above, the coating film 11 may not be formed on a part of the surface of the glass plate, particularly on the peripheral edge part that comes into contact with other members. However, also in this case, the coating film 11 should be formed on the entire surface of the main region of the glass plate that separates the room from the room when the window is closed in order to shield ultraviolet rays.

When a region where no film is formed is secured 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 region where the film is formed to the peripheral region where the film is not formed. .. If formed in this way, the boundary between the region where the film is formed and the region where the film is not formed is inconspicuous, and deterioration of the appearance can be prevented. An example of a window glass (door glass) having a region where the film thickness is gradually reduced is shown in FIG. In the form shown in FIG. 4, the window glasses 10 and 20 used as the door glass are closed, and the main regions of the window glasses 10 and 20 (the outside including the ultraviolet rays from the outside on the left side in the drawing to the inside on the right side in the drawing). A coating film 11 is formed on the inner surface of the glass plate 15 that constitutes a region through which light is transmitted so that the coating film 11 has a predetermined film thickness that is 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 with each other. The coating film 11 is formed so that the film thickness thereof gradually decreases from the peripheral edge C toward the peripheral edge B. FIG. 4 shows a configuration in which the tip of the run channel 30 is aligned with the peripheral edge C (form in which the coating film is formed with a constant film thickness over the entire surface of the glass plate which is exposed without being covered by the run channel). ) Is shown, it is not necessary that the tip of the run channel 30 and the peripheral edge C coincide with each other as long as the desired ultraviolet ray shielding ability is obtained in the main regions of the window glasses 10 and 20. Further, as shown in the figure, the film thickness may be gradually reduced to zero at the position retracted from the peripheral edge B toward the peripheral edge C side, but the peripheral edge B and the position where the film thickness becomes zero may coincide. Absent. Although FIGS. 2 to 4 show the door glass in which the film is not formed on the peripheral portion of the glass plate, it goes without saying that the glass plate according to the present invention is not limited to such a form. Even when it is used as a door glass, a coating film may be formed on the entire surface of the glass plate, or a film is formed in the peripheral region 12 contacting the end holding member, while the coating film is formed in the bottom regions 13 and 14. It does not matter if the film is not formed.

Hereinafter, the present invention will be described in more detail with reference to Examples. First, an ultraviolet shielding component used as the 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 0.1 g, 174.2 mmol) and potassium iodide (0.9 g, 5.5 mmol) were reacted in DMF (N,N-dimethylformamide, meaning the same hereinafter) 62.5 g at 125° C. for 12 hours. did. After completion of the reaction, 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, 1390 cm ^-1: triazole ring stretching vibration 665 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 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), 7.38 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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) is an attribution of the absorption wave number and its absorption in the Fourier transform infrared spectroscopy spectrum by the sample prepared by the KBr tablet method.
Further, ¹ H-NMR (CDCl ₃ 400 MHz) and ¹³ C-NMR (CDCl ₃ 400 MHz) show 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 assignment are shown for a sample prepared by using deuterated trichloroform as a solvent under the conditions. In the parentheses following the NMR chemical shift δ, some of the atoms are underlined to indicate that the nucleus of the atom is the origin of the NMR signal. Further, s, d, t, q and m in parentheses following the chemical shift δ in ¹ H-NMR indicate that the NMR signals are singlet, doublet, triplet, quartet and multiplet, s, d, t, q, nH (n is a natural number) followed by m, the integral value of the signal corresponding to n ^{1 H, "insg. X arom} . C H" (X is a natural number), having aromatic character It is shown that the integrated value of the NMR signal based on ¹ H bound to carbon corresponds to X ¹ H. In addition, C _arom 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 completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain compound 2.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1444, 1390 cm ^-1: triazole ring stretching vibration 668cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): 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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 31.3 (-S-Ph-C( C H 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 completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 3.

FT-IR (KBr): 3000 cm ^-1 :OH stretching vibration 1447, 1385 cm ^-1 :triazole ring stretching vibration 665 cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.47 (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 ₃ 400 MHz): 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 completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain compound 4.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.48 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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) are meant. The same applies hereinafter) in 50 g at 60° C. for 4 hours. After completion of the reaction, toluene and water were added, and then hydrochloric acid was added for acid treatment, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was column-refined to obtain a solid intermediate 5-1. The obtained Intermediate 5-1 was reacted in 50 g of sulfolane at 240° C. for 4 hours. After completion of the reaction, toluene and water were added to wash with water, and the residue was distilled off 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, cooled, hydrochloric acid was added and the mixture was stirred, washed with water, recrystallized, and purified by column to give 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 D2.5 (62.5 g) at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 5.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 0.72 (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 ₃ 400 MHz): 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( C H ₃ ) ₂ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and 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 ₃ 400 MHz): δ1.30 (d, 6H, (C H ₃ ) ₂ CH-Ph-S-), 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 ), 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 ₃ 400 MHz): 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( C H 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 (25.0 g, 121.2 mmol), dimethylcarbamoyl chloride (22.5 g, 181.7 mmol), sodium hydride (5.8 g, 133.3 mmol) ) Was reacted in 50 g of THF at 60° C. for 4 hours. After completion of the reaction, toluene and water were added, and then hydrochloric acid was added for acid treatment, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was column-purified to obtain a solid intermediate 7-1. The obtained Intermediate 7-1 was reacted in 50 g of sulfolane at 240° C. for 4 hours. After completion of the reaction, toluene and water were added to wash with water, and the mixture was distilled off 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, cooled, hydrochloric acid was added and the mixture was stirred, washed with water, recrystallized, and purified by column to give 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 125 g of DMF 60 g for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain compound 7.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 0.76 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 DMF62.5 g at 125° C. for 12 hours. After the completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and 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 665 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): 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 ₃ 400 MHz): 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 (25.0 g, 79.2 mmol), p-toluenethiol (19.7 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol), potassium iodide (0.92 g, 5.54 mmol), and DMF62.5 g were reacted at 125° C. for 12 hours. After the completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and 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 667 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 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 ), 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 ₃ 400 MHz): 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( C H 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), sodium hydride (5.1 g, 117.4 mmol) in THF 50 g. The reaction was carried out at 60°C for 4 hours. After completion of the reaction, toluene and water were added, and then hydrochloric acid was added for acid treatment, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was subjected to column purification 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 completion of the reaction, toluene and water were added to wash with water, and the solvent was distilled off under reduced pressure to obtain a liquid intermediate 10-2. The obtained Intermediate 10-2 and potassium hydroxide are stirred in ethanol at 60° C. for 3 hours, cooled, hydrochloric acid is added and the mixture is stirred, washed with water, recrystallized, and purified by column to give 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 DMF 60 g at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 10.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 0.60 (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 ₃ 400 MHz): 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( C H ₃ ) ₂ ), 28.8 (-S-Ph-C( C H 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 (25.0 g, 79.2 mmol), 4-hydroxybenzenethiol (20.0 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 completion of the reaction, the pH was adjusted, and then filtration, MeOH washing, and water washing were performed, and recrystallization and column purification were performed to obtain Compound 11.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1445, 1390 cm ^-1: triazole ring stretching vibration 667 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.48 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 (25.0 g, 79.2 mmol), 2-naphthalenethiol (25.4 g, 158.3 mmol), potassium carbonate (24.1 g, 174.2 mmol) and potassium iodide (0.92 g, 5.54 mmol) were reacted in 62.5 g of DMF at 125° C. for 12 hours. After the completion of the reaction, the pH was adjusted, and then filtration, MeOH washing, and water washing were performed, and recrystallization and column purification were performed to obtain compound 12.

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1444, 1389cm ^-1: triazole ring stretching vibration 667 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.48 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 DMF62.5 g at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and 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 667 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.48 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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), and THF 100 g. The reaction was carried out at 60° C. for 4 hours. After completion of the reaction, toluene and water were added, and then hydrochloric acid was added for acid treatment, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was subjected to column purification 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 completion of the reaction, toluene and water were added to wash with water, and the residue was distilled off under reduced pressure to obtain solid intermediate 14-2. The obtained Intermediate 14-2 and potassium hydroxide are stirred in ethanol at 60° C. for 3 hours, cooled, hydrochloric acid is added and the mixture is stirred, washed with water, recrystallized, and purified by column. 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 DMF 60 g at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 14.
FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration

¹ H-NMR (CDCl ₃ 400 MHz): δ 1.49 (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 (CH _{3) 3)}
¹³ C-NMR (CDCl ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H ₃ ) ₃ ), 30.6 (-S-Ph-C( C H 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), sodium hydride (10.3 g, 236.1 mmol) in 100 g of THF at 60° C. Reacted for 4 hours. After completion of the reaction, toluene and water were added, and then hydrochloric acid was added for acid treatment, and the organic layer washed with water was distilled off under reduced pressure. The obtained liquid was subjected to column purification 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 completion of the reaction, toluene and water were added to wash with water, and the residue was distilled off under reduced pressure to obtain solid intermediate 15-2. The obtained Intermediate 15-2 and potassium hydroxide are stirred in ethanol at 60° C. for 3 hours, cooled, hydrochloric acid is added, and the mixture is stirred, washed with water, recrystallized, and purified by column to obtain biphenyl-4. 4'-dithiol was obtained.

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

FT-IR (KBr): 3000cm -1: O-H stretching vibration 1450, 1380 cm ^-1: triazole ring stretching vibration 660 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.48 (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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 (32.3 g, 0.102 mol), cyclohexanethiol (23.8 g, 0.205 mol), potassium carbonate (31 0.1 g, 0.225 mol) and potassium iodide (1.2 g, 0.007 mol) were reacted at 125° C. for 12 hours in 100 g of DMF. After completion of the reaction, the pH was adjusted, and then filtration, MeOH washing, and water washing were performed, and recrystallization and column purification were performed to obtain Compound 16.

FT-IR (KBr): 2930cm ^-1 :OH stretching vibration 1450, 1391cm ^-1 :triazole ring stretching vibration 667cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): 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 C H 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 ₃ 400 MHz): δ 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 25.7 (CH ₂ ( C H ₂ ) ₂ (CH ₂ ) ₂ CH-S), 26.0 ( C H ₂ (CH ₂ ) ₂ (CH ₂ ) ₂ CH-S), 29.5 (-Ph-OH-CH ₃ -C( C H 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 HS), 117.2, 117.5, 119.3 , 128.3, 128.8 ( C _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 the mixture was stirred for 30 minutes, cooled to room temperature, and 500 mL of ice-cooled ion-exchanged water was slowly added. Then, the aqueous layer was removed, the organic layer was washed with water, distilled off under reduced pressure, and then recrystallized to obtain Intermediate 17-1. 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 completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 17.

FT-IR(KBr): 2950cm ^-1 :OH stretching vibration 1459, 1388cm ^-1 :Triazole ring stretching vibration 670cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 2.38 (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 )
¹³ C-NMR (CDCl ₃ 400 MHz): 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) and cooled to 5 to 10°C, and a 50% sodium nitrite aqueous solution was added. (119.7 g, 0.869 mol) was added dropwise at 5 to 10°C over 2 hours. After dropping, the mixture was stirred for 1 hour, diethyl ether was added, the crystals were filtered, and then washed to obtain Intermediate 18-1.

4-tert-octylphenol (130.0 g, 0.630 mol), sodium hydroxide (26.5 g, 0.663 mol), sodium carbonate (35.4 g, 0.334 mol) were added to 850 mL of methanol and 450 mL of ion-exchanged water. Intermediate mixture 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 dropping, 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 the mixture was stirred at 85°C for 2 hours. After completion of the reaction, filtration and washing were carried out, and recrystallization was carried out to obtain Intermediate 18-3.

Intermediate 18-3 (5.0 g, 0.014 mol), 4-tert-butylbenzenethiol (3.5 g, 0.021 mol), potassium carbonate (4.3 g, 0.031 mol) and potassium iodide (0. 2 g, 0.001 mol) was reacted in DMF 50 g at 125° C. for 12 hours. After completion of the reaction, pH was adjusted, filtration, MeOH washing, and water washing were performed, and recrystallization and column purification were performed 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 150° C. for 17 hours. Reacted. After completion of the reaction, column purification was performed to obtain Intermediate 18-5.

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

FT-IR (KBr): 2953cm ^-1 :OH stretching vibration 1460, 1389cm ^-1 :triazole ring stretching vibration 670cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 0.68 (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 ₃ 400 MHz): δ30.9 (-Ph-OH- C H ₂ -OH-Ph-), 31.3 (-S-Ph-C( C H ₃ ) ₃ ), 31.7 (-Ph- _{OH-C (C H 3)} 2 CH 2 C (CH 3) 3), 31.8 (-Ph-OH-C (CH 3) 2 CH 2 C (C H 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 0.1 g, 0.348 mol) and potassium iodide (1.8 g, 0.011 mol) were reacted in 125 g of DMF at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, and recrystallization to obtain Compound 19.

FT-IR (KBr): 2956cm ^-1 :OH stretching vibration 1445, 1392cm ^-1 :triazole ring stretching vibration 662cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 0.89 (t, 3H, C H ₃ (CH ₂ ) ₇ -S), 1.33 (m, 8H, CH ₃ (C H ₂ ) ₄ (CH ₂ ) ₃ -S ), 1.49 (m, 11H, -Ph-OH-CH ₃ -C(C H ₃ ) ₃ , CH ₃ (CH ₂ ) ₄ C H 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 ₃ 400 MHz): δ 14.0 ( C H ₃ (CH ₂ ) ₇ -S), 20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 22.6 (CH ₃ C H ₂ (CH ₂ ) ₅ CH ₂ -S), 28.7 (CH ₃ CH ₂ ( C H ₂ ) ₄ CH ₂ CH ₂ -S), 29.5 (-Ph-OH-CH ₃ -C( C H 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 .3 g, 139.4 mmol) and potassium iodide (0.74 g, 4.5 mmol) were reacted in 50.0 g of DMF at 125° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, and recrystallization to obtain Compound 20.

FT-IR (KBr): 2960cm ^-1 :OH stretching vibration 1441, 1392cm ^-1 :triazole ring stretching vibration 664cm ^-1 :CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 1.49 (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 to 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 ₃ 400 MHz): δ20.9 (-Ph-OH- C H ₃ -C(CH ₃ ) ₃ ), 29.5 (-Ph-OH-CH ₃ -C( C H 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 0.75 g, 63.3 mmol) and potassium iodide (0.37 g, 2.2 mmol) were reacted in 50 g of DMF at 130° C. for 12 hours. After completion of the reaction, the pH was adjusted, followed by filtration, washing with MeOH and washing with water, recrystallization and column purification to obtain Compound 21.

FT-IR (KBr): 3009cm ^-1 :OH stretching vibration 1431, 1391cm ^-1 :Triazole ring stretching vibration 656cm ^-1 :CS stretching vibration
1H-NMR (CDCl3 400MHz): δ 1.49 (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 C H ₂ -S-), 7.16 (s, 2H), 7.37 (d, 2H), 7.70 (s, 2H), 7.81 (d, 2H), 8.05 (s, 2H) (insg.10arom. CH), 11.60 (s, 2H, -Ph-O H -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 the 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) in a toluene solution in consideration of the solubility of the compound at the following mass ratios, and then coated on a soda glass plate at 80°C. It was dried for 10 minutes to obtain an evaluation sample.

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

About the obtained evaluation sample, an ultraviolet-visible transmission spectrum was measured with an ultraviolet-visible spectrophotometer (Hitachi Ltd. spectrophotometer U-3310), and the initial (before irradiation) ultraviolet transmittance (% T _{(1 ) 400} :%), and then, using an ultraviolet irradiation device (Xenon weather meter X25FL-Z manufactured by Suga Test Instruments Co., Ltd.), irradiate ultraviolet rays under the conditions of wavelength 300 to 400 nm, illuminance 42 W/m ² , and black panel temperature 63° C. After the irradiation time of 140 hours, the ultraviolet-visible transmission spectrum was measured, the transmittance (%T ₍₂₎₄₀₀ :%) at a wavelength of 400 nm was read, and the transmittance difference Δ% _T400 (%) was calculated by the following formula. (Table 1A, 1B).

Transmittance difference (Δ% T ₄₀₀ )=% T ₍₂₎₄₀₀ −% T ₍₁₎₄₀₀ (%)

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

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

In formula (2-1), the compound 2, 5, 6, 7, 9 having a hydrocarbon group (alkyl group) as R ^{1a at the} para position with respect to the -S- bond of the thioalkoxy group (melting point) 140 to 155° C.) has a higher melting point than Compound 1 (melting point 136° C.) in which all R ^1a are hydrogen atoms and Compound 4 (melting point 115° C.) in which R ^1a is an alkoxy group, and among them, carbon number of alkyl group is 3 Compounds 2, 5, 6 and 7 (melting points 141 to 155° C.) having a carbon number of 1 to 8 are higher than those of compound 9 having a carbon number of 1 (melting point 140° C.), and further, compounds 2 and 6 having 3 to 4 carbon atoms of an alkyl group It was confirmed that the melting point 148 to 155° C.) was higher than that of the compounds 5,7,9 having 1,5,8 carbon atoms (melting points 141,146,140° C.), and the compound 2 having 4 carbon atoms tended to have a higher melting point.

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

Further, when 1=1 or 2, R ^1a is a hydrocarbon group compound 2, 3, 5 to 10 (melting point 131 to 155° C.), R ^1a is a hydrogen atom-containing compound 1 (melting point 136° C.) and R ^1a is R ^11a is a hydroxy group compound 11 (melting point 208° C.), compound 14 (melting point 196° C.), compound 15 (melting point 236° C.) and X ^1a is a naphthyl group, as compared with alkoxy group compound 4 (melting point 115° C.). Compound 12 (melting point 161° C.) and compound 18 (melting point 176° C.) have high melting points, and are particularly useful in terms of bleed-out and processability.

Next, a glass plate with a coating film was prepared and evaluated using the compound obtained above as the organic compound A. The evaluation items are as follows.
<Optical properties>
The optical characteristics were measured using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corp.). The measured characteristics are visible light transmittance YA according to JIS R3212 measured using a CIE standard A light source, ultraviolet light transmittance T _UV 380 calculated according to ISO 9050 (1990 version), and ultraviolet light transmittance calculated according to ISO 13837 (convention A). Rate T _UV 400, blue light cut rate BLcut calculated based on the above-mentioned JIS T7330 blue light obstruction function, L ^* a ^* b ^* color system according to JIS Z8729 of transmitted light measured using a C light source of CIE standard, Yellowness YI according to JIS K7373 (2006) of transmitted light measured using a CIE standard C light source, main wavelength and stimulation purity according to JIS Z8701 (1999) of transmitted light measured with a CIE standard C light source, wavelength 1500 nm Is the light transmittance T1500. Note that T _UV 380 is based on the transmittance of light rays at wavelengths of 280 to 380 nm, T _UV 400 is based on the transmittance of light rays at wavelengths of 300 to 400 nm, and the blue light cut rate is the transmittance of light rays at wavelengths of 380 to 500 nm. Is a value calculated based on the above.

<Light resistance (UV resistance)>
The light resistance (UV resistance property) is measured by using an Iwasaki Denki Co., Ltd. UV irradiation device (EYE SUPER UV TESTER SUV-W13), wavelength 295 to 450 nm, illuminance 76 mW/cm ² , black panel temperature 83° C., humidity 50% RH. The above conditions were applied, and the glass plate with a coating film was irradiated with ultraviolet rays for a predetermined time (100 hours) from the surface of the glass plate on which the film was not formed. The optical characteristics (YA, T _UV 400) before and after the test were measured, and the change (ΔYA, ΔT _UV 400) was calculated.

(Example 1)
In Example 1, the compound 16 was used as the organic compound A. Specifically, a dispersion liquid containing an ultraviolet ray shielding component which is the organic compound A as a dispersoid and water as a dispersion medium (ultraviolet ray shielding component content rate 10% by weight, average particle size 100 nm) was prepared. The organic compound A was previously pulverized by mixing with zirconia beads using a paint conditioner so as to have the above average particle size. Together with this dispersion, pure water, ethyl alcohol, tetraethoxysilane (TEOS), silane coupling agent glycidoxypropyltrimethoxysilane (GPTMS; 3-glycidyloxypropyltrimethoxysilane), and polyol compound triethylene. Glycol (TEG), polyether phosphate ester polymer as a polyether compound (Solvers 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 ratio) of each component was the value shown in Table 2. Table 2 also shows the concentration of each component in the film forming solutions prepared in Examples and Comparative Examples described later.

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

The UV cut green glass used had 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 into Fe ₂ O ₃ .

The above measurement was performed on the glass plate with a coating film thus obtained. The results are shown in Table 2. Table 2 also shows the measurement results of the glass sheets with a coating film produced in Examples and Comparative Examples described later.

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

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

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

Moreover, in Examples 12 to 14, the temperature of the oven in the heating and drying step was set to 180° C. and was made higher than the melting point of the organic compound A. Therefore, in Examples 12 to 14, the 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 kind and the amount of the ultraviolet ray shielding component added were adjusted as shown in Table 2. In Comparative Example 1, only the organic compound B is added as the ultraviolet ray 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 kind and the amount of the ultraviolet ray shielding component added were adjusted as shown in Table 2. In Comparative Example 2, instead of the organic compound A, Uvinul3050 (manufactured by BASF Japan Ltd.), which is an ultraviolet shielding component having a benzophenone skeleton, was used. Uvinul 3050 was previously dissolved in ethyl alcohol and added to the film forming solution. Further, as the organic compound C, (polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd.) was used instead of Solsperse.

Not lower T _UV 400 is obtained from the Comparative Example 1, although lower T _UV 400 was obtained was higher yellowness YI from Comparative Example 2. On the other hand, in the embodiment, it is possible to lower the T _UV 400 while suppressing significant coloring of the yellow. Further, it was confirmed from the comparison between Examples 1 and 2 and Examples 12 to 13 that the light resistance of the film was improved by adding the organic compound A as fine particles. In addition, as in Compounds 2, 6, and 7 (Examples 3 to 11, 16), an organic compound A in which the thioorganic group has a thioaryl ring group to which a chain alkyl group having a branch as a substituent of a hydrogen atom is connected When these compounds were used alone, the ΔT _UV 400 of the film could be sufficiently suppressed although the shielding properties against long-wavelength ultraviolet rays and the light resistance of these compounds alone were not necessarily excellent (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 light, considering that compound alone (42J / m ²⁾ film than (760J / m ²⁾ is orders of magnitude stronger irradiation of (T _UV 400 of the glass plate is 24.6% Then, about 1/4 of the ultraviolet rays reach the film, but even considering this, the film is irradiated with stronger ultraviolet rays). Even when the temperature at the time of ultraviolet irradiation is compared, the film (83° C.) is higher than the compound alone (63° C.) (generally, the deterioration of the organic material is accelerated about 10 times at every 10° C. The conditions under which deterioration of about 4 times progresses are applied). Considering the above, it can be understood that the deterioration of the organic compound A is sufficiently suppressed, particularly when the organic compound A is held in the state of fine particles in the coating film. In particular, with respect to Compounds 2, 6 and 7 (Examples 3 to 11 and 16), ΔT _UV 400 was suppressed to an extremely low level that could not be expected from the characteristics of the compound alone.

The X-ray diffraction pattern of the glass plate with a coating film obtained from each example was observed by a RAD-RC apparatus manufactured by Rigaku Denki Co., Ltd. A sharp diffraction peak assigned 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 (51)

A glass plate for transportation equipment having a glassy coating film containing an additive imparting ultraviolet absorption ability,
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 comprises an organic compound A,
A glass plate in which the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thio organic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR when the organic group is R. The glass plate according to claim 1, wherein the organic compound A includes a unit represented by the following formula (1).

However, in the formula (1), A ^{1 to} A ⁹ are each independently 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 the thioorganic group. The glass plate according to claim 2,
A glass plate in which at least one of A ^{6 to} A ⁹ is the thioorganic group. It is a glass plate of Claim 2 or 3, Comprising:
A glass plate in which the thioorganic group is a thioalkyl group optionally having a hydrogen atom substituent or a thioaryl ring group optionally having a hydrogen atom substituent.
Here, the thioalkyl group is a group represented by -S-Alk when an alkyl group which may have a hydrogen atom substituent is represented by Alk, and the thioaryl ring group is a hydrogen atom-substituted group. It is a group represented by -S-Ary when an aryl ring group which may have a group is represented by Ary. The glass plate according to claim 4, wherein
The alkyl group which may have a substituent of the hydrogen atom contained in the thioalkyl group,
A glass plate, which is an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 6 carbon atoms having a phenyl group as a substituent of a hydrogen atom. It is a glass plate of Claim 2 or 3, Comprising:
The organic compound A contains two of the 2-phenylbenzotriazole skeletons,
The two 2-phenylbenzotriazole skeletons are connected via the thio organic group,
The glass plate in which the thio organic group is connected to each of the two 2-phenylbenzotriazole skeletons via a sulfide bond. The glass plate according to claim 4, wherein
A glass plate in which the thioorganic group is the thioaryl ring group. The glass plate according to claim 7,
The glass plate in which the thioaryl ring group has an alkyl group having 4 to 9 carbon atoms as the substituent. The glass plate according to claim 8,
A glass plate in which the thioaryl ring group has, as the substituent, a chain alkyl group containing a quaternary carbon atom and having a branch of 4 to 9 carbon atoms. The glass plate according to claim 4, wherein
A glass plate in which the aryl ring contained in the thioaryl ring group is a benzene ring and/or a naphthalene ring. The glass plate according to claim 4, wherein
A glass plate in which the alkyl group contained in the thioalkyl group is a cyclohexyl group. The glass plate according to claim 4, wherein
A glass plate in which the alkyl group contained in the thioalkyl group and the aryl ring group contained in the thioaryl ring group have a carbon number in the range of 1 to 18. The glass plate according to claim 4, wherein
The substituent is an atom or group 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, Glass plate. It is a glass plate of any one of Claims 1-3, Comprising:
The organic compound A is
A 2-phenylbenzotriazole derivative represented by any of the following formulas (2-1) to (2-3), having a thioaryl ring group optionally having a substituent of a hydrogen atom or a thiohexyl ring group, Glass plate.
^{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 -...) optionally having the above-mentioned substituent is bonded, and X ^1a is a phenyl ring or naphthyl. Represents a ring residue, and 1 R ^1a each independently represents a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydroxy group, and l represents an integer of 0 to 5 .)
^{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 is bonded, and Cy represents a cyclohexyl ring residue. In the formula, 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-), which may have the substituent, is bonded, A ^1c is the following formula:
-[ ^X1c- ( ^R1c ) _n ]-( ^A2c ) _q- [ ^X2c- ( ^R2c ) _p ]-
(In the formula, X ^1c and X ^2c each independently represent a residue of a phenyl ring or a naphthyl ring, and n R ^1c and p R ^2c are each independently a hydrocarbon group having 1 to 18 carbon atoms or a carbon atom. The number 1 to 18 represents an alkoxy group or a hydroxy group, n and p represent integers of 0 to 4, A ^2c represents an aromatic group, an unsaturated group, a nitrogen atom-containing group, a sulfur atom-containing group, an oxygen atom. A hydrogen atom is replaced by at least one of the both ends with a monovalent or divalent group selected from a containing group, a phosphorus atom-containing group, an alicyclic group, and a halogen atom, or a carbon- A divalent hydrocarbon group having 1 to 20 carbon atoms in which a carbon bond may be interrupted, a divalent aromatic group, or a sulfide bond, and q represents an integer of 0 or 1.). Is a group or represents a phenyl ring or naphthyl ring residue. ) The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
A glass plate in which X ^1a , X ^1c and X ^2c represent residues of a phenyl ring, and l, n and p represent 0. The glass plate according to claim 14,
A glass plate in which 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. The glass plate according to claim 16,
A glass plate in which 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 glass plate according to claim 14,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, A glass plate in which l, n, and p represent an integer of 1 to 5. The glass plate according to claim 18,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue 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 is a glass plate showing an integer of 1 to 3. The glass plate according to claim 18,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, A glass plate in which l, n and p represent 1. The glass plate according to claim 20, wherein
The organic compound A is represented by the formula (2-1),
R ^1a is a glass plate showing a linear or branched chain alkyl group having 4 to 9 carbon atoms. The glass plate according to claim 18,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c each independently represent a linear or branched chain alkyl group having 1 to 18 carbon atoms, A glass plate in which l, n and p represent 2. The glass plate according to claim 18,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c each independently represent a straight chain having 1 to 18 carbon atoms containing a tertiary carbon and/or a quaternary carbon. Alternatively, a glass plate showing a branched chain alkyl group, and l, n and p are integers of 1 to 5. The glass plate according to claim 23,
The organic compound A is represented by the formula (2-1),
X ^1a represents a residue of a phenyl ring, R ^1a represents a branched chain alkyl group having a carbon number of 4 to 9 including a quaternary carbon, and l, n and p represent an integer of 1 to 5, Glass plate. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
X ^1a , X ^1c and X ^{2c each} represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c are each independently an alkoxy containing a linear or branched chain alkyl group having 1 to 18 carbon atoms. A glass plate showing a base. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
A glass plate in which X ^1a , X ^1c and X ^2c represent a residue of a phenyl ring, and R ^1a , R ^1c and R ^2c represent a hydroxy group. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1) or the formula (2-3),
A glass plate in which X ^1a , X ^1c and X ^2c represent a residue of a naphthyl ring. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-2),
m is 0, a glass plate. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-2),
R ^<1b > shows a C1-C18 hydrocarbon group, m shows the integer of 1-5, a glass plate. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-3),
A glass plate in which X ^1c and X ^2c represent a residue of a phenyl group, A ^2c represents a sulfide bond, and q represents 1. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-3),
A glass plate in which X ^1c and X ^2c each represent a residue of a phenyl group, A ^2c represents a hydrocarbon group having 1 to 8 carbon atoms, and q represents 1. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-3),
A glass plate in which X ^1c and X ^2c represent a residue of a phenyl group and q represents 0. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1),
A glass plate in which X ^1a represents a residue of a phenyl group, R ^1a represents a linear or branched chain alkyl group having 1 to 18 carbon atoms, and 1 represents an integer of 0 to 5. The glass plate according to claim 33,
The organic compound A is represented by the formula (2-1),
X ^1a is a glass plate connected to a phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton. The glass plate according to claim 33,
R ^1a is a glass plate having a linear or branched chain alkyl group having 4 to 9 carbon atoms, and 1 is 1 or 2. The glass plate according to claim 35,
R ^1a represents a linear branched alkyl group having 4-9 carbon atoms, at least one of R ^1a is a chain alkyl group containing quaternary carbon, glass. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1),
X ^1a is connected to the phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton, and R ^1a is an alkoxy group containing a linear or branched chain alkyl group having 1 to 18 carbon atoms. , Or a hydroxy group, and 1 represents 1 or 2, a glass plate. The glass plate according to claim 14,
The organic compound A is represented by the formula (2-1),
A glass plate in which a hydroxy group and a methyl group are each connected to a phenyl group connected to the benzotriazole skeleton of the 2-phenylbenzotriazole skeleton. The glass plate according to claim 38,
The glass plate in which 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 glass plate according to claim 38,
A glass plate in which a hydroxy group, a 1,1-dimethylethyl group and a methyl group are connected to the phenyl group of the 2-phenylbenzotriazole skeleton, respectively. The glass plate according to claim 40,
A glass plate in which the phenyl group of the 2-phenylbenzotriazole skeleton has a hydroxy group at the 2-position, a 1,1-dimethylethyl group at the 3-position, and a methyl group at the 5-position. The coating film further contains an organic compound B,
42. The glass plate according to claim 1, wherein the organic compound B has a molecular structure including a 2-phenylbenzotriazole skeleton and a thioorganic group is not connected to the 2-phenylbenzotriazole skeleton. .. The glass plate according to claim 42, wherein the organic compound B has a form of fine particles having an average particle diameter of 150 nm or less. 44. The glass plate according to any one of claims 1 to 43, wherein the organic compound A has a form of fine particles having an average particle size of 150 nm or less. ISO13837 (convention A) is a T _UV 400 is 2% or less calculated according to the visible light transmittance is measured using CIE standard illuminant A YA is 70% or more, any one of claims 1 to 44 The glass plate described in. 46. The transmitted light from a CIE standard C light source has an a ^{* of} -15 or more and 0 or less and a b ^{* of} 12 or less displayed by an L ^* a ^* b ^* color system, and The glass plate according to item 1. The glass plate according to any one of claims 1 to 46, which has a yellowness YI defined by JIS K7373:2006 of transmitted light from a C light source of CIE standard of 14 or less. The difference ΔT _UV 400 obtained by subtracting the _UV transmittance T _UV 400 before the UV irradiation from the _UV transmittance T _UV 400 after the UV irradiation at the wavelength of 295 to 450 nm and the illuminance of 76 mW/cm ² for 100 hours is 2% or less. The glass plate according to any one of claims 1 to 47, which is A composition for forming a coating film for a glass plate for transportation equipment with a glassy coating film, which contains an additive imparting ultraviolet absorbing ability,
Containing a silicon oxide precursor and an organic compound A which is an additive imparting ultraviolet absorbing ability,
The organic compound A has a form of fine particles,
The composition for forming a coating film, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thio organic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR when the organic group is R. The coating film forming composition according to claim 49, wherein the average particle size of the fine particles is 150 nm or less. A fine particle dispersion composition for use in a glass plate for transportation equipment having a glassy coating film, which contains an additive imparting ultraviolet absorbing ability,
Including an organic compound A that is an additive that imparts ultraviolet absorption capacity,
The organic compound A has a form of fine particles having an average particle size of 150 nm or less,
The fine particle dispersion composition, wherein the organic compound A has a molecular structure including a 2-phenylbenzotriazole skeleton and at least one thio organic group connected to the 2-phenylbenzotriazole skeleton.
However, the thioorganic group is a group represented by -SR when the organic group is R.

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