KR102265628B1 - Composition for self-cleaning having stain resistance by visible light irradiation and water repellency - Google Patents

Abstract

The present invention relates to a self-cleaning composition having stain resistance and water repellency by irradiation with visible light, which primarily prevents contamination by water-repellent effect on gaseous and liquid contaminants, and the remaining contaminants are secondary through photolysis contamination can be prevented.
In addition, contamination can be prevented through the super water-repellent effect on the surface of gaseous and liquid pollutants, and the effect of decomposing pollutants, removing bacteria and removing viruses by irradiation with visible light is excellent.
The present invention can provide a fabric that can exhibit excellent stain resistance and water repellency, and can maintain excellent stain resistance and water repellency even during repeated use, by including the composition on one or both surfaces of paper, film and fabric.

Description

Composition for self-cleaning having stain resistance by visible light irradiation and water repellency

The present invention relates to a composition for self-cleaning having stain resistance and water repellency by irradiation with visible light, and more specifically, the composition has excellent self-cleaning effect and excellent water repellency by irradiation with visible light.

Superhydrophobicity refers to the physical properties of a surface on which the surface of an object is extremely difficult to wet. The superhydrophobic surface was first discovered on the surface of a lotus leaf in nature, and the structure and self-cleaning effect of the surface of the lotus leaf were investigated. has been reported

The surface of the lotus leaf has a contact angle of 160.40° with water, and micro-scale bumps and nanometer-scale columns exist on the surface of the lotus leaf, and at the same time, chemicals with low surface energy similar to wax are distributed on the surface. It has been reported that superhydrophobicity is maintained, and due to this, particles such as dust are absorbed by water droplets and self-cleaning is possible.

Recently, as various kinds of organic compounds such as pollution in daily life and industrial pesticides and solvents have been synthesized and widely used in large amounts, there are many cases where the environment exceeds the decomposition capacity that the environment has originally passed. There are concerns about health and hygiene problems due to contamination and bacterial propagation.

Therefore, extensive research on the treatment of these organic compounds has been conducted from various angles, and among them, a lot of interest has been focused on the photolysis reaction treatment method that decomposes organic compounds using ultraviolet rays, but various solutions are suggested. , and face many problems in its application to real life.

Harmful compounds that impair a comfortable indoor environment include nitrogen dioxide, carbon monoxide, carbon dioxide, formaldehyde, volatile organic compounds (VOC), and other harmful gases. It is widely applied because of its advantages.

_{TiO 2} widely used as a photocatalyst absorbs UV to generate electrons and holes, and the generated electrons and holes generate OH radicals through oxidation/reduction reactions. It is known to decompose organic matter by reacting with organic matter of

Such a photocatalyst can be effectively used in various industrial fields, such as water purification, synthesis of hydrogen by decomposition of water, wastewater treatment, and deodorization of various spaces such as refrigerators and vehicles, in addition to the decomposition of organic compounds described above.

However, the conventional photocatalyst can exhibit a photolysis effect by absorption of UV, so there is a problem in that it cannot be easily used in real life.

In addition, as it simultaneously exhibits a water repellent effect as well as a pollutant decomposition effect through visible light sensitivity that can be easily decomposed under real living conditions, it primarily prevents contamination by a water repellent effect on liquid contaminants, and furthermore It is necessary to develop a composition that can prevent secondary contamination through photolysis.

KR 10-2010-0079749 A1

It is an object of the present invention to provide a self-cleaning composition having stain resistance and water repellency by irradiation with visible light.

Another object of the present invention is to prevent contamination of gaseous and liquid contaminants through a water repellent effect, and to prevent secondary contamination of the remaining contaminants through photolysis. It is to provide a composition for self-cleaning having.

Another object of the present invention is to provide a self-cleaning composition having stain resistance and water repellency by visible light irradiation that can prevent contamination through a super water-repellent effect on the surface of liquid contaminants.

Another object of the present invention is to provide a self-cleaning composition having excellent stain resistance and water repellency by visible light irradiation, which is excellent in decomposition of contaminants, removal of bacteria and removal of viruses by irradiation with visible light.

Another object of the present invention is to provide a fabric that can exhibit excellent stain resistance and water repellency, and can maintain excellent stain resistance and water repellency even when repeatedly used, by including the composition on one or both sides of paper, film and fabric will be.

In order to achieve the above object, a self-cleaning composition having stain resistance and water repellency by visible light irradiation according to an embodiment of the present invention is titanium dioxide (TiO ₂ ); a compound represented by the following formula (1); and a compound represented by the following Chemical Formula 2, wherein the titanium dioxide (TiO _{2 ) forms a TiO 2} layer on one or both surfaces of the substrate, and the compound represented by the Chemical Formula 1; And the compound represented by Formula 2 is each _{bonded to the TiO 2} layer, and has excellent stain resistance and water repellency:

[Formula 1]

[Formula 2]

here,

X ₁ to X ₄ may form a coordination bond with a metal selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,

If the X ₁ to X ₄ do not form a coordination bond with the metal,

X ₁ and X ₃ are the same as or different from each other and are each independently _{selected from the group consisting of N(R 14} ), C(R ₁₅ )(R ₁₆ ), O and S,

X ₂ And X _{4 Are} the same as or different from each other, each independently N or C (R ₁₇ ),

L _{1 To} L _{4 Are} the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted A C 1 to C 20 alkylene group, a substituted or unsubstituted C 3 to C 20 cycloalkylene group, a substituted or unsubstituted C 2 to C 20 alkenylene group, a substituted or unsubstituted C 3 to C 20 cycloalkenylene group , a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 heterocycloalkylene group, a substituted or unsubstituted C1 to C20 heteroalkenylene group, a substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R ₁ to R ₆ and R ₈ to R ₁₇ are the same as or different from each other, and each independently represent hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted C1-4 Alkylthio group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C20 24 alkynyl group, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted A heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or An unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero arylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 It is selected from the group consisting of an arylsilyl group and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to or bonded to adjacent groups to form a substituted or unsubstituted ring,
R ₁₈ to R ₂₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, and a substituted or unsubstituted C number It is selected from the group consisting of 2 to 24 alkynyl groups,
L ₅ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group,
When L ₁ to L ₅ and R ₁ to R ₆ and R ₈ to R ₂₀ are substituted, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, alkoxy having 1 to 10 carbon atoms group, an alkylthio group having 1 to 4 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, A substituent selected from the group consisting of an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. is substituted with, and when substituted with a plurality of substituents, they are the same as or different from each other.

delete

delete

delete

delete

delete

The fabric according to another embodiment of the present invention is characterized in that a self-cleaning and water-repellent layer is formed using the composition.

In the present invention, "hydrogen" is hydrogen, light hydrogen, deuterium or tritium.

As used herein, the “halogen group” is fluorine, chlorine, bromine or iodine.

In the present invention, “alkyl” refers to a monovalent substituent derived from a saturated hydrocarbon having 1 to 40 carbon atoms in a straight or branched chain. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl) and the like.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, "alkylthio" refers to the above-described alkyl group bonded through a sulfur linkage (-S-).

In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, and the like.

In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, and carbazolyl, and 2-furanyl, N-imidazolyl, and 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, “alkoxy” may be a straight chain, branched chain or cyclic chain. Although carbon number of alkoxy is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be, but is not limited thereto.

As used herein, "aralkyl" refers to an aryl-alkyl group where aryl and alkyl are as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Binding to the parent moiety is through an alkyl.

In the present invention, “arylamino group” refers to an amine substituted with an aryl group having 6 to 30 carbon atoms.

In the present invention, “alkylamino group” refers to an amine substituted with an alkyl group having 1 to 30 carbon atoms.

In the present invention, “aralkylamino group” refers to an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

In the present invention, “heteroarylamino group” refers to an amine group substituted with an aryl group having 6 to 30 carbon atoms and a heterocyclic group.

In the present invention, “heteroaralkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, “heterocycloalkyl” means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or Se substituted with a hetero atom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 6 to 60 carbon atoms.

In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

In the present invention, 　 "adjacent 　 groups are combined with each other to form a ring" means 　 adjacent 　 groups are bonded to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; Or it means to form a condensed ring thereof.

As used herein, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other. The substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a carboxy group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, A heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, It may be substituted with one or more substituents selected from the group consisting of an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms and a heteroarylamino group having 2 to 24 carbon atoms, and a plurality of When substituted with a substituent, they are the same as or different from each other, and the examples are not limited thereto.

The present invention relates to a self-cleaning composition having stain resistance and water repellency by irradiation with visible light, which primarily prevents contamination by water-repellent effect on gaseous and liquid contaminants, and the remaining contaminants are secondary through photolysis contamination can be prevented.

In addition, contamination can be prevented through the super water-repellent effect on the surface of gaseous and liquid pollutants, and the effect of decomposing pollutants, removing bacteria and removing viruses by irradiation with visible light is excellent.

The present invention can provide a fabric that can exhibit excellent stain resistance and water repellency, and can maintain excellent stain resistance and water repellency even during repeated use, by including the composition on one or both surfaces of paper, film and fabric.

1 is a view of forming a coating layer having stain resistance and water repellency on a PET sample according to an embodiment of the present invention.
2 is an SEM photograph of a PET sample according to an embodiment of the present invention.
3 is an XRD spectrum result of a PET sample according to an embodiment of the present invention.
4 is an XPS spectrum result of a PET sample according to an embodiment of the present invention.
5 is a UV-Vis spectrum result of a PET sample according to an embodiment of the present invention.
6 is a contact angle measurement result of a PET sample according to an embodiment of the present invention.
7 is a contact angle measurement result of a fabric sample according to an embodiment of the present invention.
8 is a photolysis test result over time of a PET sample according to an embodiment of the present invention.
9 is a solid-state ultraviolet and visible light spectroscopic analysis result of a PET sample according to an embodiment of the present invention.
10 is a test result of photolysis and water repellency according to coffee contamination of PET sample according to an embodiment of the present invention.
11 is a photolysis test result according to the lapse of time, according to an embodiment of the present invention.
12 is a photolysis test result over time, according to an embodiment of the present invention.
13 is a photolysis test result according to the lapse of time, according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

The self-cleaning composition having stain resistance and water repellency by irradiation with visible light of the present invention is titanium dioxide (TiO ₂ ); a compound represented by the following formula (1); and a compound represented by the following Chemical Formula 2, wherein the titanium dioxide (TiO _{2 ) forms a TiO 2} layer on one or both surfaces of the substrate, and the compound represented by the Chemical Formula 1; and the compound represented by Formula 2 may be bonded to the _{TiO 2 layer, respectively:}

[Formula 1]

[Formula 2]

here,

X ₁ to X ₄ may form a coordination bond with a metal selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,

If the X ₁ to X ₄ do not form a coordination bond with the metal,

X ₁ and X ₃ are the same as or different from each other and are each independently _{selected from the group consisting of N(R 14} ), C(R ₁₅ )(R ₁₆ ), O and S,

X ₂ And X _{4 Are} the same as or different from each other, each independently N or C (R ₁₇ ),

L _{1 To} L _{4 Are} the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted A C 1 to C 20 alkylene group, a substituted or unsubstituted C 3 to C 20 cycloalkylene group, a substituted or unsubstituted C 2 to C 20 alkenylene group, a substituted or unsubstituted C 3 to C 20 cycloalkenylene group , a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 heterocycloalkylene group, a substituted or unsubstituted C1 to C20 heteroalkenylene group, a substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R ₁ to R ₆ and R ₈ to R ₁₇ are the same as or different from each other, and each independently represent hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted C1-4 Alkylthio group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C20 24 alkynyl group, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted A heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or An unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero arylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 It is selected from the group consisting of an arylsilyl group and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to or bonded to adjacent groups to form a substituted or unsubstituted ring,
R ₁₈ to R ₂₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, and a substituted or unsubstituted C number It is selected from the group consisting of 2 to 24 alkynyl groups,
L ₅ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group,
When L ₁ to L ₅ and R ₁ to R ₆ and R ₈ to R ₂₀ are substituted, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxyl group, carboxyl group, alkoxy having 1 to 10 carbon atoms group, an alkylthio group having 1 to 4 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 60 carbon atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, A substituent selected from the group consisting of an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms. is substituted with, and when substituted with a plurality of substituents, they are the same as or different from each other.

delete

delete

delete

delete

delete

As shown in FIG. 1 , a TiO ₂ layer is formed _{on one or both surfaces of the substrate, and when the compound represented by Formula 1 is bonded to the TiO 2} , the titanium dioxide photocatalyst absorbs visible light, thereby causing a photocatalytic oxidation reaction.

The photocatalytic oxidation reaction of the present invention refers to the generation of electrons and holes when light energy above the band gap energy is irradiated to the photocatalyst, and the strong oxidizing power of OH radicals (·OH) generated by the holes is adsorbed to the photocatalyst surface. It refers to a reaction in which organic substances in a gaseous or liquid phase are decomposed.

That is, the photocatalyst exhibits catalytic activity by absorbing light energy, which oxidizes and decomposes pollutants with the strong oxidizing power generated at this time.

Existing photocatalyst systems used only a single phase or liquid phase, and the gas phase has an excellent removal rate of harmful substances, but the durability is reduced by fine dust and the lifespan is short. There are difficulties in commercialization.

The liquid phase has excellent durability by removing dust and the like from water, but due to the hydrophilic properties of the photocatalyst, it reacts more easily with water than the time it takes to contact harmful substances, so the removal rate is very low.

In addition, there is a problem that the purification treatment of harmful substances and fine dust dissolved in the liquid is not performed.

Porphyrin-based compounds have a strong absorption region at 400-450 nm in the 'soret band' and a weak absorption region in the 'Q-band' 550-600 nm, so unlike other materials, they have absorption wavelengths up to near IR, used

In order to improve the visible light absorption coefficient of the _{TiO 2 -based photocatalyst, a porphyrin-based compound having a functional group reactive to TiO 2} may be introduced, and thus the energy in the visible light region may be sensitized with a significantly lowered bandgap energy.

Existing photocatalysts only react in the ultraviolet region, effectively solving the problem of decomposition of harmful substances and harmful gases.

The titanium dioxide photocatalyst of the present invention efficiently absorbs visible light (400-800 nm band light) and has a low bandgap energy. In addition, it exhibits excellent thermal and chemical stability, suppresses loss due to recombination, etc., and enables very effective energy transfer.

In addition, the titanium dioxide photocatalyst of the present invention can rapidly decompose a target material to be decomposed, that is, a harmful substance and a noxious gas with a high photodegradation rate, so that it can quickly and effectively decompose and remove a material harmful to the human body or the environment.

In addition, when the titanium dioxide photocatalyst of the present invention is used, it is possible to exhibit excellent effects in removing bacteria and viruses.

Hereinafter, the novel organic compound according to the present invention and a titanium dioxide photocatalyst comprising the same will be described in detail.

The novel organic compound according to the present invention relates to a porphyrin-based compound having a functional group reactive to _{TiO 2 .}

The porphyrin-based compound responds to energy in the visible light region with a lower bandgap energy by exhibiting fast charge transfer and low charge recombination.

The compound represented by Formula 1 may be a compound represented by Formula 2 or a compound represented by Formula 3:

[Formula 2]

[Formula 3]

here,

M is selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,

L ₁ to L ₄ and R ₁ to R ₁₇ are as defined in Formula 1 above.

The L ₁ to L ₄ are a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

wherein R ₁₀ to R ₁₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted It may be selected from the group consisting of a cyclic aralkylamino group having 6 to 30 carbon atoms.

The compound represented by Formula 1 may be selected from the group consisting of the following compounds:

The bond of the compound of Formula 1 to titanium dioxide (TiO ₂ ) may be in the form of a chemical bond, a physical bond, or a bond including them at the same time, specifically, may be in the form of a chemical bond, more specifically, a covalent bond It may be bound in the form of a bond or an ionic bond.

The compound of Formula 1 is bound to the surface of the titanium dioxide (TiO ₂ ) layer to make it difficult to reversibly recombine the structure, thereby acting as a titanium dioxide photocatalyst.

This effect is due to the introduction of a functional group having an anion such as a functional group reactive to _{TiO 2} or an acidic group at any one or more positions selected from _{R 10} and R _{12 .}

From these results, the introduction of an additional ionic functional group does not inhibit the reversible recombination of the structure, such as preventing the induction of high charge density and bond polarization, and thus low charge transfer and high charge recombination are induced, resulting in low photocatalytic efficiency. .

In terms of suppression of loss due to recombination, etc. and effective transfer of charge and energy by absorbed energy, the compound represented by Formula 1 is a porphyrin to which a metal is coordinated, like the compound represented by Formula 3 It may be a system compound.

When the metal-coordinated porphyrin-based compound is combined with the TiO ₂ layer, it exhibits excellent luminous efficiency and excellent reusability by realizing remarkable synergy in charge and energy transfer.

That is, when the metal-coordinated porphyrin-based compound is combined with the TiO ₂ layer, the decomposition efficiency of the contaminant is excellent, and the effect thereof may not be substantially deteriorated.

The porphyrin-based compound represented by Formula 1 of the present invention has a different substituent or added the number of substituents in order to improve the binding force of the porphyrin-based compound bonded to titanium dioxide, compared to the conventional titanium dioxide photocatalyst.

Compared to the case of using only -COOH as a substituent corresponding _{to R 10} to R ₁₃ in the porphyrin-based compound, a _{different substituent such as -SO 3} H, or even using a -COOH substituent, increase the number of substituents, TiO ₂ and improved binding force.

When the bonding strength is improved as described above, TiO ₂ is coated _{on one or both sides of the fabric to form a TiO 2} layer, and when the porphyrin-based compound of the present invention and the alkylsilane compound are combined and used, washing is repeated By maintaining the binding force even during use, the photocatalyst and the water repellency effect can be maintained to the same degree as the first.

In addition, in the porphyrin-based compound represented by Formula 1, a plurality of substituents are bonded to the cyclic ring that absorbs light, or it is composed of a dendrimer or a macro compound to facilitate energy and electron movement by absorbing light.

As described above, by facilitating the movement of energy and electrons by absorption of light, the photolysis effect may be further increased.

The porphyrin-based compound represented by Formula 1 may improve durability by metal coordination, thereby facilitating light absorption.

The metal may be selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca, and is preferably Zn or Sn, but is not limited thereto.

The porphyrin-based compound represented by Formula 1 is _{combined with the TiO 2} layer to act as a titanium dioxide photocatalyst, and the titanium dioxide photocatalyst has a low bandgap energy (eV).

In _{the case of a photocatalyst using only TiO 2} , the band gap energy is 3.2 eV, and when the band gap energy in the corresponding region is the wavelength of light that can be absorbed is in the ultraviolet region, the conventional titanium dioxide photocatalyst shows a photolysis effect only by irradiation of ultraviolet rays. can

On the other hand, when the porphyrin-based compound represented by Formula 1 of the present invention _{is bound to TiO 2} , the bandgap energy may be less than 3.2 eV, preferably 2.5 eV or less, more preferably 2.0 eV or less, more preferably Usually 1.5 to 1.9 eV.

As it has a low bandgap energy in the above range, the wavelength of the absorbable light is in the visible ray region, and an excellent photolysis effect can be exhibited even by irradiation with visible ray.

In addition, it exhibits excellent thermal and chemical stability, suppresses loss due to recombination, etc., and enables very effective energy transfer.

As it has a low bandgap energy in the above range, visible light is absorbed, the hydroxide ions are oxidized to OH radicals by electrons in the conduction band, and oxygen molecules are reduced to reactive oxygen species by holes in the valence band.

That is, when the porphyrin-based compound represented by Formula 1 of the present invention _{is bound to TiO 2} , the band gap energy acts as a titanium dioxide photocatalyst of less than 3.2 eV, and the titanium dioxide photocatalyst absorbs visible light, OH radicals and It generates reactive oxygen species (ROS) such as reactive oxygen species.

By the active oxygen, the decomposition and removal effect of harmful compounds and harmful gases (eg, greenhouse gases, etc.) can be exhibited, and even a sterilization and disinfection effect such as removal of bacteria and viruses can be provided.

The reactive oxygen species may be selected from the group consisting of hydroxyl radicals, superoxide anion radicals, and singlet oxygen ( ¹ O _{2 ) and mixtures thereof.}

The titanium dioxide photocatalyst may exhibit a photodegradation rate according to the following Relational Equation 1:

[Relational Expression 1]

C/C ₀ ≤ 0.3

here,

C is the maximum absorption intensity of the material to be decomposed when 30 minutes have elapsed after the visible light is irradiated,

C ₀ is the maximum absorption intensity of the material to be decomposed before the visible light is irradiated.

The photodegradation rate (C/C ₀ ) may be specifically in the range of 0.01 to 0.30, and more specifically in the range of 0.1 to 0.25.

More specifically, the titanium dioxide photocatalyst of the present invention may exhibit a photodegradation rate according to the following relation 2:

[Relational Expression 2]

0.0001≤ C ₁ /C ₀ ≤ 0.1

C1 is the maximum absorption intensity of the material to be decomposed when 60 minutes have elapsed after the visible light is irradiated.

The photodegradation rate according to Equation 2 may be preferably 0.001 to 0.05.

The photodegradation rate will mean that when the titanium dioxide photocatalyst of the present invention is used, an excellent decomposition effect of harmful substances is exhibited.

In addition, the above-described photodegradation rate is confirmed at the same level even when a reused titanium dioxide photocatalyst is used, and thus can be effectively applied to decomposition of liquid or gaseous hazardous substances.

The rate of change with respect to the photocatalyst of the photocatalyst of the n times reuse of titanium dioxide may be 5% or less, specifically 0.01 to 5%, more specifically 0.01 to 3%.

According to the present invention, by using a titanium dioxide photocatalyst having excellent thermal and chemical stability and high visible light reactivity, stable and excellent photocatalytic activity for a long period of time even in a harsh environment in contact with materials to be decomposed such as wastewater or waste gas, and photocatalytic reaction There is little change before and after, and it can be effectively applied to the decomposition of liquid or gaseous hazardous substances and the removal and extinction of biological pollutants such as bacteria and viruses.

In addition, _{when the compound represented by Formula 2 is bonded to the TiO 2} , it exhibits a superhydrophobic property, thereby exhibiting a super water-repellent effect.

Specifically, according to FIG. 1 , the compound represented by Formula 1 and the compound represented by Formula 2 are each bonded to the _{TiO 2 layer.}

The compound represented by Chemical Formula 1 is _{bonded to the TiO 2} layer, which acts as a titanium dioxide photocatalyst as described above, thereby exhibiting the decomposition effect of contaminants by irradiation with visible light.

In particular, the titanium dioxide photocatalyst is able to respond to sunlight in daily life or indoor lighting in the room, thereby showing excellent practicality and usability.

The indoor lighting is, for example, an incandescent lamp, LED, halogen, and fluorescent lamps, such as, lighting capable of irradiating visible light can be used without limitation.

The titanium dioxide photocatalyst is an effective visible light 　 response type 　 photocatalyst, and has excellent effects of removing harmful substances, deodorizing, and sterilizing bacteria and viruses under visible light as well as ultraviolet light.

In another embodiment of the present invention, when a stain-resistant and water-repellent layer is formed on one or both sides of a fabric by using the composition of the present invention, the liquid contaminants are not absorbed by the water-repellent effect, and the remaining contaminants Through the photolysis of the contamination, it is possible to show the effect of preventing pollution.

In addition, in addition to the effect of preventing contamination by photolysis, it may exhibit a sterilizing effect on bacteria and viruses.

Accordingly, as well as the fabric according to the above example, it can be variously applied to all living spaces such as interior and exterior walls of buildings, building materials, interiors of vehicles, interiors without windows, and household goods. That is, it can be used without limitation for products used where visible light can be irradiated.

The above household goods mean masks, gloves, shoes, clothing, protective clothing, hats, etc. that can be manufactured by processing fabrics, but are not limited to household goods that require removal of harmful substances, deodorization, and sterilization effect against bacteria, viruses, etc. All are available

In addition, when the _{compound represented by Formula 2 is bonded to the TiO 2} layer, a water repellent effect may be exhibited due to the alkyl chain.

In order to hydrophobically modify the surface of the substrate including the protrusions, a super water-repellent surface was implemented using fluorinated silane in the prior art.

In this case, when a fluorine compound is used, such as fluorinated silane, the water repellency effect is very excellent, but when used in a material that comes into contact with the human body, such as fabric, toxicity becomes a problem.

More specifically, perfluorinated octasulfuric acid (PFOS) was found to be a causative agent of thyroid disease and lower immunity and fertility among the perfluorinated compounds with 8 carbon atoms used as water repellents.

In the present invention, in order to prevent this problem, the compound represented by Chemical Formula 2 is _{bonded to the TiO 2} layer to exhibit a super water-repellent effect, and there is no safety problem even when applied to a material in contact with the human body.

More specifically, in the compound represented by Formula 2, L ₅ is a single bond, R ₂₁ is a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms, and more preferably R ₂₁ is an alkyl group having 10 carbon atoms. All functional groups capable of exhibiting a water-repellent effect can be used without limitation.

The compound represented by Formula 2 is a silane compound, and an alkyl group having 10 carbon atoms is bonded to silane, so that the alkyl group having 10 carbon atoms is positioned in a direction perpendicular _{to the TiO 2 layer, thereby exhibiting a water repellent effect.}

According to another embodiment of the present invention, when the composition of the present invention is used on one or both surfaces of paper, film and fabric, stain resistance and water repellency by visible light irradiation can be exhibited at the same time.

In this case, the fabric means that it is made of a fiber selected from the group consisting of PET fiber, nylon fiber, cotton fiber, and mixtures thereof, and the fabric on which a coating layer can be formed by a _{TiO 2 coating method that can be easily selected by those skilled in the art is} All are available without restrictions.

In the case of the film, it is also selectable from the group consisting of PC, PES, TAC, PMMA, PET, ABS, nylon, PVA, PI, COC, and mixtures thereof, preferably PET or nylon, but is not limited to the above examples. .

Using a dip coating method on one surface of the paper, film and fabric, a TiO ₂ coating layer is formed on one or both surfaces. A porphyrin compound and a silane compound may be bonded to the TiO ₂ coating layer to form a self-cleaning and water repellent layer.

Preparation of 5,10,15,20-tetraphenylporphyrin (TPP)

To a solution of propionic acid (50 mL) and benzaldehyde (3 g, 28 mmol) was added pyrrole (1.9 g, 28 mmol), and the reaction mixture was refluxed in the dark for 12 hours. Then, the reaction mixture was filtered, and the solid was washed with water and purified by column chromatography to obtain the desired product as a purple solid (yield: 1.2 g, 27.6 %).

1H NMR (CDCl3, 300 MHz), δ (ppm): -2.84 (s, 2H), 7.65 (m, 12H), 8.13 (m, 8H), 8.77 (s, 8H).

ESI-MS (m/z) calculated: C.614.2, found: 615.4 (M ⁺ H ⁺ ).

Preparation of 4,4′,4″,4-(porphyrin-5,10,15,20-tetrayl)tetrabenzenesulfonic acid (TPPS)

A solution of TPP (1 g, 1.63 mmol) in 20 mL of diluted sulfuric acid (conc. H2SO4) was stirred at 105° C. for 5 hours, followed by stirring at room temperature overnight. The reaction was stopped by adding ice cubes and the mixture was filtered to isolate a green solid. The solid was washed with acetone and neutralized sodium bicarbonate to give the above compound (yield: 0.7 g, 46%).

1H NMR (DMSO-d6, 300 MHz), δ (ppm): -2.88 (s, 2H), 8.02 (d, 8H, J = 8.1 Hz), 8.20 (d, 8H, J = 8.1 Hz) s, 8H ).

MS (MALDI-TOF): m/z calcd. 934.9, found 935.3 (M ⁺ H ⁺ ).

2.3. Preparation of 4,4', 4", 4"-(copper(II)porphyrin-5,10,15,20-tetrayl)tetrabenzene sulfonic acid (CuTPPS)

Copper acetate pentahydrate (0.43 g, 2.14 mmol) dissolved in methanol was added to a solution of chloroform (50 ml) containing TPPS (0.2 g, 0.21 mmol), and the reaction mixture was refluxed in the dark for 1 hour. did. The volatiles were evaporated to dryness, and the residual mixture was dissolved in chloroform. Water was added and the extracted organic layer was purified by column chromatography to obtain the compound as a reddish-purple solid (yield: 0.2 g, 93.9%).

MS (MALDI-TOF): m/z calcd. 996.5, found 997.4 (M ⁺ H ⁺ ).

Preparation of trimethoxy(octadecyl)silane (Si, trimethoxy(octadecyl)silane)

In a 15 mL solution of anhydrous THF containing 1-octadecene (1 g, 4 mmol), trimethoxysilane (0.8 g, 6.5 mmol) and Karstedt's catalyst [3% platinum (0) in 1,1,3,3- tetramethyl-1,3-divinyldisiloxane] was added, and the reaction mixture was refluxed under a nitrogen atmosphere for 24 hours. The resulting compound was separated by column chromatography to obtain a colorless liquid (yield: 0.45 g, 30.4%).

1H NMR (CDCl3, 300 MHz), δ (ppm): 0.56 (m, 2H), 0.79 (t, 3H, J = 7.2 Hz), 1.18 (m, 30H), 1.31 (m, 2H), 3.49 , 9H ).

ESI-MS (m/z) calculated: C. 374.3, found 375.3 (M ⁺ H ⁺ ).

Preparation of TiO ₂

Preparation of Anatase TiO ₂ Colloid: A solution of titanium tetraisopropoxide and acetic acid was added dropwise to acidified water (HNO ₃ , 1.4%). The mixture was vigorously stirred at 60° C. for 16 hours, and _{the structure of the prepared Anatase TiO 2} was confirmed by XRD showing characteristic diffraction peaks at 2θ = 25.5, 38.1 and 48.0°.

_{A thin TiO 2} coating layer was formed on the PET fabric by the dip coating method using the prepared sol. After 30 minutes, the coated samples were exposed to ammonia fumes until the surface had a pH of 7. The samples were dried in an oven at 80° C. and cured at 100° C. for 10 minutes.

Analysis method

For spectral analysis, Alice 4.0 software was used, and for proton NMR spectroscopy, an AVANCE III 300 spectrometer (Made Akishima company, Japan) was operated at 300 MHz for analysis.

The δ values (chemical shifts) of all compounds are expressed in ppm _{from an internal standard (Me 4 Si).}

HRMS spectral analysis was performed using a 1290 Infinity II/Triple TOF 5600 plus mass spectrometer. ESI mass spectral analysis was performed using a 4000 Q TRAP mass spectrometer. SEM analysis was performed using the LYRA3 XMU system. UV-Visible absorption spectrum analysis was performed using an Agilent 8453 instrument. Solid UV-Vis spectral analysis was performed using Shimadzu Solid Spec-2700. XPS experiments were performed using a Multilab 2000 spectrometer. For FT-IR experiments, ALPHA-P spectroscopy was used. XRD studies were performed using an X-ray diffractometer (PHILIPS, X'Pert-MPD System, Max P/N: 3 kW/40kV, 45Ma, Netherlands) with a CuKα (λ= 1.54056Å) X-ray tube, contact angle: DSA 100). was used.

SEM analysis

The surfaces of TiO ₂ , Porphyrin and silyl-treated (TiO 2 , Porphyrin and silyl-treated) PET fabrics and untreated PET were confirmed by SEM analysis. 2 is a result of SEM analysis after coating with _{TiO 2} /TPPS, TiO ₂ /TPPS/Si, TiO ₂ /CuTPPS and TiO _{2 /CuTPPS/Si.}

2, (A)PET, (B)PET/TiO2, (C)PET/TiO2/TPPS, (D)PET/TiO2/TPPS/Si, (E)PET/TiO2/CuTPPS and (F)PET/ TiO2/CuTPPS/Si.

According to FIG. 2 , the _{samples coated with TiO 2} , TPPS/TiO ₂ and CuTPPS/TiO ₂ showed surface roughness, and surface aggregation after silyl coating of the modified PET sample was observed.

XRD analysis

XRD analysis can confirm the nanocrystal properties of the _{prepared TiO 2} as well as the particles deposited on the PET fabric. According to FIG. 3 , in the case of untreated PET (A), the characteristic peak of Anatase TiO ₂ was not observed, but the prepared TiO 2 showed diffraction peaks at 2θ = 25.4, 38.0 and 48.0.

The XRD spectrum (B) of PET treated with TiO ₂ and treated with TPPS and trimethoxy (octadecyl) silane was recorded. This pattern showed characteristic anatase peaks at 2θ = 25.19 37.7 and 47.9.

In light of the above results, TiO ₂ maintained crystallinity in the modified PET sample even after porphyrin and silyl treatment, and maintained photocatalytic activity.

PET surface properties

To confirm the surface deformation of PET fabric, XPS measurement was performed and the chemical structure change of PET was analyzed by deconvoluted XPS spectra of _{PET/TiO 2} /TPPS/Si and PET/TiO _{2 /CuTPPS/Si heterojunctions.} did.

According to FIG. 4 , peaks of C, O, N, S, Si and Ti were observed in _{PET/TiO 2} /TPPS/Si and PET/TiO _{2 /CuTPPS/Si fabrics. The Cs spectra of PET/TiO-2} /TPPS/Si and PET/TiO ₂ /CuTPPS/Si show two deconvoluted peaks at 285.0 and 286.0 corresponding to sp2 carbon and C-OC/C=O bonds, respectively. indicates The deconvoluted O1s peaks at 531.5, 532.5 and 532.9 are due to the presence of Si-O, CO and C=O in the backbone, respectively. Also, a peak centered at 530.0 eV occurs when _{TiO 2 is present in the fabric.}

The pyrrole-like nitrogen of the porphyrin ring of PET/TiO ₂ /TPPS/Si and PET/TiO ₂ /CuTPPS/Si was confirmed by deconvoluted N1s peak at 399.2 eV.

A deconvoluted peak of 103.5 eV in the Si 2p spectrum indicates the presence of silicate (Si-O) bonds. The two deconvolved peaks of the O1s region at 530.4 eV and the Ti 2p region at 458.8 eV (Ti 2p3/2) and 464.2 eV (Ti 2p1/2) with spin-orbit splitting of 8.4 eV are TiO ₂ means peak.

The electronic state of Cu was determined by deconvolution of the Cu 2p region of the PET/TiO _{2 /CuTPPS/Si XPS spectrum.} With the sub-peak (satellite peak) of 943.7 eV 932.2 eV (Cu 2p3 / 2) and 957.3 eV The two main peaks of Cu 2p of (Cu 2p1 / 2) is a _{PET / TiO 2 / CuTPPS / Si} Cu 2 on the coated fabric ⁺ means it exists.

UV-Vis Spectroscopy

The sulfonate group of the porphyrin derivative acted as an anchoring group and the sample to which trimethoxy (octadecyl) silane was bound was confirmed through UV-Vis spectroscopy.

The result is shown in FIG. 5 . Specifically, to confirm the presence of TPPS and CuTPPS in PET fabrics, TPPS and CuTPPS samples were first dissolved in DMF (FIG. 5A), and characteristic peaks for the samples were investigated.

Strong peaks at 417 and 415 nm, respectively, were confirmed in TPPS and CuTPPS corresponding to the Soret band of porphyrin, and weak absorption peaks in the range of about 500 to 650 nm corresponding to the Q-band of porphyrin were confirmed.

In the case of TPPS, peaks at 513, 548, 590, and 646 nm were confirmed, and in the case of CuTPPS, two peaks were identified at about 538 and 573 nm. Thereafter, TPPS and CuTPPS were separately dissolved in DMF, _{adsorbed to PET pretreated with Anatase TiO 2} , and finally TPPS/TiO ₂ /PET and CuTPPS/TiO ₂ /PET samples were treated with octadecylsilane.

As a result of analyzing the sample with a UV-Vis spectrometer (FIG. 5B), as shown in FIG. 5B, separate peaks were not _{observed for PET and TiO 2 coated PET in the 400 to 650 nm region.}

On the other hand, TPPS- and CuTPPS-modified PET samples confirmed strong peaks at 422 nm and 419 nm for TPPS and CuTPPS, respectively.

Compared with the absorption peak in the solution state, the peak of the Soret band of the porphyrin-coated PET showed a shift of about 5 nm, and the red shift of the absorption peak was due to the interaction _{of the SO 3} H group with TiO _{2 of PET.}

After adsorption of octadecylsilane, no change in the absorption peak of porphyrin was observed between _{Si/TPPS/TiO 2} and Si/CuTPPS/TiO _{2 coated fabrics ( FIG. 4B ).}

Consequently, the addition of octadecylsilane does not affect the binding of _{TiO 2 with TPPS and CuTPPS.} Therefore, _{the photocatalytic properties due to the bonding of TiO 2} with TPPS and CuTPPS are maintained even after inclusion of silane.

Hydrophobicity of PET

The hydrophobicity of PET and surface-modified PET was investigated by water contact angle (WCA) measurement. The result is shown in FIG. 6 . 6, (A) PET, (B) PET/TiO ₂ , (C) PET/TiO ₂ /TPPS, (D) PET/TiO ₂ /TPPS/Si, (E) PET/TiO ₂ /CuTPPS, ( F) PET/TiO ₂ /CuTPPS/Si, and (G and H) contact angle measurement results for _{PET/TiO 2} /TPPS/Si and PET/TiO _{2 /CuTPPS/Si.}

The contact angle of water to the original PET was 133°, and, as expected, the sample was partially wetted by contact with the droplet, and the droplet did not roll off easily when tilted.

After further treatment with TiO ₂ , the surface became rough and exhibited increased hydrophobicity, confirmed with a WCA of 138°.

After bonding with TPPS or CuTPPS, TiO ₂ treated PET was confirmed as a WCA of 0° because the sulfonic acid group of the porphine derivative made the fabric hydrophilic and made the fabric completely wet, showing hydrophilicity.

Finally, when TiO ₂ /TPPS and TiO ₂ /CuTPPS were modified with octadecylsilane, the PET fabric exhibited hydrophobicity with a WCA of 147° (FIG. 6).

As a result, _{superhydrophobicity was obtained due to the presence of TiO 2} roughening the surface of the fabric, and the fabric has a low surface energy due to the silane treatment.

Hydrophobicity evaluation of cotton and nylon fabrics

It was evaluated whether the type of fabric can exhibit superhydrophobicity not only for PET, but also for cotton fiber and nylon fiber.

_{In order to measure the contact angle, after modifying TiO 2} /TPPS and TiO ₂ /CuTPPS with octadecylsilane on cotton fabric and nylon fabric, respectively, the contact angle was measured.

The measurement result is shown in FIG. 7 .

As shown in FIG. 7, similarly to the previous experimental results, in the conventional PET fabric, it was measured at 141 to 146.3°, and in the cotton fabric, it was confirmed that it showed superhydrophobicity at 143 to 148.1°, and in the nylon fabric, it was measured at 142°. It was confirmed that it exhibits hydrophobicity.

photocatalytic properties

Self-cleaning of PET samples by photocatalysis was confirmed. TiO ₂ , TPPS/TiO ₂ , CuTPPS/TiO ₂ , Si/TPPS/TiO _{2 ,} and Si/CuTPPS/TiO ₂ RB was adsorbed to the treated sample, and then visible light was irradiated. The photolysis effect over time is shown in FIG. 8 . The degradation of RB as a function of light intensity was measured by solid-state UV visible spectroscopy, and the results are shown in FIG. 9 .

The photolysis efficiency of RB by the sample was determined by comparing the sample to the initial PET.

_{For the samples coated with TiO 2} , TPPS/TiO ₂ , CuTPPS/TiO ₂ , Si/TPPS/TiO _{2 ,} and Si/CuTPPS/TiO ₂ , after 4 hours of irradiation with visible light, the ability to decompose RB was 20, respectively. %, 65%, 77%, 48% and 50%.

The photolysis effect of the porphyrin-coated sample showed superior photoactivity compared to the _{TiO 2 coated sample.}

This is due to the improved photosensitivity of the porphyrin-attached TiO _{2 coated PET sample.} While irradiated with visible light, electrons of the porphyrin _{are excited to the conduction band of TiO 2} to form free radicals, which react with RB adsorbed on PET and decompose. _{Even after bonding octadecylsilane to TiO 2} coated on PET, the photolysis properties of the sample were maintained.

Evaluation of the stability of porphyrins

The stability of porphyrins in modified PET is a very essential factor in confirming reusability.

_{The light stability and stability of porphyrins before and after washing PET coated with TPPS/TiO 2} and CuTPPS/TiO ₂ in detergent and water were measured by measuring the change in porphyrin concentration before and after irradiation under visible light using UV-Vis spectral technique.

As a result, by confirming the strong absorption peak at 415 to 417 nm (soret band), the concentration change of TPPS and CuTPPS can be confirmed. As a result, the porphyrin concentration before and after washing with detergent and water is compared with before washing. Thus, it was measured to be 85 to 90%, confirming excellent stability.

Evaluation of the stability of silanes

The stability of the PET sample coated with octadecylsilane was confirmed. Sample durability is an important factor to ensure that the superhydrophobicity of PET fabrics can be maintained when exposed to different media, treatment processes such as washing and heat treatment. To check the stability of octadecylsilane in PET, WCA was measured after washing with detergent 10 times or more. As a result, _{the contact angles of PET/TiO 2} /TPPS/Si and PET/TiO ₂ /CuTPPS/Si samples exhibited hydrophobic behavior.

In addition, the light stability of the silane coating on PET was checked by exposing the sample to visible light for 24 h. As a result, it was confirmed that the contact angle was 144°.

As a result, the PET sample coated with octadecylsilane exhibited excellent stability even after washing and heat treatment, as well as excellent stability even when exposed to visible light for a long time.

Whether it can show stain resistance and water repellency at the same time

Quantitatively the photolytic activity and superhydrophobicity of PET samples modified using PET/TiO ₂ , PET/TiO ₂ /TPPS, PET/TiO ₂ /TPPS/Si, PET/TiO ₂ /CuTPPS, PET/TiO _{2 /CuTPPS} Confirmed. FIG. 10 shows that when visible light is irradiated to a PET sample coated with porphyrin, the photodegradation of the coffee stain is shown, and the discoloration of the coffee stain is observed at different time intervals.

The samples coated with octadecylsilane are superhydrophobic to coffee drops and can easily come off, indicating the excellent self-cleaning behavior of the modified PET samples when the coffee drops come in contact.

However, for oil stains such as ketchup, the water repellency effect due to the coating effect of octadecylsilane decreases, and in this case, the original PET, PET/TiO ₂ , PET/TiO ₂ /TPPS, PET/TiO ₂ /TPPS/Si, PET/ Adsorbed to TiO ₂ /CuTPPS, PET/TiO ₂ /CuTPPS/Si. PET/TiO ₂ /TPPS, PET/TiO ₂ /TPPS/Si, PET/TiO ₂ /CuTPPS and PET/TiO ₂ /CuTPPS/Si faded stains due to the photolysis effect upon irradiation with visible light.

Preparation and data of additional porphyrin compounds

4,4'-(porphyrin-5,15-diyl)dibenzoic acid (PORPC-1)

Compound 2a (0.8 g, 1.4 mmol) was added to a mixed solvent of tetrahydrofuran (THF) and methanol (180 mL, 1:1 vol/vol). Next, potassium hydroxide solution (30 mL, 2M) was added. The reaction solution was refluxed for 12 hours. After completion of the reaction, the reaction solution was neutralized. Filtration gave a dark purple product, which was washed with distilled water and diethyl ether and dried (94%, 0.71 g).

Mp:>350°C, 1H NMR (600MHz, DMSOd6): δ 10.68 (s, 2H), 9.69 (d,J=3.6, 4H) 9.06 (d, J=3.6, 4H), 8.38-8.48 (m, 8H) ), 3.22 (s, 2H) ppm; 13C NMR (150MHz, DMSOd6): δ 170.2, 167.4, 150.8, 144.7, 134.7, 132.8, 130.2, 129.2, 128.0, 113.8, 106.0, 101.3.

IR (KBr tablet) νmax/cm-1: 3220, 3021, 1695, 1550, 1501, 1320, 1205, 1050, 990, 952, 886, 801.

4,4'-(porphyrin-5,15-diyl)dibenzoic acid (PORPC-2)

Compound 3a (0.64 g, 1 mmol) was added to a mixed solvent of tetrahydrofuran (THF) and methanol (90 mL, 1:1 v/v). Next, potassium hydroxide solution (28 mL, 2M) was added. The reaction solution was refluxed for 12 hours. After completion of the reaction, half of the solvent of the reaction solution was evaporated, and the reaction solvent was converted to acid (pH=3) using 1M HCl. Filtration gave a dark red product, which was washed with distilled water and diethyl ether and dried (0.6 g, 98%).

Mp:>350°C, 1H NMR (600MHz, DMSOd6):δ 13.24 (s, 2H), 10.42 (s,2H) 9.54 (d, J=4.3, 4H), 8.95 (d, J=4.3, 4H), 8.26-8.48 (m, 8H) ppm; 13C NMR (150MHz, DMSOd6): δ 167.6, 148.9, 148.7, 147.0, 134.6, 132.3, 131.5, 129.7, 127.5, 117.9, 106.3.

IR (KBr tablet) v max/cm-1:3210, 3011, 1690,1552, 1571, 1310, 1225, 1055, 990, 957, 889, 809.

2,2'-((3,5-di-tert-butylphenyl)methylene)bis(1Hpyrrole)(1b)

A mixture of di-t-butyl benzaldehyde (1.6g, 7.4mmol, Di-tert-butyl benzaldehyde) and pyrrole (25mL, 91mmol, pyrrole) was mixed with BF3.OEt2 solution (0.5mL, 3.2M, in CHCl ₃ ) was slowly added. The reaction solution was stirred for 2 hours. After the reaction, the solvent of the reaction solution was removed. Thereafter, it was redissolved using methylene chloride, washed with 1M NaOH solution (40 mL, in H 2 O), and the solvent was removed. The obtained product was subjected to column separation (hexane/DCM=1/1) to obtain a brown solid product (1b) (1.73 g, 70%).

Mp: 70-72°C, 1H NMR (600MHz, CDCl3): δ 7.83 (s, 2H), 7.00 (s,2H), 6.62 (s, 2H), 6.08-6.11 (m, 2H), 5.88 (s, 2H) ppm; 13C NMR (150MHz, DMSOd6): δ 150.9, 140.8, 132.9, 122.7, 120.8, 116.9, 108.3, 107.1, 44.5, 34.8, 31.4 ppm.

IR (KBr tablet) v max/cm-1: 3250, 1594, 1361, 1247, 1090, 1027, 879, 774, 710.

4,4'-(10,20-bis(3,5-di-tert-butylphenyl)porphyrin-5,15diyl)dibenzoic acid (PORPC-3)

Compound 2b (1.43 g, 1.5 mmol) was added to a mixed solvent of tetrahydrofuran (THF) and methanol (190 mL, 1:1 v/v). Next, potassium hydroxide solution (32 mL, 2M) was added. The reaction solution was refluxed for 12 hours. After completion of the reaction, the reaction solution was neutralized. By filtration, a dark red product was obtained, washed with distilled water and diethyl ether and dried (46%, 0.64 g).

Mp:>350℃, 1H NMR (600MHz, CDCl3): δ 8.84 (d, J=4.4Hz, 4H), 8.78 (d, J=4.4Hz, 4H), 8.36 (d, J=7.6Hz, 4H) , 8.26 (d, J=7.6Hz, 4H), 7.99-8.01 (m, 4H), 7.76-7.78 (m, 2H), 1.48 (s, 36H), 2.90 (s, 2H) ppm; 13C NMR (150MHz, DMSOd6): δ 174.3, 160.2, 159.9, 154.0, 149.0, 146.3, 145.8, 140.2, 139.5, 135.6, 132.1, 131.9, 130.7128.3, 127.3, 123.5, 32.0, 31.1 ppm.

IR (KBr tablet) v max/cm ^-1 : 3230, 3001, 1706, 1542, 1591, 1320, 1235, 1046, 995, 944, 891, 810.

4,4'-(10,20-bis(3,5-di-tert-butylphenyl) porphyrin-5,15-diyl)dibenzoate (2b)

Dipyrromethane (3.34g, 10mmol, Dipyrromethane) was added to a solution of methyl 4-romylbenzoate (1.642g, 10mmol, methyl 4-formylbenzoate) dissolved in 100mL pyropionic acid. The reaction solution was refluxed for 4 hours. After completion of the reaction, the solvent of the reaction solution was removed, and ethanol (30 mL) was added to react for 1 hour. The reaction solution was cooled and filtered. The obtained product was subjected to column separation (hexane/DCM=1/1) to obtain a pale purple solid product (2b) (40%).

Mp:>350℃, 1H NMR (600MHz, CDCl3):δ 8.83 (d, J=4.3Hz,4H), 8.71(d,J=4.3Hz,4H),8.36(d,J=7.9Hz,4H) , 8.24 (d,J=7.9Hz,4H), 7.98-8.02(m,4H), 7.72-7.75(m,2H), 4.03(s,6H), 1.45 (s, 36H), 2.81 (s, 2H) ) ppm; 13C NMR (150MHz, DMSOd6): δ 167.3, 148.8, 147.2, 140.9, 134.3, 129.9, 129.5, 127.8, 121.9, 121.1, 118.6, 53.4, 52.4, 35.0, 31.7, 29.7 ppm.

IR (KBr tablet) v max/cm-1: 3223, 2952, 1720, 1591, 1432, 1276, 1111, 970, 796, 765, 716.

Step 2. Preparation of zinc dimethyl 4,4'-(10,20-bis(3,5-di-tert-butylphenyl)porphyrin-5,15-diyl)dibenzoate (3b)

A mixture of compound 2b (0.955 g, 1 mmol) and Zn(OAc)2.2H 2 O (2.20 g, 10 mmol) was dissolved in dichloromethane (240 mL). To this, methanol (120 mL) was added and vigorously stirred at room temperature for 3 hours. Distilled water (50 mL) was added to the reaction solution to terminate the reaction, and the mixture was extracted twice with dichloromethane. Then, the organic layer was washed with distilled water, and the solvent in the reaction solution was removed to obtain compound 3b (0.99 g, 97.2%) (0.99 g, 97.2%).

Mp:>350℃, 1H NMR (600MHz, CDCl3): δ 8.83 (d, J=4.3Hz,4H), 8.75(d,J=4.3Hz,4H), 8.34(d,J=7.7Hz,4H) , 8.27 (d,J=7.7Hz,4H), 7.95-8.02(m,4H), 7.73-7.77(m,2H), 4.02(s,6H), 1.49 (s, 36H) ppm; 13C NMR (150MHz, DMSOd6): δ 167.5, 147.7, 142.1, 133.4, 131.1, 130.6, 128.8, 122.9, 122.2, 120.1, 52.7, 35.7, 32.1 ppm.

IR (KBr tablet) v max/cm-1: 3002, 1709, 1597, 1432, 1323, 1207, 1148, 1050, 990, 856, 772.

Step 3. Preparation of 4,4'-(10,20-bis(3,5-di-tert-butylphenyl)porphyrin5,15-diyl)dibenzoic acid (PORPC-4)

Compound 3b (808 mg, 0.5 mmol) was added to a mixed solvent of tetrahydrofuran (THF) and methanol (90 mL, 1:1 v/v). Next, potassium hydroxide solution (14 mL, 2M) was added. The reaction solution was refluxed for 12 hours. After completion of the reaction, half of the solvent of the reaction solution was evaporated, and the reaction solvent was converted to acid (pH=3) using 1M HCl. Filtration gave a dark red product, which was washed with distilled water and diethyl ether and dried (485 mg, 98%).

Mp:>350℃, 1H NMR (600MHz, CDCl3): δ 9.39 (d, J=4.3Hz, 4H), 9.21 (d, J=4.3Hz, 4H), 8.89 (d, J=7.5Hz, 4H) , 8.59 (d, J=7.5Hz, 4H), 8.50-8.55 (m, 4H), 8.07-8.11 (m, 2H), 1.60 (s, 36H) ppm; 13C NMR (150MHz, DMSOd6): δ 169.3, 151.6, 149.6, 148.6, 143.5, 133.5, 133.4, 132.7, 132.3, 131.4, 128.9, 121.6, 120.9, 35.6, 32.2 ppm.

IR (KBr tablet) vmax/cm-1: 3220, 3021, 1716, 1539, 1561, 1220, 1210, 1035, 991, 945, 887, 811.

5,15-diphenylporphyrin

Dichloromethane (6.7 g, 20 mmol) and benzaldehyde (2.1 g, 20 mmol) were dissolved in 1000 mL of dichloromethane, and trifluoroacetic acid (1.14 g, 10 mmol) was added to the resulting mixture, followed by stirring at room temperature for 4 hours. did.

Then, 2,3-dichloro-5,6-dicyanobenzoquinone (6.8 g, 30 mmol) was added and stirred for an additional 1 hour, and the reaction mixture was finally quenched with triethylamine (20 mL). ) was done. The solvent was removed under vacuum distillation. The crude mixture was further purified using silica gel column chromatography using hexane and DCM (weight ratio of 1:1) to obtain Preparation Example 5 as a purple solid (yield: 4.25 g, 46%).

1H NMR (600 MHz, CDCl3): δ 10.21 (s, 2H), 9.29 (d, J = 4.5 Hz, 4H), 8.99 (d, J = 4.5 Hz, 4H), 8.17-8.21 (m, 4H), 7.70-7.75 (m, 6H), -3.19 (s, 2H) ppm;

13C NMR (150 MHz, CDCl3): δ 146.1, 144.1, 140.3, 133.8, 130.5, 130.0, 126.6, 125.9, 118.0, 104.2 ppm.

IR (KBr tablet) νmax/cm-1: 3301, 3010, 2991, 1640, 1522, 1421, 1322, 1301, 1251, 899, 801, 780. HRMS (ESI-MS) m/z calcd for C ₃₂ H ₂₃ N ₄ [M ⁺ H] ⁺ : 463.1917, found 463.1910.

Dihydroxo(5,15-diphenylporphyrinato)tin(IV)

The compound of Preparation 5 (462 mg, 1 mmol) was dissolved in pyridine (120 mL), tin(II) chloride dihydrate (451 mg, 2 mmol) was slowly added, and the reaction mixture was heated under reflux for 6 hours. did. Thereafter, the reaction mixture was concentrated and washed with excess water and ether, and the obtained crude product was dissolved in a RB flask containing THF:water (8:2 weight ratio, 50 mL) and potassium carbonate (2.1 g, 15 mmol) was added. Then, the mixture was stirred under reflux for 4 hours. DCM (100 mL) was added to the reaction mixture, the solution was washed with water (2x50 mL), and the product was finally recrystallized from hexane:chloroform (1:1 weight ratio) to obtain the compound of Preparation Example 6 in purple. (yield 86%).

1H NMR (600 MHz, CDCl3): δ 10.81 (s, 2H), 9.75 (d, J = 4.3 Hz, 4H), 9.32 (d, J = 4.3 Hz, 4H), 8.34-8.39 (m, 4H), 7.85-7.94 (m, 6H) ppm;

13C NMR (150 MHz, CDCl3): δ 146.6, 145.7, 140.9, 135.3, 133.3, 132.3, 128.2, 127.1, 120.4, 105.7.

IR (KBr tablet) νmax/cm-1: 3011, 2899, 1670, 1577, 1455, 1422, 1366, 1310, 1211, 865, 791. C ₃₂ H ₂₂ N ₄ O ₂ Sn; Calculated, %: C 62.67; H 3.62; N 9.14, Found, %: C 62.64; H 3.64; N 9.11. MS (MALDI-TOF): 614.512 [M] ⁺ .

1H NMR (600 MHz, CDCl3): δ 11.05 (s, 5H), 8.19 (d, J = 4.7 Hz, 2H), 8.15 (d, J = 4.7 Hz, 2H), 8.45 (d, J = 7.9 Hz, 2H), 7.66 (m, 16H), -2.33 (s, 2H) ppm;

max/cm-1: 3027, 3001, 2809, 1660, 1507, 1315, 1233, 1214, 806, 729. ESI-MS: 807 [M+H]+.IR (KBr tablet)

max/cm-1: 3027, 3001, 2809, 1660, 1507, 1315, 1233, 1214, 806, 729. ESI-MS: 807 [M+H]+.

1H NMR (600 MHz, CF3COOD): δ 11.11 (s, 2H), 9.69 (d, J = 4.7 Hz, 4H), 9.25 (d, J = 4.7 Hz, 4H), 8.66 (d, J = 7.9 Hz, 4H), 8.36 (d, J = 7.9 Hz, 4H), 8.30 (d, J = 7.9 Hz, 4H), 8.08 (d, J = 7.9 Hz, 4H), -3.61 (s, 2H) ppm;

13C NMR (150 MHz, CF3COOD): δ 167.3, 150.2, 149.8, 149.5, 146.2, 145.4, 142.9, 138.2, 130.4, 130.3, 128.4, 127.3, 127.1, 122.6.

max/cm-1: 3357, 3001, 2889, 1660, 1571, 1405, 1433, 1377, 1333, 1214, 896, 789. ESI-MS: 703.25 [M+H]+.IR (KBr tablet)

max/cm-1: 3357, 3001, 2889, 1660, 1571, 1405, 1433, 1377, 1333, 1214, 896, 789. ESI-MS: 703.25 [M+H]+.

5,10,15,20-tetraphenylporphyrin

1H NMR (CDCl3, 300 MHz), δ (ppm): -2.84 (s, 2H), 7.65 (m, 12H), 8.13 (m, 8H), 8.77 (s, 8H). ESI-MS (m/z) calcd. 614.2, found 615.4 (M + H+).

4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid

1H NMR (CDCl3, 600 MHz), δ (ppm): -2.92 (s, 2H), 8.34 (d, 8H, J = 7.8 Hz), 8.38 (d, 8H, J = 7.8 Hz), 8.86 (s, s, 8H), 13.29 (s, 4H).

ESI-MS (m/z) calcd. 790.2, found 791.3.3 (M+H+). Mp: >350 °C.

5,10,15,20-tetra(pyridin-3-yl)porphyrin

1H NMR (CDCl3, 600 MHz), δ (ppm): -2.91 (s, 2H), 7.67 (t, 4H, J = 6 Hz), 8.44 (d, 4H, J = 3.6 Hz), 8.77 (s, 8H), 8.96 (m, 4H), 9.36 (s, 4H),

ESI-MS (m/z) calcd. 618.2, found 619.4 (M+H+). Mp: >350 °C.

4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrabenzonitrile

1H NMR (CDCl3, 600 MHz), δ (ppm): -2.94 (s, 2H), 8.02 (d, 8H, J = 8.4 Hz), 8.25 (d, 8H, J = 8.4 Hz), 8.72 (s, s, 8H), ESI-MS (m/z) calcd. 714.2, found 715.3 (M+H+). Mp: >350 °C.

Copper (II) complex of 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrabenzonitrile

ESI-MS (m/z) calcd. 776.3, found 777.3 (M+H+). Mp: >350 °C.

Nickel (II) complex of 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrabenzonitrile

ESI-MS (m/z) calcd. 771.4, found 772.3 (M+H+). Mp: >350 °C.

Zinc (II) complex of 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrabenzonitrile

ESI-MS (m/z) calcd. 778.1, found 779.2 (M+H+). Mp: >350 °C.

(4,4',4'',4'''-(2,3,7,8,12,13,17,18-octabromoporphyrin-5,10,15,20-tetrayl)tetrabenzoic acid)

1H NMR (DMSO-d6, 600 MHz), δ (ppm): 8.39 (m, 16H), 13.31 (s, 4H). MALDI-TOF: m/z found 1421.4, calcd. 1421.9 (M + H+). Mp: >350 °C.

(4,4',4'',4'''-(2,3,7,8,12,13,17,18-octabromo-copper porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid)

MALDI-TOF: m/z found 1482.3, calcd. 1483.4 (M + H +). Mp: >350 °C.

4,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoic acid

1H NMR (DMSO-d6, 600MHz), δ(ppm): 6.64 (m, 40H), 7.61 (s, 8H), 8.12 (s, 8H), 12.83 (s, 4H). MALDI-TOF: m/z found 1400.7, calcd. 1399.5 (M+H+). Mp: >350 °C.

4,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenyl-copperporphyrin-5,10,15,20-tetrayl)tetrabenzoicacid

ESIMS: m/z found 1462.3, calcd. 1461.1 (M+H+). Mp: >350 °C.

1H NMR (DMSO-d6, 600 MHz), δ (ppm): 4.03 (s, 12H), 8.29 (s, 32H), 8.43 (m, 16H), 12.95 (s, 8H). MALDI-TOF: m/z found 1807.5, calcd. 1806.4 (M + H +). Mp: >350 °C.

(4,4',4'',4''',4'''',4''''',4'''''',4''''''',4'''' '''',4''''''''',4'''''''''',4'''''''''''-(porphyrin-2,3,5, 7,8,10,12,13,15,17,18,20-dodecayl)dodecabenzoic acid)

1H NMR (DMSO-d6, 600 MHz), δ (ppm): 8.44 (m, 48H), 13.40 (s, 12H). MALDI-TOF: m/z found 1751.5, calcd. 1750.3 (M + H+). Mp: >350℃

photocatalytic decomposition effect

After binding the porphyrin compounds of Table 1 to the TiO2-coated PET sample, the photolysis effect on contaminants was measured.

One TCPP

2 TCNPP

3 TPyP

4 S1

5 S2

6 S3

7 S4

8 S5

9 S6

The degree of RB (Rhodamine B) degradation of the PET sample coated with the porphyrin compounds of 1 to 3, the untreated PET sample, and _{the PET sample treated only with TiO 2 was confirmed.}

The PET sample coated with the porphyrin compounds of 1 to 3, the untreated PET sample, and the TiO ₂ only-treated PET sample were treated with RB, exposed to visible light, and then monitored.

According to FIG. 11 , in the case of the untreated PET sample, it was confirmed that there was no change in RB, and _{even when only TiO 2} was treated, it was confirmed that some level of decomposition was exhibited.

On the other hand, in the case of the PET samples coated with the porphyrin compounds of 1 to 3, a very high level of photolysis effect was confirmed as a result of checking up to 3 hours.

12 is a result of confirming the degree of photolysis after coating the porphyrin compounds of 4 to 9 on a PET sample in the same manner.

According to FIG. 12, it can be confirmed that the excellent photolysis effect was exhibited in _{TiO 2} to which the porphyrin compounds of 4 to 9 were bound.

13 and 14 show the photolysis effect according to the binding of the porphyrin compounds of 4 to 7, and it is possible to visually confirm the superior photolysis effect compared to the _{untreated PET sample and the TiO 2 treated PET sample.}

Although the preferred embodiment of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (12)

titanium dioxide (TiO ₂ );
a compound represented by the following formula (1); and
A composition comprising a compound represented by the following formula (2),
The titanium dioxide (TiO ₂ ) forms a _{TiO 2} layer on one or both sides of the substrate,
a compound represented by Formula 1; And the compound represented by Formula 2 is each bonded to the _{TiO 2 layer,}
The composition has a photodegradation rate according to the following relation 1, and has excellent stain resistance and water repellency,
Self-cleaning composition having stain resistance and water repellency by irradiation with visible light:
[Formula 1]

[Formula 2]

[Relational Expression 1]
C/C ₀ ≤ 0.3
here,
C is the maximum absorption intensity of the material to be decomposed when 30 minutes have elapsed after the visible light is irradiated,
C ₀ is the maximum absorption intensity for the material to be decomposed before the visible light is irradiated
X ₁ to X ₄ may form a coordination bond with a metal selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,
If the X ₁ to X ₄ do not form a coordination bond with the metal,
X ₁ and X ₃ are N(R ₁₄ ),
X ₂ and X ₄ are N,
L _{1 To} L _{4 Are} the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted A C 1 to C 20 alkylene group, a substituted or unsubstituted C 3 to C 20 cycloalkylene group, a substituted or unsubstituted C 2 to C 20 alkenylene group, a substituted or unsubstituted C 3 to C 20 cycloalkenylene group , a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C3 to C20 heterocycloalkylene group, a substituted or unsubstituted C1 to C20 heteroalkenylene group, a substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R ₁ to R ₆ and R ₈ to R ₁₄ are the same or different from each other, and each independently represent hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted C1-4 Alkylthio group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C20 24 alkynyl group, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted A heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or An unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero arylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 It is selected from the group consisting of an arylsilyl group and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to or bonded to adjacent groups to form a substituted or unsubstituted ring,
R ₁₈ to R ₂₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, and a substituted or unsubstituted C number It is selected from the group consisting of 2 to 24 alkynyl groups,
L ₅ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group,
When the L ₁ to L ₅ and R ₁ to R _{6 ,} R ₈ to R ₁₄ and R ₁₈ to R ₂₀ are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, An alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, 7 carbon atoms to 30 aralkyl group, C 6 to C 30 aryl group, C 2 to C 60 heteroaryl group, C 6 to C 30 heteroarylalkyl group, C 1 to C 30 alkoxy group, C 1 to C 30 alkylamino group, C 6 to 30 arylamino group, C6-C30 aralkylamino group, C2-C24 hetero arylamino group, C1-C30 alkylsilyl group, C6-C30 arylsilyl group and C6-C30 aryloxy group It is substituted with a substituent selected from the group consisting of, and when substituted with a plurality of substituents, they are the same or different from each other. According to claim 1,
That the composition exhibits photocatalytic activity under visible light
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. According to claim 1,
The composition generates reactive oxygen species under visible light to self-clean contaminants.
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. delete According to claim 1,
The composition has a bandgap energy (eV) of less than 3.2.
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. According to claim 1,
The composition has a contact angle of 140° or more on the fiber surface.
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. According to claim 1,
Wherein L _{1 To} L _{4 Are} a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. According to claim 1,
wherein R ₁₈ to R ₂₀ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group
A self-cleaning composition having stain resistance and water repellency by irradiation with visible light. delete A self-cleaning and water-repellent layer formed using the composition according to claim 1
Self-cleaning and water-repellent fabric. A self-cleaning and water-repellent layer formed using the composition according to claim 1
Paper for self-cleaning and water repellency. A self-cleaning and water-repellent layer formed using the composition according to claim 1
Self-cleaning and water-repellent film.

Images