WO2022146030A1 - Self-cleaning composition and self-cleaning fabric comprising same - Google Patents
Self-cleaning composition and self-cleaning fabric comprising same Download PDFInfo
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- WO2022146030A1 WO2022146030A1 PCT/KR2021/020172 KR2021020172W WO2022146030A1 WO 2022146030 A1 WO2022146030 A1 WO 2022146030A1 KR 2021020172 W KR2021020172 W KR 2021020172W WO 2022146030 A1 WO2022146030 A1 WO 2022146030A1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
Definitions
- the present invention relates to a self-cleaning composition and a self-cleaning fabric comprising the same, and more particularly, it is possible to prevent adhesion of contaminants by implementing a super water-repellent surface, and to prevent contamination through decomposition of the attached contaminants. It relates to a self-cleaning composition and a self-cleaning fabric comprising the same.
- water repellents used for fibers are largely wax-based, higher alcohol-based, silicone-based and fluorine-based water repellents.
- the fluorine-based water repellent has the most excellent water repellency due to the basic physical properties of fluorine and is the most useful water repellent because of the advantage of obtaining oil repellency.
- the fluorine-based water repellent is the most excellent hydrophobic material and has no water dissolving power, so there should be no deterioration in water repellency even during washing resistance. Therefore, it is forced to emulsify using a component called a surfactant and then goes through a process of treating the fabric.
- the surfactant component remaining in the fluororesin or in the fabric has a very hydrophilic property, it accelerates the removal of the fluorine water repellent component during washing, resulting in a decrease in water repellency performance in the process of washing several times. .
- Blocked isocyanate is used as the most used crosslinking agent type.
- the isocyanate acts as a crosslinking agent for the fluororesin, thereby improving the bonding strength between the fluorine water repellent and the fibers. It has been reported to improve durability by forming a three-dimensional network structure.
- Another object of the present invention is to form a coating layer on the surface of the fabric to provide super water repellency to prevent the adsorption of contaminants, and to decompose contaminants through the photocatalytic effect of the visible light response to the contaminants adsorbed on the surface of the fabric.
- a cleaning composition To provide a cleaning composition.
- Another object of the present invention is to provide a fabric capable of self-cleaning by digital printing of a super water-repellent ink composition on a fabric to which a photocatalytic composition is bonded, thereby superhydrophobicity and a photocatalytic effect by visible light sensitivity.
- the self-cleaning composition according to an embodiment of the present invention is TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound are bonded to TiO 2 :
- 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 13 ), C(R 14 )(R 15 ), O and S,
- 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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
- R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl
- L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
- R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
- R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and
- L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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.
- the porphyrin compound represented by Formula 1 is a compound represented by Formula 3 below:
- R 1 to R 12 and L 1 to L 4 are as defined in Formula 1 above.
- R 1 to R 8 are the same as or different from each other, and may each independently be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.
- the L 1 to L 4 may be the same as or different from each other, and each independently may be a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
- the L 5 is an alkyl group having 1 to 30 carbon atoms.
- R 18 to R 20 are an alkyl group having 1 to 30 carbon atoms.
- TiO 2 is bound to the surface of the fabric, and a porphyrin compound and a silane compound are bound to TiO 2 bound to the fabric to act as a superhydrophobic and visible light-sensitive photocatalyst.
- the self-cleaning fabric according to another embodiment of the present invention includes the self-cleaning composition.
- TiO 2 is bonded to the surface, the porphyrin compound is bonded to TiO 2 to act as a visible light-sensitive photocatalyst, and the silane compound is bonded to TiO 2 to exhibit super water repellency.
- the silane compound may be included in the ink composition and printed on the surface of the fabric through a digital printer to exhibit super water repellency.
- hydrogen is hydrogen, light hydrogen, deuterium or tritium.
- the “halogen group” is fluorine, chlorine, bromine or iodine.
- 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.
- 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, allyl, isopropenyl, 2-butenyl, and the like.
- alkynyl 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 triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.
- 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.
- 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.
- heteroaryl refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms.
- one or more carbons in the ring preferably 1 to 3 carbons, are substituted with a heteroatom such as N, O, S or Se.
- 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.
- heteroaryl examples 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, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.
- 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole
- aralkyl refers to an aryl-alkyl group wherein 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.
- heteroarylalkyl group refers to an aryl-alkyl group substituted with a heterocyclic group.
- condensed ring refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
- adjacent groups are combined with each other to form a ring
- 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.
- 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.
- a coating layer is formed on the surface of a fabric to provide super water repellency to prevent adsorption of contaminants, and contaminants can be decomposed by a photocatalytic effect by response to visible light for contaminants adsorbed on the surface of the fabric.
- 1 is a surface-modified fabric according to an embodiment of the present invention.
- FIG. 2 is a UV-VIS spectrum measurement result according to an embodiment of the present invention
- FIG. 2A is a spectrum measurement result for a porphyrin compound
- FIG. 2B is a spectrum measurement result for PET fabric, PET@TP and PET@TPS .
- 3 is an XRD measurement result of a fabric according to an embodiment of the present invention.
- 5 is an EDX analysis result for PET@TPS according to an embodiment of the present invention.
- 11 is a mechanism for MB degradation at the fabric surface according to an embodiment of the present invention.
- FIG. 13 is a result of a water repellency test for a printing area and a non-printing area and manufacturing the ink composition of a silane compound according to an embodiment of the present invention.
- the present invention is TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound are TiO 2 It relates to a self-cleaning composition that binds to:
- 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 13 ), C(R 14 )(R 15 ), O and S,
- 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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
- R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl
- L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
- R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
- R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and
- L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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.
- the self-cleaning textile material can be used in various ways in daily life for commercial purposes.
- a self-cleaning surface exhibiting self-cleaning properties due to coating the fibers with a hydrophobic or hydrophilic compound has undergone rapid development in order to exhibit the above properties.
- the material should exhibit properties such as superhydrophobicity, and due to the above properties, various uses such as anti-sticking, anti-icing, anti-fog, anti-pollution, self-cleaning and water/oil separation are possible do.
- the surface energy is low and has sufficient surface roughness, and dust can be easily removed by contacting water with the surface of the fabric.
- Fabrication for the surface of the fabric exhibiting the super water-repellent properties as described above, inspired by nature, including lotus leaves and water strider, can be manufactured.
- Metal oxide nanoparticles such as TiO 2 NPs and hydrophilic self-cleaning fiber materials through photocatalytic modification can be applied to a wide range of applications.
- TiO 2 shows high stability, is non-toxic, is inexpensive, and is one of the reliable and environmentally friendly photocatalysts with excellent oxidation ability.
- the polycrystalline semiconductor oxide exhibits optical properties, and the photoactive material can spontaneously decompose and remove contaminants absorbed by photooxidation and photoreduction reactions under light.
- Dye sensitization by the binding of porphyrin and TiO 2 produces a solid band in the 450 nm region (Soret band) and a weak Q band at about 500-700 nm.
- the modified surface obtained through the above process may have excellent self-cleaning properties and may exhibit a self-cleaning effect by exposure to visible light.
- the self-cleaning properties that can be achieved by incorporating hydrophobic and photocatalytic properties into the fabric have two advantages. 1) Water-soluble impurities are removed due to the water-repellent properties of the fabric, and 2) organic dyes and other common stain-causing substances can be decomposed by the photocatalyst.
- the present invention developed a novel porphyrin compound and a novel silane derivative in order to increase the cleaning effect, and attached them to a fabric to improve physical properties.
- it is characterized in that it contains a non-fluorine compound.
- These silanes are less toxic when compared to fluorinated silanes.
- the prepared porphyrin compound includes a phenyl group substituted with a carboxylate at the meso position, and includes a phenyl ring as a substituent at the beta position, thereby affecting the TiO2 photocatalytic behavior.
- the silane compound was prepared with a hydrophobic ink, and it was also confirmed whether printing on the surface of the fabric as a hydrophobic surface was possible through digital printing.
- the self-cleaning composition according to an embodiment of the present invention includes TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound may be combined with TiO 2 .
- 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 13 ), C(R 14 )(R 15 ), O and S,
- 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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
- R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl
- L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
- R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
- R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and
- L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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.
- the porphyrin compound represented by Formula 1 may be a compound represented by Formula 3 below:
- R 1 to R 12 and L 1 to L 4 are as defined in Formula 1 above.
- R 1 to R 8 are the same as or different from each other, and may each independently be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.
- the L 1 to L 4 may be the same as or different from each other, and each independently may be a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
- R 1 to R 8 may be an unsubstituted phenyl group
- L 1 to L 4 may be a substituted phenyl group
- L 1 to L 4 may be substituted with a carboxyl group.
- the porphyrin compound may move the light absorption region of the TiO 2 photocatalyst to the visible region by bonding with TiO 2 , and as the porphyrin compound includes four carboxyl groups, the portion bonding with TiO 2 is plural. As it is included, the efficiency of the photocatalyst can be maintained even by repeated use such as washing by increasing the binding force.
- the silane compound represented by Formula 2 is characterized in that L 5 is an alkyl group having 1 to 30 carbon atoms, and R 18 to R 20 are an alkyl group having 1 to 30 carbon atoms.
- L 5 is a methylene group having 20 carbon atoms
- R 18 to R 20 are an ethyl group having 2 carbon atoms.
- the silane compound is a silane compound to which a carbon chain having 22 carbon atoms is bonded, and is characterized in that it exhibits super water-repellent properties on the surface of the fabric by the carbon chain. That is, it is possible to exhibit a water-repellent effect due to the carbon chain without including fluorine as a substituent.
- TiO 2 is bound to the surface of the fabric, and a porphyrin compound and a silane compound are bound to TiO 2 bound to the fabric to act as a superhydrophobic and visible light-sensitive photocatalyst.
- FIG. 1 is a conceptual diagram of a surface of a fabric coated with a self-cleaning composition according to an embodiment of the present invention.
- anatase TiO 2 is bonded to the surface of the fabric, and the -OH group of TiO 2 is porphyrin. It is bound to the -COOH group of the compound, and the -COOH group of the porphyrin compound is included in one compound by four, so that it is bound to TiO 2 in four places, thereby exhibiting excellent bonding strength.
- the ethoxy group of the silane is combined with TiO 2 , so that the carbon chains of the silane compound are arranged in a direction perpendicular to the surface of the fabric, and a super water-repellent surface can be implemented by arrangement in the vertical direction.
- Methyl 4-formyl benzoate (2.5 g, 15.24 mmol) was added to 25 mL of propionic acid, and pyrrole (1.02 g, 15.24 mmol) was slowly added dropwise and heated at 150 ° C for 12 hours in the dark. , cooled, and then filtered. Purification by column chromatography was performed to prepare a purple solid with a yield of 650 mg, 20%.
- a clear coating was produced on F by an ultrasonically assisted method (ultrasonic power and frequency of 100 W and 30 kHz) using a TiO 2 (T) solution. Then, the prepared sample was exposed to ammonia vapor to neutralize the surface.
- the porphyrin compound was dissolved in DMF (1x10 -5 M) and ultrasonically deposited on the fabric coated with TiO 2 (ultrasonic power and frequency of 100 W and 30 kHz).
- the TiO 2 coated fabric was immersed in a solution in which the porphyrin compound was dissolved, sonicated for 30 minutes, washed with DMF and water to remove excess unbound porphyrin compound, and dried.
- the silane compound is deposited on the porphyrin/TiO 2 coated fabric by immersing it in a solution (1x10 -5 M) in which a silane compound is dissolved in ethanol and sonicating for 30 minutes, drying it at 100° C. for about 1 hour, and then using an excess of ethanol.
- the fabric was washed to remove unbound silane compounds.
- NP, RB, EY, IN, BB and MB in chloroform or water (1.5x10 -3 M)
- PET@TP and PET@TPS surface-modified fabrics
- the self-cleaning effect of the modified fabric sample was determined by measuring the change in intensity under visible light irradiation and confirmed by recording the UV-Vis absorption spectrum at the changed time intervals.
- Curve a of FIG. 2B is a spectrum measurement result for PET fabric
- curve b is a TP-bound fabric (PET@TP)
- curve c is a spectrum measurement result on a TPS-bound fabric (PET@TPS).
- the absorbance peak for the soret band of the porphyrin compound exhibited a distinct red shift up to 19 nm after attachment to the fabric, and the shift of the peak is due to the interaction between the carboxylic acid group of the porphyrin compound and TiO 2 .
- the XRD analysis result is shown in FIG. 3 .
- Pristine fabric did not show a characteristic peak (Fig. 3a).
- the above results mean that the anatase TiO 2 nanoparticles were bound to the surface of the fabric.
- the XRD pattern of PET@TP was not significantly different from the XRD pattern of the fabric coated with TiO 2 , meaning that even after the porphyrin compound was bound, the anatase TiO 2 maintained its crystallinity. Finally, even in the case of the fabric bonded with the silane compound, the peak strength of TiO 2 was maintained.
- Figure 4 (a) can confirm the structure of the fabric, it can be confirmed the form such as a thin sheet.
- FIG. 4(b) shows that TiO 2 nanoparticles are bound, and TiO 2 having an average particle diameter of 200 nm is uniformly dispersed on the surface of the fabric.
- the PET@TP sample it was confirmed that the TiO 2 particle size increased, and some layered structure appeared.
- a silane compound is bonded to the surface of PET@ ⁇ W, the form in which TiO 2 nanoparticles are aggregated can be further confirmed.
- Mapping analysis (EDX) results for PET@TPS are as shown in FIG. 5, and were performed to confirm the presence of C, N, O, Si and Ti. As a result, the presence of Ti and Si on the surface of the modified fabric was confirmed.
- the analysis results are the same as in FIG. 6 , and it was confirmed that the analysis results consist of C, O, N, Si and Ti, and the results indicate that TiO 2 , a porphyrin compound and a silane compound are bonded to the fabric surface.
- the peak of 530.1 eV means that TiO 2 is present in the fabric.
- the N1s peak at 399.2 eV corresponds to the porphyrin ring of the pyrrole nitrogen.
- the additional peak at 103.5 eV is due to the Si2p peak of the silicate (Si-O), the Ti2p signal appears as two peaks at 458.8 (Ti2p3/2) and 464.2 eV (Ti2p1/2), and the O1s peak at 530.0 eV. is due to TiO 2 .
- the superhydrophobicity of the surface-modified fabrics was investigated by WCA (water contact angle) measurement.
- WCA water contact angle
- the PET surface has a WCA of 134°.
- the surface of PET is hydrophobic, but water droplets do not simply flow down when the surface is tilted.
- the fabric surface was modified with TiO 2 and WCA was increased (138°) to increase the hydrophobicity.
- WCA of the fabric surface after modification with a porphyrin compound is 0°, but the porphyrin compound is bound to the fabric surface to exhibit excellent photocatalytic activity.
- Organic contaminants and dyes such as EY, NP, BB, RB and IN were individually sprayed onto the fabric and PET@TP, and then irradiated with visible light for about 3 hours. 8 shows that discoloration occurs due to almost all contaminants except IN.
- the self-cleaning function through the photocatalytic activity of the fabric surface modified with PET@T, PET@TP and PET@TPS was confirmed through the resolution of harmful MB adsorbed on the surface.
- MB decomposition by irradiation with visible light can be visually confirmed, and in the case of the fabric without surface modification, there was no apparent color change on the surface.
- the intense color of MB gradually faded on the surface of the surface-modified fabric. The color change was confirmed through the UV-DRS spectrum as shown in FIG. 9 .
- the MB decomposition efficiency is in the order of PET@TP>PET@TPS>PET@T.
- the plot of C/C 0 versus time shown in FIG. 10 showed a good linear correlation between ln(C/C 0 ) and reaction time t(99.9%).
- the rate constant k of MB discoloration is derived from the following equation.
- the photocatalytic activity was reduced due to the phenomenon that the surface of the fabric to which the silane compound is bonded is covered by the silane compound, the TiO 2 surface coated with the porphyrin compound.
- superhydrophobicity is realized on the surface by the silane compound, and PET@TPS, a fabric bonded with a silane compound, exhibits a double self-cleaning effect.
- the stability and reusability of the fabric combined with TiO 2 /porphyrin compound were confirmed.
- the TiO 2 has excellent adhesive properties and can be easily combined with fabrics and porphyrin compounds. Therefore, after exposure to water and petroleum, washing with detergent, TiO 2 and the stability of the porphyrin compound bound fabric was evaluated. As a result, no obvious change in the Q-band of the porphyrin was observed.
- the above result means that the fabric surface to which TiO 2 and the porphyrin compound are bonded maintains stability and reusability, which is due to the strong interaction by the carboxylate group of the porphyrin compound and TiO 2 .
- WCA was measured to evaluate the stability of the superhydrophobic surface. It was confirmed that the stability of the PET@TP was due to the strong affinity of TiO 2 for the carboxylate group of the porphyrin compound. Samples were washed in detergent, petroleum and water, and binding of silane compounds to the surface was assessed. After 5 wash cycles, the WCA decreased slightly from 152° to 150° for the PET@TPS fabric sample. In addition, after irradiation with visible light, the light stability of the surface was measured before and after 24 hours. As a result of the above experiment, a sharp decrease in WCA was not observed. This result means that water repellency and light stability are maintained in the fabric to which the silane compound is bonded.
- the mechanism for MB degradation on the fabric surface is shown in FIG. 11 .
- the surface-modified sample is excited to generate holes and electrons. After light absorption by the porphyrin compound, the excited electrons leave the ground state (HOMO orbital) and cross the system. The excited level electrons (in the LUMO orbital) are easily transferred to the CB of TiO 2 .
- the modified surface reacts with oxygen to generate active superoxide radicals and subsequent protons donate the HOO ⁇ radical, which competes with the dye+ ⁇ through reverse electron transfer.
- the silane-modified surface maintains superhydrophobicity even after irradiation, because OH ⁇ on the TiO2 surface is destroyed through dye sensitization to maintain hydrophobicity.
- An ink was prepared by mixing a silane compound (0.5 g) in an ethanol (10 mL) solution, and the ink composition was injected into a cartridge [dye (2.5x10 -3 M) was added to the ink to facilitate visualization]. .
- a Canon (MG2590) printer and cartridge (CL-946) were used, and an image was printed on the surface of the fabric to which TiO 2 /Porphyrin compound was bound. The water contact angle was measured by dropping water droplets on the printed image area and the non-image printed area on the fabric. Experimental results show that the printed image area is superhydrophobic with a WCA of 150°, and the remaining fabric area is hydrophilic. It was confirmed that the silin compound of the present invention can be utilized as a material capable of implementing superhydrophobicity on the surface of a fabric by using digital printing.
- the present invention relates to a self-cleaning composition and a self-cleaning fabric comprising the same, and more particularly, it is possible to prevent adhesion of contaminants by implementing a super water-repellent surface, and to prevent contamination through decomposition of the attached contaminants. It relates to a self-cleaning composition and a self-cleaning fabric comprising the same.
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Abstract
The present invention relates to a self-cleaning composition and a self-cleaning fabric comprising same, and can prevent adhesion of a contaminant by forming a coating layer on the surface of a textile and giving an ultra-hydrophobic property, and decompose the contaminant through a photocatalytic effect, caused by visible light sensitivity, for the contaminant substance adhered onto the surface of the textile. The present invention can also provide a textile capable of self-cleaning due to a photocatalytic effect caused by visible light sensitivity and due to an ultra-hydrophobic property by digitally printing an ultra-hydrophobic ink composition on a textile coated with a photocatalytic composition.
Description
본 발명은 자기 세정용 조성물 및 이를 포함하는 자기 세정용 직물에 관한 것으로, 보다 구체적으로 초발수 표면을 구현하여 오염물의 부착을 방지할 수 있고, 부착된 오염물에 대한 분해를 통해 오염을 방지할 수 있는 자기 세정용 조성물 및 이를 포함하는 자기 세정용 직물에 관한 것이다.The present invention relates to a self-cleaning composition and a self-cleaning fabric comprising the same, and more particularly, it is possible to prevent adhesion of contaminants by implementing a super water-repellent surface, and to prevent contamination through decomposition of the attached contaminants. It relates to a self-cleaning composition and a self-cleaning fabric comprising the same.
통상적으로 섬유용으로 이용되는 발수제는 크게, 왁스계, 고급알콜계, 실리콘계 및 불소계 발수제가 있다. 이 중 불소계 발수제는 불소의 기본 물성에 기인하여 가장 발수성이 우수하고, 또한 발유성까지 얻을 수 있는 장점으로 인하여 가장 유용하게 사용되고 있는 발수제이다.Generally, water repellents used for fibers are largely wax-based, higher alcohol-based, silicone-based and fluorine-based water repellents. Among them, the fluorine-based water repellent has the most excellent water repellency due to the basic physical properties of fluorine and is the most useful water repellent because of the advantage of obtaining oil repellency.
그러나 섬유에 적용되는 특성상 사용 중 각종 오염물에 노출되며, 반복적인 세탁과정을 거치면서 발수성능의 저하는 필연적이다. 통상 세탁과정을 10여 회를 거치면 초기 발수성능의 50% 이하의 발수도만을 나타내게 된다. However, due to the nature of its application to textiles, it is exposed to various contaminants during use, and the decrease in water repellency performance is inevitable through repeated washing processes. In general, if the washing process is repeated 10 times, only the water repellency of 50% or less of the initial water repellency is displayed.
이는 불소계 발수제는 가장 우수한 발수(Hydrophobic)성 물질로써 물에 대한 용해력이 전혀 없기 때문에 내세탁시에도 발수성능의 저하가 없어야 함에도 불구하고, 불소계 발수제를 섬유에 처리하기 위해서는 물에 용해시키는 공정을 거쳐야 하기 때문에 계면활성제라는 성분을 사용하여 강제 유화시킨 후 원단에 처리하는 과정을 거치게 된다. This is because the fluorine-based water repellent is the most excellent hydrophobic material and has no water dissolving power, so there should be no deterioration in water repellency even during washing resistance. Therefore, it is forced to emulsify using a component called a surfactant and then goes through a process of treating the fabric.
이때, 불소계 수지 내에 혹은 원단 내에 잔류하는 계면활성제 성분은 매우 친수적(Hydrophilic) 성질을 가지고 있기 때문에 세탁 시 불소 발수제 성분의 탈락을 가속화시켜 결국 수 회 세탁과정에서 발수성능의 저하를 초래하게 되는 것이다.At this time, since the surfactant component remaining in the fluororesin or in the fabric has a very hydrophilic property, it accelerates the removal of the fluorine water repellent component during washing, resulting in a decrease in water repellency performance in the process of washing several times. .
통상의 세탁 후 발수성 저하를 개선하기 위해서는 불소수지의 가교화도를 높여 탈락을 지연시키는 가교제를 별도로 첨가하여 가공하는 방법이 선호되고 있다. In order to improve the water repellency degradation after normal washing, a method of processing by separately adding a crosslinking agent that delays drop-off by increasing the degree of crosslinking of the fluororesin is preferred.
가장 많이 이용되는 가교제 종류로는 블록화 이소시아네이트가 사용되는데, 블록화 이소시아네이트는 고온(주로 150℃ 이상)에서 해리되면 이소시아네이트는 불소수지에 대해 가교결합제로서 역할을 하여 불소 발수제와 섬유간의 결합력을 향상시키며, 또한 3차원 망상구조를 이루어 내구 성을 향상시킨다고 보고되어 있다.Blocked isocyanate is used as the most used crosslinking agent type. When blocked isocyanate is dissociated at high temperature (mainly above 150° C.), the isocyanate acts as a crosslinking agent for the fluororesin, thereby improving the bonding strength between the fluorine water repellent and the fibers. It has been reported to improve durability by forming a three-dimensional network structure.
다만, 이러한 불소계 발수제의 사용은, 불소 화합물의 경우, 매우 안정적이고 고가이며, 생분해성이 없어 동물과 식물의 생명에 심각한 영향을 줄 수 있는 잠재적인 환경 오염 문제를 초래할 수 있는 문제가 있다. However, the use of such a fluorine-based water repellent, in the case of a fluorine compound, is very stable, expensive, and has a problem that it is not biodegradable and may cause a potential environmental pollution problem that can seriously affect the lives of animals and plants.
이에, 불소 화합물을 포함하지 않는 발수제의 개발이 필요하며, 발수제를 적용하여, 섬유, 종이, 직물 등에 발수성을 부여하기 위한 공정이 단순하고, 저비용이며, 친환경적인 화합물의 사용이 필요한 상황으로, 이러한 제품의 개발이 절실히 요구되고 있다.Accordingly, it is necessary to develop a water repellent that does not contain a fluorine compound, and by applying the water repellent, the process for imparting water repellency to fibers, paper, fabric, etc. is simple, low cost, and the use of an eco-friendly compound is required. Product development is urgently required.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
KR 10-2013-0075956 A1KR 10-2013-0075956 A1
본 발명의 목적은 자기 세정용 조성물 및 이를 포함하는 자기 세정용 직물을 제공하는 것이다. It is an object of the present invention to provide a self-cleaning composition and a self-cleaning fabric comprising the same.
본 발명의 다른 목적은 직물 표면에 코팅층을 형성하여, 초발수성을 부여하여 오염물의 흡착을 방지하고, 직물의 표면에 흡착된 오염 물질에 대해 가시광 감응에 의한 광촉매 효과로 오염물을 분해할 수 있는 자기 세정용 조성물을 제공하는 것이다. Another object of the present invention is to form a coating layer on the surface of the fabric to provide super water repellency to prevent the adsorption of contaminants, and to decompose contaminants through the photocatalytic effect of the visible light response to the contaminants adsorbed on the surface of the fabric. To provide a cleaning composition.
본 발명의 다른 목적은 광촉매 조성물이 결합된 직물에 초발수성 잉크 조성물을 디지털 프린팅하여 초발수 및 가시광 감응에 의한 광촉매 효과에 의한 자기 세정이 가능한 직물을 제공하는 것이다.Another object of the present invention is to provide a fabric capable of self-cleaning by digital printing of a super water-repellent ink composition on a fabric to which a photocatalytic composition is bonded, thereby superhydrophobicity and a photocatalytic effect by visible light sensitivity.
상기 목적을 달성하기 위하여, 본 발명의 일 실시예에 따른 자기 세정용 조성물은 TiO2; 하기 화학식 1로 표시되는 포피린 화합물; 및 하기 화학식 2로 표시되는 실란 화합물을 포함하며, 상기 포피린 화합물 및 실란 화합물은 TiO2와 결합하는 것이다:In order to achieve the above object, the self-cleaning composition according to an embodiment of the present invention is TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound are bonded to TiO 2 :
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
X1 및 X3는 서로 동일하거나 상이하며 각각 독립적으로 N(R13), C(R14)(R15), O 및 S로 이루어진 군으로부터 선택되며,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 13 ), C(R 14 )(R 15 ), O and S,
X2 및 X4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R16)이며,X 2 And X 4 Are the same as or different from each other, each independently N or C (R 16 ),
L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, 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,
R1 내지 R16은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며, 인접하는 기와 서로 결합하거나, 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Arylalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 An aralkylamino group of 30, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or It is selected from the group consisting of an 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,
L5는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기로 이루어진 군으로부터 선택되며,L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
R17 내지 R19는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐기 또는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기이며,R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
R20은 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기 및 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기로 이루어진 군으로부터 선택되며,R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and a substituted or unsubstituted C1-C30 heteroaryl group It is selected from the group consisting of an alkoxy group,
상기 L1 내지 L5 및 R1 내지 R20이 치환되는 경우, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 카복실기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 알킬티오기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 2 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되는 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When the L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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. group, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, ar having 6 to 30 carbon atoms It is substituted with a substituent selected from the group consisting of an alkylamino group, 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. When substituted with a substituent, they are the same as or different from each other.
상기 화학식 1로 표시되는 포피린 화합물은 하기 화학식 3으로 표시되는 화합물이다:The porphyrin compound represented by Formula 1 is a compound represented by Formula 3 below:
[화학식 3][Formula 3]
여기서, here,
R1 내지 R12 및 L1 내지 L4는 상기 화학식 1에서 정의한 바와 같다.R 1 to R 12 and L 1 to L 4 are as defined in Formula 1 above.
상기 R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기일 수 있다.Wherein R 1 to R 8 are the same as or different from each other, and may each independently be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.
상기 L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기일 수 있다.The L 1 to L 4 may be the same as or different from each other, and each independently may be a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
상기 L5는 탄소수 1 내지 30의 알킬기이다.The L 5 is an alkyl group having 1 to 30 carbon atoms.
상기 R18 내지 R20은 탄소수 1 내지 30의 알킬기이다.Wherein R 18 to R 20 are an alkyl group having 1 to 30 carbon atoms.
상기 자기 세정용 조성물은 직물의 표면에 TiO2가 결합되고, 상기 직물에 결합된 TiO2에 포피린 화합물 및 실란 화합물이 결합되어 초발수성 및 가시광 감응 광촉매로 작용하는 것이다. In the self-cleaning composition, TiO 2 is bound to the surface of the fabric, and a porphyrin compound and a silane compound are bound to TiO 2 bound to the fabric to act as a superhydrophobic and visible light-sensitive photocatalyst.
본 발명의 다른 일 실시예에 따른 자기 세정용 직물은 상기 자기 세정용 조성물을 포함한다. The self-cleaning fabric according to another embodiment of the present invention includes the self-cleaning composition.
상기 자기 세정용 직물은 표면에 TiO2가 결합되고, 상기 TiO2에 포피린 화합물이 결합되어 가시광 감응 광촉매로 작용하며, 상기 TiO2에 실란 화합물이 결합되어 초발수성을 나타낼 수 있다. In the self-cleaning fabric, TiO 2 is bonded to the surface, the porphyrin compound is bonded to TiO 2 to act as a visible light-sensitive photocatalyst, and the silane compound is bonded to TiO 2 to exhibit super water repellency.
상기 실란 화합물은 잉크 조성물에 포함되어 디지털 프린터를 통해 직물의 표면에 인쇄면으로 출력되어 초발수성을 나타낼 수 있다. The silane compound may be included in the ink composition and printed on the surface of the fabric through a digital printer to exhibit super water repellency.
본 발명에서 “수소”는 수소, 경수소, 중수소 또는 삼중수소이다.In the present invention, "hydrogen" is hydrogen, light hydrogen, deuterium or tritium.
본 발명에서 “할로겐기”는 불소, 염소, 브롬 또는 요오드이다.In the present invention, the “halogen group” is fluorine, chlorine, bromine or iodine.
본 발명에서 “알킬”은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있으나, 이에 한정되지는 않는다.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.
본 발명에서 “알케닐(alkenyl)”은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있으나, 이에 한정되지는 않는다.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, allyl, isopropenyl, 2-butenyl, and the like.
본 발명에서 “알키닐(alkynyl)”은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “alkynyl” 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 triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.
본 발명에서 “아릴”은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴, 플루오닐, 다이메틸플루오레닐 등을 들 수 있으나, 이에 한정되지는 않는다.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.
본 발명에서 “헤테로아릴”은 탄소수 6 내지 30개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있으나, 이에 한정되지는 않는다.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 in the ring, preferably 1 to 3 carbons, 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, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.
본 발명에서 "아르알킬"은, 아릴 및 알킬이 상기한 바와 같은 아릴-알킬 그룹을 의미한다. 바람직한 아르알킬은 저급 알킬 그룹을 포함한다. 적합한 아르알킬 그룹의 비제한적인 예는 벤질, 2-펜에틸 및 나프탈레닐메틸을 포함한다. 모 잔기에 대한 결합은 알킬을 통해 이루어진다.As used herein, "aralkyl" refers to an aryl-alkyl group wherein 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.
본 발명에서 “헤테로아릴알킬기”는 헤테로고리기로 치환된 아릴-알킬 그룹을 의미한다. In the present invention, “heteroarylalkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.
본 발명에서 “축합고리”는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.In the present invention, “condensed ring” refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
본 발명에서 "인접하는 기와 서로 결합하여 고리를 형성한다"는 것은 인접하는 기와 서로 결합하여 치환 또는 비치환된 지방족 탄화수소고리; 치환 또는 비치환된 방향족 탄화수소고리; 치환 또는 비치환된 지방족 헤테로고리; 치환 또는 비치환된 방향족 헤테로고리; 또는 이들의 축합고리를 형성하는 것을 의미한다.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.
본 발명에서 "치환"은 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.In the present invention, "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.
본 발명은 직물 표면에 코팅층을 형성하여, 초발수성을 부여하여 오염물의 흡착을 방지하고, 직물의 표면에 흡착된 오염 물질에 대해 가시광 감응에 의한 광촉매 효과로 오염물을 분해할 수 있다. According to the present invention, a coating layer is formed on the surface of a fabric to provide super water repellency to prevent adsorption of contaminants, and contaminants can be decomposed by a photocatalytic effect by response to visible light for contaminants adsorbed on the surface of the fabric.
또한, 광촉매 조성물이 코팅된 직물에 초발수성 잉크 조성물을 디지털 프린팅하여 초발수 및 가시광 감응에 의한 광촉매 효과에 의한 자기 세정이 가능한 직물을 제공할 수 있다.In addition, by digitally printing the super water-repellent ink composition on the fabric coated with the photocatalyst composition, it is possible to provide a fabric capable of self-cleaning by the photocatalytic effect of super water repellency and visible light sensitivity.
도 1은 본 발명의 일 실시예에 따른 표면 개질된 직물에 관한 1 is a surface-modified fabric according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 UV-VIS 스펙트럼 측정 결과이며, 도 2A는 포피린 화합물에 대한 스펙트럼 측정 결과이고, 도 2B는 PET 직물, PET@TP 및 PET@TPS에 대한 스펙트럼 측정 결과이다.2 is a UV-VIS spectrum measurement result according to an embodiment of the present invention, FIG. 2A is a spectrum measurement result for a porphyrin compound, and FIG. 2B is a spectrum measurement result for PET fabric, PET@TP and PET@TPS .
도 3은 본 발명의 일 실시예에 따른 직물의 XRD 측정 결과이다.3 is an XRD measurement result of a fabric according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 직물의 SEM 측정 사진이다. 4 is an SEM measurement photograph of a fabric according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 PET@TPS에 대한 EDX 분석 결과이다.5 is an EDX analysis result for PET@TPS according to an embodiment of the present invention.
도 6은 본 발명의 일 실시예에 따른 PET@TPS에 대한 XPS 측정 결과이다. 6 is an XPS measurement result for PET@TPS according to an embodiment of the present invention.
도 7은 본 발명의 일 실시예에 따른 직물 표면에 대한 발수각 측정 결과이다. 7 is a water repellency measurement result for the surface of the fabric according to an embodiment of the present invention.
도 8은 본 발명의 일 실시예에 따른 직물 표면에 대한 유기 염료의 광분해 분석 결과이다. 8 is a photolysis analysis result of an organic dye on a fabric surface according to an embodiment of the present invention.
도 9는 본 발명의 일 실시예에 따른 직물 표면에 대한 UV-DRS 스펙트럼 측정 결과이다. 9 is a UV-DRS spectrum measurement result of the fabric surface according to an embodiment of the present invention.
도 10은 본 발명의 일 실시예에 따른 시간의 경과에 따른 C/C0의 상관 관계에 대한 결과이다.10 is a result of the correlation of C/C0 over time according to an embodiment of the present invention.
도 11은 본 발명의 일 실시예에 따른 직물 표면에서의 MB 분해에 대한 메커니즘이다.11 is a mechanism for MB degradation at the fabric surface according to an embodiment of the present invention.
도 12는 본 발명의 일 실시예에 따른 직물 표면에서의 오염 분해에 대한 실험 결과이다.12 is an experimental result for decomposition of contamination on the surface of the fabric according to an embodiment of the present invention.
도 13은 본 발명의 일 실시예에 따른 실란 화합물의 잉크 조성물로의 제조 및 인쇄 영역 및 비인쇄 영역에 대한 발수 실험 결과이다.13 is a result of a water repellency test for a printing area and a non-printing area and manufacturing the ink composition of a silane compound according to an embodiment of the present invention.
본 발명은 TiO2; 하기 화학식 1로 표시되는 포피린 화합물; 및 하기 화학식 2로 표시되는 실란 화합물을 포함하며, 상기 포피린 화합물 및 실란 화합물은 TiO2와 결합하는 자기 세정용 조성물에 관한 것이다:The present invention is TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound are TiO 2 It relates to a self-cleaning composition that binds to:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
X1 및 X3는 서로 동일하거나 상이하며 각각 독립적으로 N(R13), C(R14)(R15), O 및 S로 이루어진 군으로부터 선택되며,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 13 ), C(R 14 )(R 15 ), O and S,
X2 및 X4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R16)이며,X 2 And X 4 Are the same as or different from each other, each independently N or C (R 16 ),
L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, 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,
R1 내지 R16은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며, 인접하는 기와 서로 결합하거나, 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Arylalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 An aralkylamino group of 30, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or It is selected from the group consisting of an 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,
L5는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기로 이루어진 군으로부터 선택되며,L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
R17 내지 R19는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐기 또는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기이며,R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
R20은 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기 및 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기로 이루어진 군으로부터 선택되며,R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and a substituted or unsubstituted C1-C30 heteroaryl group It is selected from the group consisting of an alkoxy group,
상기 L1 내지 L5 및 R1 내지 R20이 치환되는 경우, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 카복실기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 알킬티오기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 2 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되는 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When the L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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. group, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, ar having 6 to 30 carbon atoms It is substituted with a substituent selected from the group consisting of an alkylamino group, 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. When substituted with a substituent, they are the same as or different from each other.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.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 several different forms and is not limited to the embodiments described herein.
자기 세정, 오염 물질 및 미생물로부터 보호, 탈취와 같은 특정 요구 사항을 충족하기 위해 섬유를 기능화하기 위한 다양한 시도가 존재하였다. 특히, 자가 세정용 섬유 소재는 상업적 용도로 일상 생활에서 다양하게 활용이 가능하다. Various attempts have been made to functionalize fibers to meet specific requirements, such as self-cleaning, protection from contaminants and microorganisms, and deodorization. In particular, the self-cleaning textile material can be used in various ways in daily life for commercial purposes.
섬유를 소수성 또는 친수성 화합물로 코팅함으로 인한 자기 세정 특성을 나타내는 자기 세정용 표면은 상기의 특성을 발휘하기 위해, 급격한 발전이 진행되었다. 상기 재료는 섬유 또는 직물로써의 기본적인 특성 외에도 초소수성과 같은 특성을 나타내야 하며, 상기 특성으로 인해, 점착 방지, 결빙 방지, 김서림 방지, 오염 방지, 자가 세정 및 물/오일 분리 등의 다양한 활용이 가능하다. A self-cleaning surface exhibiting self-cleaning properties due to coating the fibers with a hydrophobic or hydrophilic compound has undergone rapid development in order to exhibit the above properties. In addition to the basic properties of fibers or fabrics, the material should exhibit properties such as superhydrophobicity, and due to the above properties, various uses such as anti-sticking, anti-icing, anti-fog, anti-pollution, self-cleaning and water/oil separation are possible do.
표면의 물 접촉각이 150°보다 큰 경우에 초소수성을 나타낸다고 한다. 또한, 표면이 10° 미만이면 발수성이 있어 자가 세정 효과를 나타낸다고 한다. When the surface water contact angle is greater than 150°, it is said to exhibit superhydrophobicity. In addition, if the surface is less than 10°, it is said that it has water repellency and shows a self-cleaning effect.
상기와 같은 특성이 나타나는 경우는 표면 에너지가 낮고 충분한 표면 거칠기를 가져, 직물의 표면에 물을 접촉시킴으로 먼지를 쉽게 제거할 수 있다. 상기와 같은 초발수 특성을 나타내는 직물 표면에 대한 제작은 연잎 및 소금쟁이를 포함한 자연에서 영감을 받아, 제조될 수 있다. When the above characteristics appear, the surface energy is low and has sufficient surface roughness, and dust can be easily removed by contacting water with the surface of the fabric. Fabrication for the surface of the fabric exhibiting the super water-repellent properties as described above, inspired by nature, including lotus leaves and water strider, can be manufactured.
TiO2 NPs와 같은 금속 산화물 나노 입자 및 광촉매 변형을 통한 친수성 자가 세정용 섬유 재료는 광범위한 용도로 적용될 수 있다.Metal oxide nanoparticles such as TiO 2 NPs and hydrophilic self-cleaning fiber materials through photocatalytic modification can be applied to a wide range of applications.
일반적으로 TiO2는 높은 안정성을 나타내며, 무독성이고, 저렴하며 우수한 산화 능력을 가진 신뢰할 수 있는 친환경적인 광촉매 중 하나이다. 이러한 다결정 반도체 산화물은 광학적 특성을 나타내며 상기 광활성 물질은 빛 아래에서 광산화 및 광 환원 반응에 의해 흡수된 오염 물질을 자발적으로 분해하여 제거할 수 있다. In general, TiO 2 shows high stability, is non-toxic, is inexpensive, and is one of the reliable and environmentally friendly photocatalysts with excellent oxidation ability. The polycrystalline semiconductor oxide exhibits optical properties, and the photoactive material can spontaneously decompose and remove contaminants absorbed by photooxidation and photoreduction reactions under light.
다만, 종이, 직물 및 플라스틱과 같은 유연한 표면은 열적, 내화학적인 문제로 인해, TiO2를 부착이 용이하지 않다. 최근 연구에 의하면, 나노 크기의 TiO2를 섬유질 재료에 증착하기 위해, 졸-겔, 열수, 함침, 화학적 스페이서 부착 및 스퍼터링 방법을 포함한 다양한 방법이 제시되고 있다. However, it is not easy to attach TiO 2 to flexible surfaces such as paper, fabric, and plastic due to thermal and chemical resistance problems. According to recent studies, various methods including sol-gel, hot water, impregnation, chemical spacer attachment and sputtering methods have been proposed to deposit nano-sized TiO 2 on fibrous materials.
최근 UV 활성 특성을 가진 자기 세정 특성을 가진 직물을 위해, 천연 섬유 및 합성 섬유에 이산화 티타늄 나노 결정을 생산하기 위한 다양한 연구가 진행되고 있다. 다만, 상기 재료는 TiO2(~ 3.2eV)의 광범위한 밴드갭으로 인해 가시 광선에서 자기 세정 특성을 나타내지 않는다. 상기 TiO2는 광 흡수 영역이 약 385nm이므로, 금속 및 비금속의 도핑을 통해, 광 흡수 영역을 가시광선 영역으로 이동하기 위해 다양한 접근 방식이 연구되었다. 염료 감응은 관찰 가능한 영역에서 광촉매 활성을 가져 또 다른 방법이다. 포피린 및 TiO2의 결합에 의한 염료 감응은 450nm 영역 (Soret 밴드)에서 고체 밴드가 생성되고 약 500-700nm에서 약한 Q 밴드가 생성된다. 상기 공정을 통해 얻은 개질된 표면은 뛰어난 자기 세정 특성을 가질 수 있으며 가시 광선에 노출에 의해 자기 세정 효과를 발휘할 수 있다. Recently, various studies have been conducted to produce titanium dioxide nanocrystals on natural fibers and synthetic fibers for fabrics with self-cleaning properties with UV activity properties. However, the material does not exhibit self-cleaning properties in visible light due to the wide bandgap of TiO 2 (~ 3.2 eV). Since the TiO 2 has a light absorption region of about 385 nm, various approaches have been studied to move the light absorption region to the visible light region through doping of metals and non-metals. Dye sensitization is another method with photocatalytic activity in the observable region. Dye sensitization by the binding of porphyrin and TiO 2 produces a solid band in the 450 nm region (Soret band) and a weak Q band at about 500-700 nm. The modified surface obtained through the above process may have excellent self-cleaning properties and may exhibit a self-cleaning effect by exposure to visible light.
소수성 및 광촉매 특성을 직물에 통합하여 얻을 수 있는 자체 세척 특성은 두 가지 장점이 있다. 1) 직물의 발수성 특성으로 인해 물에 녹는 불순물이 제거되고 2) 유기 염료 및 기타 일반적인 얼룩 유발 물질이 광촉매에 의해 분해될 수 있다.The self-cleaning properties that can be achieved by incorporating hydrophobic and photocatalytic properties into the fabric have two advantages. 1) Water-soluble impurities are removed due to the water-repellent properties of the fabric, and 2) organic dyes and other common stain-causing substances can be decomposed by the photocatalyst.
본 발명은 세정 효과를 높이기 위해 신규한 포피린 화합물 및 신규한 실란 유도체를 개발하고 이를 직물에 부착하여 물성을 높였다. 본 발명에서는 비불소 화합물을 포함하는 것을 특징으로 한다. 상기 실란은 플루오르화 실란과 비교할 때 독성이 덜하다. 제조된 포피린 화합물은 메조 위치에 카르복실레이트 치환된 페닐기를 포함하며, 베타 위치는 페닐 고리를 치환기로 포함하여, TiO2 광촉매 거동에 영향을 미친다. The present invention developed a novel porphyrin compound and a novel silane derivative in order to increase the cleaning effect, and attached them to a fabric to improve physical properties. In the present invention, it is characterized in that it contains a non-fluorine compound. These silanes are less toxic when compared to fluorinated silanes. The prepared porphyrin compound includes a phenyl group substituted with a carboxylate at the meso position, and includes a phenyl ring as a substituent at the beta position, thereby affecting the TiO2 photocatalytic behavior.
또한, 다수의 탄소가 결합된 사슬을 가진 실란 화합물을 직물의 표면에 결합시켜, 직물 표면에 소수성을 부여하였다. In addition, by bonding a silane compound having a chain to which a plurality of carbons are bonded to the surface of the fabric, hydrophobicity was imparted to the surface of the fabric.
이후, 본 발명의 유기 오염 물질의 분해 효과를 확인하기 위해, 가시광선 조사 하에서, 니트로페놀 (NP), 로다민 B(RB), 에오신 Y(EY), 인디고(IN), 브로모 페놀 블루(BB) 및 메틸렌 블루(MB)와 같은 유기 오염 물질에 대한 분해 능력 및 커피, 간장 등의 물질에 대한 분해 능력을 확인하고, 물 접촉각을 측정하여 소수성 특성을 평가하였다. Then, in order to confirm the decomposition effect of the organic pollutants of the present invention, under visible light irradiation, nitrophenol (NP), rhodamine B (RB), eosin Y (EY), indigo (IN), bromophenol blue ( BB) and organic contaminants such as MB) and decomposing ability for substances such as coffee and soy sauce were checked, and hydrophobicity properties were evaluated by measuring a water contact angle.
또한, 상기 실란 화합물은 소수성 잉크로 제조하여, 디지털 프린팅을 통해, 직물의 표면에 소수성 표면으로의 출력 가능 여부에 대해서도 확인하였다. In addition, the silane compound was prepared with a hydrophobic ink, and it was also confirmed whether printing on the surface of the fabric as a hydrophobic surface was possible through digital printing.
본 발명의 일 실시예에 따른 자기 세정용 조성물은 TiO2; 하기 화학식 1로 표시되는 포피린 화합물; 및 하기 화학식 2로 표시되는 실란 화합물을 포함하며, 상기 포피린 화합물 및 실란 화합물은 TiO2와 결합할 수 있다:The self-cleaning composition according to an embodiment of the present invention includes TiO 2 ; a porphyrin compound represented by the following formula (1); and a silane compound represented by the following Chemical Formula 2, wherein the porphyrin compound and the silane compound may be combined with TiO 2 .
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
X1 및 X3는 서로 동일하거나 상이하며 각각 독립적으로 N(R13), C(R14)(R15), O 및 S로 이루어진 군으로부터 선택되며,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 13 ), C(R 14 )(R 15 ), O and S,
X2 및 X4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R16)이며,X 2 And X 4 Are the same as or different from each other, each independently N or C (R 16 ),
L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, 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,
R1 내지 R16은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며, 인접하는 기와 서로 결합하거나, 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Arylalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 An aralkylamino group of 30, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or It is selected from the group consisting of an 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,
L5는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기로 이루어진 군으로부터 선택되며,L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,
R17 내지 R19는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐기 또는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기이며,R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,
R20은 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기 및 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기로 이루어진 군으로부터 선택되며,R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and a substituted or unsubstituted C1-C30 heteroaryl group It is selected from the group consisting of an alkoxy group,
상기 L1 내지 L5 및 R1 내지 R20이 치환되는 경우, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 카복실기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 알킬티오기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 2 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되는 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When the L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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. group, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, ar having 6 to 30 carbon atoms It is substituted with a substituent selected from the group consisting of an alkylamino group, 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. When substituted with a substituent, they are the same as or different from each other.
상기 화학식 1로 표시되는 포피린 화합물은 하기 화학식 3으로 표시되는 화합물일 수 있다:The porphyrin compound represented by Formula 1 may be a compound represented by Formula 3 below:
[화학식 3][Formula 3]
여기서, here,
R1 내지 R12 및 L1 내지 L4는 상기 화학식 1에서 정의한 바와 같다. R 1 to R 12 and L 1 to L 4 are as defined in Formula 1 above.
상기 R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기일 수 있다. Wherein R 1 to R 8 are the same as or different from each other, and may each independently be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.
상기 L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기일 수 있다. The L 1 to L 4 may be the same as or different from each other, and each independently may be a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
보다 바람직하게, 상기 R1 내지 R8은 비치환된 페닐기이고, L1 내지 L4는 치환된 페닐기이며, 상기 L1 내지 L4는 카복실기로 치환될 수 있다. More preferably, R 1 to R 8 may be an unsubstituted phenyl group, L 1 to L 4 may be a substituted phenyl group, and L 1 to L 4 may be substituted with a carboxyl group.
상기 포피린 화합물은 TiO2와 결합에 의해, TiO2 광촉매의 광 흡수 영역대를 가시광 영역으로 이동하게 할 수 있고, 상기 포피린 화합물은 4개의 카복실기를 포함함에 따라, TiO2와 결합하는 부분이 복수로 포함됨에 따라, 결합력을 높여 세탁 등의 반복 사용에 의해서도 광촉매의 효율을 유지할 수 있다.The porphyrin compound may move the light absorption region of the TiO 2 photocatalyst to the visible region by bonding with TiO 2 , and as the porphyrin compound includes four carboxyl groups, the portion bonding with TiO 2 is plural. As it is included, the efficiency of the photocatalyst can be maintained even by repeated use such as washing by increasing the binding force.
상기 화학식 2로 표시되는 실란 화합물은 보다 구체적으로 상기 L5는 탄소수 1 내지 30의 알킬기이며, 상기 R18 내지 R20은 탄소수 1 내지 30의 알킬기인 것을 특징으로 한다. More specifically, the silane compound represented by Formula 2 is characterized in that L 5 is an alkyl group having 1 to 30 carbon atoms, and R 18 to R 20 are an alkyl group having 1 to 30 carbon atoms.
보다 구체적으로, 상기 L5는 탄소수 20인 메틸렌기이며, R18 내지 R20은 탄소수 2의 에틸기이다. 상기 실란 화합물은 탄소수 22개의 탄소 사슬이 결합된 실란 화합물로, 탄소 사슬에 의해 직물의 표면에서 초발수 특성을 나타내는 것을 특징으로 한다. 즉, 치환기로 불소를 포함하지 않으면서도, 탄소 사슬에 의한 발수 효과를 나타낼 수 있다. More specifically, L 5 is a methylene group having 20 carbon atoms, and R 18 to R 20 are an ethyl group having 2 carbon atoms. The silane compound is a silane compound to which a carbon chain having 22 carbon atoms is bonded, and is characterized in that it exhibits super water-repellent properties on the surface of the fabric by the carbon chain. That is, it is possible to exhibit a water-repellent effect due to the carbon chain without including fluorine as a substituent.
보다 구체적으로, 상기 자기 세정용 조성물은 직물의 표면에 TiO2가 결합되고, 상기 직물에 결합된 TiO2에 포피린 화합물 및 실란 화합물이 결합되어 초발수성 및 가시광 감응 광촉매로 작용할 수 있다. More specifically, in the self-cleaning composition, TiO 2 is bound to the surface of the fabric, and a porphyrin compound and a silane compound are bound to TiO 2 bound to the fabric to act as a superhydrophobic and visible light-sensitive photocatalyst.
도 1은 본 발명의 일 실시예에 따른 자기 세정용 조성물이 코팅된 직물의 표면에 대한 개념도로, 상기 개념도에 따르면, 직물의 표면에 아나타제 TiO2가 결합되고, 상기 TiO2의 -OH기는 포피린 화합물의 -COOH기와 결합하게 되며, 상기 포피린 화합물의 -COOH기는 하나의 화합물에 4개씩 포함하고 있어, 4곳에서 TiO2와 결합하게 되어, 우수한 결합력을 나타낼 수 있다. 또한, 실란 화합물 역시, 실란의 에톡시기가 TiO2와 결합하게 되어, 직물의 표면에 대한 수직 방향으로 실란 화합물의 탄소 사슬이 배열되게 되고, 수직 방향으로 배열에 의해 초발수 표면을 구현할 수 있다. 1 is a conceptual diagram of a surface of a fabric coated with a self-cleaning composition according to an embodiment of the present invention. According to the conceptual diagram, anatase TiO 2 is bonded to the surface of the fabric, and the -OH group of TiO 2 is porphyrin. It is bound to the -COOH group of the compound, and the -COOH group of the porphyrin compound is included in one compound by four, so that it is bound to TiO 2 in four places, thereby exhibiting excellent bonding strength. In addition, in the silane compound, the ethoxy group of the silane is combined with TiO 2 , so that the carbon chains of the silane compound are arranged in a direction perpendicular to the surface of the fabric, and a super water-repellent surface can be implemented by arrangement in the vertical direction.
제조예production example
(4,4',4'',4'''-(2,3,7,8,12,13,17,18-옥타페닐포피린-5,10,15,20- 테트라일) 테트라 벤조익산)의 합성(4,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoic acid ) synthesis
테트라 메틸 4,4',4'',4'''-(카퍼포피린-5,10,15,20-테트라일) 테트라 벤조에이트(tetra methyl 4,4',4'',4'''-(copperporphyrin-5,10,15,20-tetrayl) tetra benzoate)의 제조 (1)의 제조 tetramethyl 4,4',4'',4'''-(capperporphyrin-5,10,15,20-tetrayl) tetra benzoate (tetra methyl 4,4',4'',4''' Preparation of -(copperporphyrin-5,10,15,20-tetrayl)tetra benzoate) (1)
프로피온산(propionic acid) 25mL에 메틸 4-포밀벤조에이트(Methyl 4-formyl benzoate, 2.5g, 15.24mmol)를 넣고 피롤(1.02g, 15.24mmol)을 천천히 적가하고 어두운 상태에서 12시간 동안 150℃로 가열하고 냉각한 다음 여과하였다. 컬럼 크로마토그래피로 정제하여 수율이 650mg, 20 %인 보라색 고체를 제조하였다.Methyl 4-formyl benzoate (2.5 g, 15.24 mmol) was added to 25 mL of propionic acid, and pyrrole (1.02 g, 15.24 mmol) was slowly added dropwise and heated at 150 ° C for 12 hours in the dark. , cooled, and then filtered. Purification by column chromatography was performed to prepare a purple solid with a yield of 650 mg, 20%.
1H NMR (CDCl3, 600 MHz), δ (ppm): -2.88 (s, 2 H), 4.03 (s, 12 H), 8.20 (d, 8 H), 8.36 (d, 8 H), 8.73 (s, 8 H). 1 H NMR (CDCl 3 , 600 MHz), δ (ppm): -2.88 (s, 2 H), 4.03 (s, 12 H), 8.20 (d, 8 H), 8.36 (d, 8 H), 8.73 (s, 8 H).
ESI-MS: m/z calcd. 846.3, found 847.3 [M+H+].ESI-MS: m/z calcd. 846.3, found 847.3 [M+H + ].
테트라 메틸 4,4 ', 4' ', 4' ''-(카퍼포피린-5,10,15,20- 테트라일) 테트라 벤조에이트(tetra methyl 4,4',4'',4'''-(copperporphyrin-5,10,15,20-tetrayl) tetra benzoate)(2)의 제조 tetramethyl 4,4 ', 4' ', 4' ''-(capperporphyrin-5,10,15,20-tetrayl) tetra benzoate (tetra methyl 4,4',4'',4''' Preparation of -(copperporphyrin-5,10,15,20-tetrayl) tetra benzoate) (2)
클로로포름에 용해된 테트라메틸 4,4', 4'', 4'''-(포피린-5,10,15,20- 테트라일) 테트라 벤조에이트(0.3g, 0.35mmol)에 메탄올에 용해된 Cu(OAc)2.H2O 0.7g (3.5mmol)을 첨가하고 약 45분 동안 60℃로 가열하였다. 그 후 농축 건조하고 클로로포름을 이용하여 재용해하고 물로 세척하여 Cu(OAc)2를 제거하였다. 수율은 300mg, 93 %이다. Cu dissolved in methanol in tetramethyl 4,4', 4'', 4'''-(porphyrin-5,10,15,20-tetrayl) tetrabenzoate (0.3 g, 0.35 mmol) dissolved in chloroform 0.7 g (3.5 mmol) of (OAc) 2 .H 2 O was added and heated to 60° C. for about 45 minutes. Then, concentrated to dryness, redissolved using chloroform, and washed with water to remove Cu(OAc) 2 . The yield is 300 mg, 93%.
ESI-MS: m/z calcd. 907.2, found 908.3 [M+H+].ESI-MS: m/z calcd. 907.2, found 908.3 [M+H + ].
테트라메틸 4,4', 4'', 4'''-(2,3,7,8,12,13,17,18- 옥타브로모포피린-5,10,15,20-테트라일) 테트라벤조에이트(tetramethyl 4,4',4'',4'''-(2,3,7,8,12,13,17,18-octabromoporphyrin-5,10,15,20-tetrayl)tetrabenzoate) (3)의 제조 Tetramethyl 4,4', 4'', 4'''-(2,3,7,8,12,13,17,18-octabromoporphyrin-5,10,15,20-tetrayl) tetrabenzo Eate (tetramethyl 4,4',4'',4'''-(2,3,7,8,12,13,17,18-octabromoporphyrin-5,10,15,20-tetrayl)tetrabenzoate) (3 ) manufacturing
클로로포름에 용해된 테트라메틸 4,4', 4'', 4'''-(카퍼포르피린 -5,10,15,20- 테트라일) 테트라 벤조에이트 (0.3g, 0.33mmol)에 클로로폼에 용해된 브롬(0.2g, 1.32mmol)을 첨가하고 12시간 동안 교반하였다. 티오 황산나트륨을 첨가하여 과량의 브롬을 급냉 시킨 다음 반응 혼합물에 물을 첨가하였다. 이후, 혼합물에서 클로로포름으로 추출하고 유기층을 농축하고 건조시켰다. 상기 조반응 혼합물은 클로로포름에 용해시키고, 0℃로 냉각시킨 후, 냉각된 용액에 H2SO4 농축액(3 mL)을 첨가하였다. 이후, 20분 동안 교반하고 암모니아로 중화시키고, 반응 혼합물을 클로로포름으로 추출하고 수득된 조 생성물을 컬럼 크로마토 그래피로 정제하였다. 수율은 250mg, 51 %이다. Tetramethyl 4,4', 4'', 4'''-(capperporphyrin-5,10,15,20-tetrayl) dissolved in chloroform dissolved in chloroform in tetrabenzoate (0.3 g, 0.33 mmol) bromine (0.2 g, 1.32 mmol) was added and stirred for 12 hours. Excess bromine was quenched by addition of sodium thiosulfate, and then water was added to the reaction mixture. Then, the mixture was extracted with chloroform, and the organic layer was concentrated and dried. The crude reaction mixture was dissolved in chloroform, cooled to 0° C., and H2SO4 concentrated solution (3 mL) was added to the cooled solution. Thereafter, the mixture was stirred for 20 minutes, neutralized with ammonia, the reaction mixture was extracted with chloroform, and the obtained crude product was purified by column chromatography. The yield is 250 mg, 51%.
1H NMR (CDCl3, 300MHz), δ(ppm): 4.03 (s, 12 H), 8.22 (d, 8 H), 8.37 (d, 8 H). 1 H NMR (CDCl 3 , 300 MHz), δ (ppm): 4.03 (s, 12 H), 8.22 (d, 8 H), 8.37 (d, 8 H).
ESI-MS: m/z calcd. 1478.1, found 1478.5 [M+H+].ESI-MS: m/z calcd. 1478.1, found 1478.5 [M+H + ].
테트라 메틸 -4,4', 4'', 4'''(2,3,7,8,12,13,17,18- 옥타페닐포피린-5,10,15,20-테트라일) 테트라 벤조에이트(tetramethyl-4,4',4'',4'''(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoate, 4)의 제조Tetramethyl-4,4', 4'', 4''' (2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl) tetrabenzo Eate (tetramethyl-4,4',4'',4'''(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoate, 4) manufacture of
둥근 바닥 플라스크에 테트라메틸 4,4', 4'', 4'''-(2,3,7,8,12,13,17,18-옥타브로모포피린-5,10,15,20-테트라일) 테트라 벤조에이트(0.5g, 0.33mmol), 페닐 보론산(0.96g, 7.92mmol) 및 탄산 칼륨(2.08g, 15mmol) 및 톨루엔(15mL)을 첨가하였다. 혼합물을 질소 하에서 탈기시키고 테트라 키스 팔라듐(0.078 g, 0.07 mmol)을 첨가하였다. 상기 반응 혼합물을 100 ℃에서 12 시간 동안 교반하고, 진공 하에서 톨루엔을 제거하고, 톨루엔이 제거된 잔류물을 다시 클로로포름에 용해시키고 물로 세척하였다. 컬럼 크로마토그래피를 이용하여 원하는 생성물을 수득하였다. 수율은 230mg, 46.7 %이다.In a round bottom flask, tetramethyl 4,4', 4'', 4'''-(2,3,7,8,12,13,17,18-octabromoporphyrin-5,10,15,20-tetra 1) Tetrabenzoate (0.5 g, 0.33 mmol), phenyl boronic acid (0.96 g, 7.92 mmol) and potassium carbonate (2.08 g, 15 mmol) and toluene (15 mL) were added. The mixture was degassed under nitrogen and tetrakis palladium (0.078 g, 0.07 mmol) was added. The reaction mixture was stirred at 100° C. for 12 hours, toluene was removed under vacuum, and the toluene-free residue was dissolved again in chloroform and washed with water. Column chromatography was used to obtain the desired product. The yield is 230 mg, 46.7%.
1H NMR (DMSO-d6, 600 MHz), δ (ppm): 3.94 (s, 12H), 6.65 (m, 40H), 7.38 (s, 8 H), 7.61 (s, 8 H). 1 H NMR (DMSO-d6, 600 MHz), δ (ppm): 3.94 (s, 12H), 6.65 (m, 40H), 7.38 (s, 8 H), 7.61 (s, 8 H).
ESI-MS: m/z calcd. 1455.6, found 1456.5 [M+H+].ESI-MS: m/z calcd. 1455.6, found 1456.5 [M+H + ].
4,4 ', 4' ', 4' ''-(2,3,7,8,12,13,17,18- 옥타 페닐 포르피린 -5,10,15,20- 테트라 일) 테트라 벤조산(4,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoic acid, P)의 제조4,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenyl porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid (4 Preparation of ,4',4'',4'''-(2,3,7,8,12,13,17,18-octaphenylporphyrin-5,10,15,20-tetrayl)tetrabenzoic acid, P)
THF (20 mL)에 용해된 테트라 메틸 4,4', 4'', 4'''(2,3,7,8,12,13,17,18- 옥타 페닐 포피린-5,10,15,20- 테트라일) 테트라 벤조에이트(0.2g, 0.14 mmol)에 물(10 mL)에 용해시킨 2M 수산화 칼륨을 첨가하였다. 상기 반응 혼합물은 실온에서 1시간 동안 교반한 다음 80℃에서 48시간 동안 교반하였다. 이어서 THF를 반응 혼합물로부터 증발시키고 여기에 2N HCl (25 mL)을 첨가하였다. 생성된 녹색 침전물은 증류수로 세척하였다. 이후, 메탄올에서 결정화하여 생성물을 수득하였다. 수율은 120mg, 62.5 %이다. Tetramethyl 4,4', 4'', 4''' (2,3,7,8,12,13,17,18-octaphenyl porphyrin-5,10,15, dissolved in THF (20 mL); To 20-tetrayl) tetrabenzoate (0.2 g, 0.14 mmol) was added 2M potassium hydroxide dissolved in water (10 mL). The reaction mixture was stirred at room temperature for 1 hour and then at 80° C. for 48 hours. THF was then evaporated from the reaction mixture and 2N HCl (25 mL) was added thereto. The resulting green precipitate was washed with distilled water. Thereafter, crystallization in methanol gave the product. The yield is 120 mg, 62.5%.
1H NMR (DMSO-d6, 600MHz), δ(ppm): 6.64 (m, 40H), 7.61 (s, 8H), 8.12 (s, 8H), 12.83 (s, 4H). 1 H NMR (DMSO-d6, 600 MHz), δ(ppm): 6.64 (m, 40H), 7.61 (s, 8H), 8.12 (s, 8H), 12.83 (s, 4H).
MALDI-TOF: m/z calcd. 1399.5, found 1400.7 [M+H+].MALDI-TOF: m/z calcd. 1399.5, found 1400.7 [M+H + ].
도코실 트리에톡시실란(docosyl triethoxysilane, (S)의 합성Synthesis of docosyl triethoxysilane (S)
10mL THF에 용해시킨 1- 도코센(0.5g, 1.6mmol) 용액을 트리에톡시 실란 (1.46g, 8.9mmol) 및 1mL의 m-자일렌(meta-xylene)에 용해한 Karstedt's 촉매 [0.1mL, 15mol%]를 혼합하고, 아르곤 대기 하에서, 36시간 동안 환류 온도에서 교반 하였다. 반응 완료 후 수득된 조생성물을 정제하여 순수한 액체(무색)를 수득하였다.Karstedt's catalyst [0.1mL, 15mol] dissolved in 1-dococene (0.5g, 1.6mmol) solution dissolved in 10mL THF in triethoxysilane (1.46g, 8.9mmol) and 1mL m-xylene (meta-xylene) %], and stirred under argon atmosphere at reflux temperature for 36 hours. After completion of the reaction, the obtained crude product was purified to obtain a pure liquid (colorless).
수율: 0.2 g, 26.l %. Yield: 0.2 g, 26.l %.
1H NMR (CDCl3, 600MHz), δ (ppm): 0.53 (m, 2 H), 0.79 (t, 3 H, J = 7.2 Hz), 1.14 (m, 47 H), 1.30 (m, 2 H), 3.72 (q, 6 H). 1 H NMR (CDCl 3 , 600 MHz), δ (ppm): 0.53 (m, 2 H), 0.79 (t, 3 H, J = 7.2 Hz), 1.14 (m, 47 H), 1.30 (m, 2 H) ), 3.72 (q, 6 H).
13C NMR (CDCl3, 150MHz), δ (ppm): 9.36, 13.09, 17.27, 21.68, 21.74, 28.26, 28.35, 28.55, 28.69, 30.92, 32.19, 57.26. 13 C NMR (CDCl 3 , 150 MHz), δ (ppm): 9.36, 13.09, 17.27, 21.68, 21.74, 28.26, 28.35, 28.55, 28.69, 30.92, 32.19, 57.26.
ESI-MS: m/z calcd. 472.4, found 473.4 [M+H+].ESI-MS: m/z calcd. 472.4, found 473.4 [M+H + ].
TiO2 (T)의 준비 및 특성Preparation and characterization of TiO 2 (T)
30 wt%, 0.5 mL의 NH4OH 용액 및 1.0 mL의 H2O를 강한 교반 하에 에탄올(150 mL)과 아세토니트릴(100 mL)의 혼합 용액에 첨가하였다. 이후, 5 mL의 티타늄 이소프로폭사이드를 빠르게 주입하고 몇 초 내에 유백색 현탁액이 형성되었으며, 반응 혼합물의 pH는 약 7 내지 8 범위이다. 200℃에서 6시간 동안 계속 교반 한 후, 형성된 침전물을 원심 분리로 수집하고 에탄올로 2회 세척하고 60℃에서 건조하였다. 준비된 TiO2는 XRD로 분석하였으며, 2O = 25.3, 37.9, 47.7 및 54.4 °에서 개별 회절 피크를 나타냈다.30 wt%, 0.5 mL of NH 4 OH solution and 1.0 mL of H 2 O were added to a mixed solution of ethanol (150 mL) and acetonitrile (100 mL) under strong stirring. Then, 5 mL of titanium isopropoxide was rapidly injected and a milky suspension was formed within a few seconds, and the pH of the reaction mixture was in the range of about 7-8. After stirring at 200°C for 6 hours, the precipitate formed was collected by centrifugation, washed twice with ethanol and dried at 60°C. The prepared TiO 2 was analyzed by XRD, and showed individual diffraction peaks at 2O = 25.3, 37.9, 47.7 and 54.4 °.
PET의 TiO2 증착 공정TiO 2 deposition process on PET
TiO2(T) 용액을 사용하여 초음파 보조 방법(초음파 전력 및 주파수는 100W 및 30kHz)에 의해 F에 투명한 코팅을 생성하였다. 이후, 상기 제조된 샘플을 암모니아 증기에 노출시켜 표면을 중화하였다.A clear coating was produced on F by an ultrasonically assisted method (ultrasonic power and frequency of 100 W and 30 kHz) using a TiO 2 (T) solution. Then, the prepared sample was exposed to ammonia vapor to neutralize the surface.
TiO2 결합된 PET에 포피린 화합물 및 실란 화합물의 증착Deposition of porphyrin compounds and silane compounds on TiO 2 bonded PET
포피린 화합물은 DMF에 용해된 상태(1x10-5M)로, 용 TiO2로 코팅된 직물에 초음파로 증착하였다(초음파 전력 및 주파수는 100W 및 30kHz). 이 과정은 TiO2 코팅된 직물을 포피린 화합물이 용해된 용액에 담그고 30분 동안 초음파 처리하고 DMF와 물로 세척하여 결합되지 않은 과량의 포피린 화합물을 제거하고 건조하였다. 이후, 에탄올에 실란 화합물을 용해한 용액(1x10-5M)에 담궈 30분 동안 초음파 처리하여 포피린/TiO2 코팅된 직물에 실란 화합물을 증착하고 100 ℃에서 약 1 시간 동안 건조시킨 다음 과량의 에탄올로 직물을 세척하여 결합되지 않은 실란 화합물을 제거하였다.The porphyrin compound was dissolved in DMF (1x10 -5 M) and ultrasonically deposited on the fabric coated with TiO 2 (ultrasonic power and frequency of 100 W and 30 kHz). In this process, the TiO 2 coated fabric was immersed in a solution in which the porphyrin compound was dissolved, sonicated for 30 minutes, washed with DMF and water to remove excess unbound porphyrin compound, and dried. After that, the silane compound is deposited on the porphyrin/TiO 2 coated fabric by immersing it in a solution (1x10 -5 M) in which a silane compound is dissolved in ethanol and sonicating for 30 minutes, drying it at 100° C. for about 1 hour, and then using an excess of ethanol. The fabric was washed to remove unbound silane compounds.
유기 오염 물질의 광촉매 자기 세정 기능Photocatalytic self-cleaning function of organic pollutants
NP, RB, EY, IN, BB 및 MB를 클로로포름 또는 물 (1.5x10-3M)에 용해한 후, 이를 표면 개질된 직물(PET@TP 및 PET@TPS)에 드롭 캐스트(Drop cast)하고 어둠 속에서 1 시간 동안 건조시켜 흡착-탈착 평형을 유지하였다. 변형된 직물 샘플의 자기 세정 효과는 가시광선 조사에서 강도의 변화를 측정하여 결정하고 변경된 시간 간격으로 UV-Vis 흡수 스펙트럼을 기록하여 확인하였다.After dissolving NP, RB, EY, IN, BB and MB in chloroform or water (1.5x10 -3 M), drop cast them onto surface-modified fabrics (PET@TP and PET@TPS) and place in the dark. The adsorption-desorption equilibrium was maintained by drying for 1 hour. The self-cleaning effect of the modified fabric sample was determined by measuring the change in intensity under visible light irradiation and confirmed by recording the UV-Vis absorption spectrum at the changed time intervals.
UV-Vis 분광법UV-Vis spectroscopy
TiO2, 실란 화합물 및 포피린 화합물의 직물에 대한 부착 여부는 샘플의 UV- 가시 광선 스펙트럼을 이용하여 확인하였다. PET@TP(TiO2 및 포피린 화합물의 결합), PET@TPS(TiO2, 포피린 화합물 및 실란 화합물의 결합) 직물로 인한 표면의 변형은 도 2B와 같다. Whether TiO 2 , a silane compound, and a porphyrin compound adhered to the fabric was confirmed by using the UV-visible light spectrum of the sample. PET@TP (combination of TiO 2 and porphyrin compound), PET@TPS (combination of TiO 2 , porphyrin compound and silane compound) The deformation of the surface due to the fabric is shown in FIG. 2B.
도 2B의 곡선 a는 PET 직물에 대한 스펙트럼 측정 결과이고, 곡선 b는 TP가 결합된 것(PET@TP)이며, 곡선 c는 TPS가 결합된 직물(PET@TPS)에 대한 스펙트럼 측정 결과이다.Curve a of FIG. 2B is a spectrum measurement result for PET fabric, curve b is a TP-bound fabric (PET@TP), and curve c is a spectrum measurement result on a TPS-bound fabric (PET@TPS).
도 2B(곡선 a)에 표시된 스펙트럼은 가시 영역에서 피크가 관찰되지 않았다. 도 2B (곡선 b)에서 볼 수 있듯이 포피린 화합물을 부착한 후 505 nm에서 강한 흡수 피크가 관찰되었고, 이는 포피린 화합물의 Soret 밴드에 의한 것으로, 포피린 화합물에 대한 스펙트럼 상의 피크와 유사하다. 포피린 화합물에 대해 656 및 764 nm에서 관찰된 두 개의 약한 밴드는 포피린 화합물의 Q 밴드에 해당한다(도 2A). 상기 결과는 직물 표면에 포피린 화합물이 성공적으로 결합되었음을 의미한다. In the spectrum shown in FIG. 2B (curve a), no peak was observed in the visible region. As shown in FIG. 2B (curve b), a strong absorption peak at 505 nm was observed after attaching the porphyrin compound, which is due to the Soret band of the porphyrin compound, and is similar to the peak on the spectrum for the porphyrin compound. The two weak bands observed at 656 and 764 nm for the porphyrin compound correspond to the Q band of the porphyrin compound (Fig. 2A). These results indicate that the porphyrin compound was successfully bound to the fabric surface.
포피린 화합물의 soret 밴드에 대한 흡광도 피크는 직물에 부착된 후, 19nm까지 뚜렷한 적색 편이를 보였으며, 상기 피크의 이동(shift)은 포피린 화합물의 카르복시산기 및 TiO2의 상호 작용으로 인한 것이다. The absorbance peak for the soret band of the porphyrin compound exhibited a distinct red shift up to 19 nm after attachment to the fabric, and the shift of the peak is due to the interaction between the carboxylic acid group of the porphyrin compound and TiO 2 .
또한, Si 결합 직물의 흡수 스펙트럼은 포피린 화합물보다 새로운 흡수 피크가 관찰되지 않았지만 포피린 화합물에서 피크의 강도는 도 2B(곡선 c)에서 볼 수 있듯이 더 낮다. 이는 직물에 코팅된 TiO2 및 포르피린의 표면을 스크리닝하거나 차폐하는 실란 화합물에 의한 것이다.In addition, in the absorption spectrum of the Si-bonded fabric, no new absorption peak was observed than that of the porphyrin compound, but the intensity of the peak in the porphyrin compound is lower as shown in Fig. 2B (curve c). This is due to the silane compound screening or masking the surface of TiO 2 and porphyrin coated on the fabric.
XRD 분석XRD analysis
XRD 분석 결과는 도 3과 같다. Pristine 직물은 특징적인 피크를 나타내지 않았다(도 3 a). TiO2로 코팅된 직물은 (101), (004), (200), (211) 및 (204)의 격자면에 대해, 2θ = 25.7, 38.0 47.9, 54.5 및 62.8의 회절 피크 값을 확인하였다. 상기 결과는 직물 표면에 아나타제 TiO2 나노 입자가 결합하였음을 의미한다. The XRD analysis result is shown in FIG. 3 . Pristine fabric did not show a characteristic peak (Fig. 3a). The fabric coated with TiO 2 confirmed the diffraction peak values of 2θ = 25.7, 38.0 47.9, 54.5 and 62.8 for the lattice planes of (101), (004), (200), (211) and (204). The above results mean that the anatase TiO 2 nanoparticles were bound to the surface of the fabric.
PET@TP의 XRD 패턴은 TiO2로 코팅된 직물의 XRD 패턴과 크게 다르지 않았는데, 이는 포피린 화합물이 결합된 후에도, 아나타제 TiO2가 결정성을 유지함을 의미한다. 마지막으로, 실란 화합물이 결합된 직물의 경우에도, TiO2의 피크 강도를 유지하였다.The XRD pattern of PET@TP was not significantly different from the XRD pattern of the fabric coated with TiO 2 , meaning that even after the porphyrin compound was bound, the anatase TiO 2 maintained its crystallinity. Finally, even in the case of the fabric bonded with the silane compound, the peak strength of TiO 2 was maintained.
SEM 및 EDX 분석SEM and EDX analysis
도 4(a)는 직물의 구조를 확인할 수 있고, 얇은 시트와 같은 형태를 확인할 수 있다. 도 4(b)는 TiO2 나노 입자가 결합된 것으로, 입자의 평균 직경이 200nm인 TiO2가 직물 표면에 균일하게 분산되어 있음을 확인할 수 있다. PET@TP 샘플의 경우 TiO2 입자 크기가 증가하고, 일부 층 구조가 나타남을 확인하였다. 또한, PET@쎼의 표면에 실란 화합물을 결합한 경우, TiO2 나노 입자가 응집된 형태를 추가로 확인할 수 있다. PET@TPS에 대한 매핑 분석(EDX) 결과는 도 5와 같고, C, N, O, Si 및 Ti의 존재를 확인하기 위해 수행하였다. 그 결과, 개질된 직물의 표면에 Ti 및 Si의 존재를 확인하였다.Figure 4 (a) can confirm the structure of the fabric, it can be confirmed the form such as a thin sheet. FIG. 4(b) shows that TiO 2 nanoparticles are bound, and TiO 2 having an average particle diameter of 200 nm is uniformly dispersed on the surface of the fabric. In the case of the PET@TP sample, it was confirmed that the TiO 2 particle size increased, and some layered structure appeared. In addition, when a silane compound is bonded to the surface of PET@㎼, the form in which TiO 2 nanoparticles are aggregated can be further confirmed. Mapping analysis (EDX) results for PET@TPS are as shown in FIG. 5, and were performed to confirm the presence of C, N, O, Si and Ti. As a result, the presence of Ti and Si on the surface of the modified fabric was confirmed.
XPS 측정XPS measurement
직물 표면 변형의 화학적 상태를 분석하기 위해 XPS 측정을 진행하였다. In order to analyze the chemical state of the deformation of the fabric surface, XPS measurement was performed.
상기 분석 결과는 도 6과 같고, 분석 결과 C, O, N, Si 및 Ti로 구성됨을 확인하였으며, 상기 결과는 직물 표면에 TiO2, 포피린 화합물 및 실란 화합물이 결합하고 있음을 의미한다. PET@TPS의 XPS 스펙트럼에서 C1s 피크는 285.4 및 286.3에서 두 개의 비권취된(deconvoluted) 피크로 나타나며, 이는 sp2- 하이브리드(C-O-C 및 C = O) 결합을 의미한다. 533.3, 532.6 및 531.7에서의 비권취된 O1s 피크는 골격에 각각 C=O, C-O 및 Si-O이 존재함을 의미한다. 또한, 530.1 eV의 피크는 직물에 TiO2가 존재함을 의미한다. 399.2 eV에서의 N1s 피크는 피롤형 질소의 포피린 고리에 해당한다. 103.5eV에서의 추가 피크는 실리케이트(Si-O)의 Si2p 피크에 의한 것이며, Ti2p 신호는 458.8(Ti2p3/2) 및 464.2eV(Ti2p1/2)에서 두 개의 피크로 나타나고, 530.0eV에서의 O1s 피크는 TiO2에 기인한 것이다.The analysis results are the same as in FIG. 6 , and it was confirmed that the analysis results consist of C, O, N, Si and Ti, and the results indicate that TiO 2 , a porphyrin compound and a silane compound are bonded to the fabric surface. In the XPS spectrum of PET@TPS, the Cls peak appears as two deconvoluted peaks at 285.4 and 286.3, indicating sp2-hybrid (COC and C = O) bonding. The unwound O1s peaks at 533.3, 532.6 and 531.7 indicate the presence of C=O, CO and Si-O in the backbone, respectively. In addition, the peak of 530.1 eV means that TiO 2 is present in the fabric. The N1s peak at 399.2 eV corresponds to the porphyrin ring of the pyrrole nitrogen. The additional peak at 103.5 eV is due to the Si2p peak of the silicate (Si-O), the Ti2p signal appears as two peaks at 458.8 (Ti2p3/2) and 464.2 eV (Ti2p1/2), and the O1s peak at 530.0 eV. is due to TiO 2 .
개질된 직물 표면의 발수 특성의 평가Evaluation of water-repellent properties of modified fabric surfaces
표면 개질된 직물의 초소수성은 WCA(물 접촉각) 측정에 의해 조사하였다. 도 7에 의하면, PET 표면은 WCA가 134°이다. 일반적으로 PET의 표면은 소수성이지만 표면이 기울어졌을 때 물방울이 단순히 흘러내리지 않는다. 이를 달성하기 위해 직물 표면을 TiO2로 개질하고 WCA를 증가시켜(138°) 소수성을 높였다. 비교를 위해 포피린 화합물로 개질한 후 직물 표면의 WCA는 0° 이지만, 직물 표면에 포피린 화합물이 결합되어 우수한 광촉매 활성을 나타낼 수 있다. The superhydrophobicity of the surface-modified fabrics was investigated by WCA (water contact angle) measurement. According to FIG. 7 , the PET surface has a WCA of 134°. In general, the surface of PET is hydrophobic, but water droplets do not simply flow down when the surface is tilted. To achieve this, the fabric surface was modified with TiO 2 and WCA was increased (138°) to increase the hydrophobicity. For comparison, the WCA of the fabric surface after modification with a porphyrin compound is 0°, but the porphyrin compound is bound to the fabric surface to exhibit excellent photocatalytic activity.
반면 PET@TP 표면에 실란을 추가로 개질하면 초소수성 또는 발수성이 나타 나며 WCA 값은 각각 152°로 PET보다 높은 발수각을 나타냈다.On the other hand, when the surface of PET@TP was further modified with silane, superhydrophobicity or water repellency appeared, and the WCA value was 152°, respectively, indicating a higher water repellency angle than PET.
유기 오염 물질의 광분해 결과Photolysis results of organic pollutants
EY, NP, BB, RB 및 IN와 같은 유기 오염 물질 및 염료를 직물 및 PET@TP에 개별적으로 뿌린 후, 약 3시간 동안 가시 광선을 조사하였다. 도 8은 IN을 제외한 거의 대부분의 오염 물질에 의한 변색이 일어남을 확인하였다.Organic contaminants and dyes such as EY, NP, BB, RB and IN were individually sprayed onto the fabric and PET@TP, and then irradiated with visible light for about 3 hours. 8 shows that discoloration occurs due to almost all contaminants except IN.
광촉매 활성photocatalytic activity
본 발명의 일 실시예에 따른, PET@T, PET@TP 및 PET@TPS로 개질된 직물 표면의 광촉매 활성을 통한 자가 세정 기능은 표면에 흡착된 유해 MB에 대한 분해능을 통해 확인하였다. 가시 광선의 조사에 의한 MB 분해는 시각적으로 확인할 수 있고, 표면 개질이 없는 직물의 경우, 표면에서 뚜렷한 색상 변화가 나타나지 않았다. 반면 MB의 강렬한 색상은 표면 개질된 직물의 표면에서 서서히 희미 해졌다. 상기의 색상 변화는 도 9와 같이 UV-DRS 스펙트럼을 통해 확인하였다. 도 9에 의하면, MB의 분해 효율은 PET@TP> PET@TPS> PET@T의 순서대로이다. 도 10에 표시된 C/C0 대 시간의 플롯은 ln(C/C0) 및 반응 시간 t(99.9 %) 사이에 좋은 선형 상관 관계를 나타냈다. MB 변색의 속도 상수 k는 다음 방정식에서 파생하였다.According to an embodiment of the present invention, the self-cleaning function through the photocatalytic activity of the fabric surface modified with PET@T, PET@TP and PET@TPS was confirmed through the resolution of harmful MB adsorbed on the surface. MB decomposition by irradiation with visible light can be visually confirmed, and in the case of the fabric without surface modification, there was no apparent color change on the surface. On the other hand, the intense color of MB gradually faded on the surface of the surface-modified fabric. The color change was confirmed through the UV-DRS spectrum as shown in FIG. 9 . According to FIG. 9 , the MB decomposition efficiency is in the order of PET@TP>PET@TPS>PET@T. The plot of C/C 0 versus time shown in FIG. 10 showed a good linear correlation between ln(C/C 0 ) and reaction time t(99.9%). The rate constant k of MB discoloration is derived from the following equation.
-ln C/C0 = kt(1)-ln C/C 0 = k t (1)
여기서 k는 속도 상수이고 t는 반응 시간이다. C0는 초기 MB 농도이고 C는 시간 t에서의 MB 농도이다. 상기 비교 결과는 PET@TP가 광촉매 성능을 크게 향상시켰으며, 이는 포피린 화합물의 광과민화 증가에 기인한 것이다. where k is the rate constant and t is the reaction time. C 0 is initial MB concentration and C is the MB concentration at time t. The comparative results show that PET@TP significantly improved the photocatalytic performance, which is due to the increased photosensitivity of the porphyrin compound.
또한, 실란 화합물이 결합한 직물의 표면은 실란 화합물에 의해, 포피린 화합물이 코팅된 TiO2 표면이 가려지는 현상으로 인해, 광촉매 활성이 감소하였다. 다만, 실란 화합물에 의해 표면에 초소수성이 구현되어, 실란 화합물이 결합된 직물인 PET@TPS는 이중 자기 세정 효과를 나타낸다.In addition, the photocatalytic activity was reduced due to the phenomenon that the surface of the fabric to which the silane compound is bonded is covered by the silane compound, the TiO 2 surface coated with the porphyrin compound. However, superhydrophobicity is realized on the surface by the silane compound, and PET@TPS, a fabric bonded with a silane compound, exhibits a double self-cleaning effect.
TiO2/포피린 화합물의 안정성 평가TiO 2 /Porphyrin compound stability evaluation
TiO2/포피린 화합물이 결합된 직물의 안정성 및 재사용성을 확인하였다. 상기 TiO2는 우수한 접착 특성을 가지고 있어 직물 및 포피린 화합물과 쉽게 결합할 수 있다. 따라서 물 및 석유에 노출시키고, 세제로 세척 후, TiO2 및 포피린 화합물이 결합된 직물의 안정성을 평가하였다. 그 결과, 포르피린의 Q-밴드에서의 명백한 변화는 관찰되지 않았다. 상기 결과는 TiO2 및 포피린 화합물이 결합된 직물 표면이 안정성 및 재사용성을 유지했음을 의미하며, 이는 포피린 화합물 및 TiO2의 카복실레이트기에 의한 강한 상호 작용 때문이다. The stability and reusability of the fabric combined with TiO 2 /porphyrin compound were confirmed. The TiO 2 has excellent adhesive properties and can be easily combined with fabrics and porphyrin compounds. Therefore, after exposure to water and petroleum, washing with detergent, TiO 2 and the stability of the porphyrin compound bound fabric was evaluated. As a result, no obvious change in the Q-band of the porphyrin was observed. The above result means that the fabric surface to which TiO 2 and the porphyrin compound are bonded maintains stability and reusability, which is due to the strong interaction by the carboxylate group of the porphyrin compound and TiO 2 .
실란 화합물에 대한 코팅의 안정성Stability of coatings to silane compounds
초소수성 표면의 안정성을 평가하기 위해 WCA를 측정하였다. 상기 PET@TP의 안정성이 포피린 화합물의 카복실레이트기에 대한 TiO2의 강한 친화성 때문이라는 것을 확인하였다. 세제, 석유 및 물에서 샘플을 세척하고, 표면에서의 실란 화합물의 결합을 평가하였다. 5회의 세탁 사이클 후, WCA는 PET@TPS 직물 샘플의 경우 152°에서 150°로 약간 감소하였다. 또한 가시광선을 조사한 후, 24시간 전후에 표면의 광 안정성을 측정하였다. 상기 실험 결과, WCA의 급격한 감소는 관찰되지 않았다. 상기 결과는 실란 화합물이 결합된 직물에서 발수성 및 광 안정성이 유지됨을 의미한다.WCA was measured to evaluate the stability of the superhydrophobic surface. It was confirmed that the stability of the PET@TP was due to the strong affinity of TiO 2 for the carboxylate group of the porphyrin compound. Samples were washed in detergent, petroleum and water, and binding of silane compounds to the surface was assessed. After 5 wash cycles, the WCA decreased slightly from 152° to 150° for the PET@TPS fabric sample. In addition, after irradiation with visible light, the light stability of the surface was measured before and after 24 hours. As a result of the above experiment, a sharp decrease in WCA was not observed. This result means that water repellency and light stability are maintained in the fabric to which the silane compound is bonded.
MB 분해 메커니즘MB decomposition mechanism
직물 표면에서의 MB 분해에 대한 메커니즘은 도 11과 같다. 직물이 가시 광선으로 조사되면 표면 개질된 샘플이 여기되어 정공과 전자를 생성한다. 포피린 화합물에 의해 빛을 흡수한 후 여기된 전자는 기저 상태(HOMO 궤도)를 벗어나 시스템간 교차한다. 상기 여기된 레벨 전자(LUMO 궤도에서)는 TiO2의 CB로 쉽게 전달된다. 개질된 표면은 산소와 반응하여 활성 수퍼 옥사이드 라디칼을 생성하고 이후의 양성자는 HOO· 라디칼을 제공하며, 이는 역전자 전달을 통해 염료+·로 대항(compete)한다. 한편, 실란으로 개질 된 표면은 조사 후에도 초 소수성을 유지하는데, 이는 TiO2 표면의 OH·가 염료 민감화를 통해 파괴되어 소수성을 유지하기 때문이다.The mechanism for MB degradation on the fabric surface is shown in FIG. 11 . When the fabric is irradiated with visible light, the surface-modified sample is excited to generate holes and electrons. After light absorption by the porphyrin compound, the excited electrons leave the ground state (HOMO orbital) and cross the system. The excited level electrons (in the LUMO orbital) are easily transferred to the CB of TiO 2 . The modified surface reacts with oxygen to generate active superoxide radicals and subsequent protons donate the HOO· radical, which competes with the dye+· through reverse electron transfer. On the other hand, the silane-modified surface maintains superhydrophobicity even after irradiation, because OH· on the TiO2 surface is destroyed through dye sensitization to maintain hydrophobicity.
샘플 분석sample analysis
광촉매 자가 세정 활성 및 초 소수성에 대한 개질된 직물의 표면을 평가하기 위해 실제 샘플(커피 및 오일 얼룩)을 테스트하였으며, 그 결과는 도 12와 같다. 개질되지 않은 직물의 표면 및 표면 개질된 직물의 표면에 커피 방울을 뿌렸다. 가시 광선 조사 하에서 PET@TP 표면은 다른 표면과 비교하여, 최대로 분해되었다. 이는 직물의 표면이 우수한 광촉매 활성을 갖는 것을 의미한다. 반면, 실란 화합물이 부착된 직물 PET@TPS에서는 커피 방울이 흡수되지 않음을 확인하였다. Real samples (coffee and oil stains) were tested to evaluate the surface of the modified fabric for photocatalytic self-cleaning activity and superhydrophobicity, and the results are shown in FIG. 12 . Coffee drops were sprinkled on the surface of the unmodified fabric and on the surface of the surface-modified fabric. Under visible light irradiation, the PET@TP surface was maximally degraded compared to the other surfaces. This means that the surface of the fabric has excellent photocatalytic activity. On the other hand, it was confirmed that coffee drops were not absorbed in the fabric PET@TPS to which the silane compound was attached.
추가적으로 간장과 같은 기름 얼룩의 분해도 평가하였다. 소스에 존재하는 기름은 직물 표면에 쉽게 흡착되었고, 개질된 직물에 흡착된 얼룩은 일반적으로 6 시간 내에 분해되었다(도 12B). 상기 결과는 실란 화합물로 개질 전후 직물 표면이 우수한 광 분해능과 초 소수성을 가지고 있어, 우수한 자가 세정 효과를 나타냄을 의미한다고 할 것이다. Additionally, the degradation of oil stains such as soy sauce was also evaluated. The oil present in the sauce was readily adsorbed to the fabric surface, and the adsorbed stains on the modified fabric were generally decomposed within 6 hours (Fig. 12B). The above results will mean that the fabric surface before and after modification with a silane compound has excellent photo-resolution and superhydrophobicity, thereby exhibiting an excellent self-cleaning effect.
인쇄 응용printing application
에탄올(10 mL) 용액에 실란 화합물(0.5 g)을 혼합하여 잉크로 제조하고, 상기 잉크 조성물을 카트리지[시각화를 용이하게 하기 위해 염료(2.5x10-3 M)를 잉크에 추가하였다]에 주입하였다. Canon (MG2590) 프린터 및 카트리지(CL-946)를 사용하였으며, TiO2/포피린 화합물이 결합된 직물의 표면에 이미지를 인쇄하였다. 직물에 인쇄된 이미지 영역 및 이미지가 인쇄되지 않은 영역에 물방울을 떨어뜨려 물 접촉각을 측정하였다. 실험 결과 인쇄된 이미지 영역은 WCA가 150°인 초 소수성이고 나머지 직물 영역은 친수성이다. 본 발명의 실린 화합물은, 디지털 인쇄를 이용하여, 직물의 표면에 초소수성을 구현할 수 있는 재료로 활용이 가능함을 확인하였다.An ink was prepared by mixing a silane compound (0.5 g) in an ethanol (10 mL) solution, and the ink composition was injected into a cartridge [dye (2.5x10 -3 M) was added to the ink to facilitate visualization]. . A Canon (MG2590) printer and cartridge (CL-946) were used, and an image was printed on the surface of the fabric to which TiO 2 /Porphyrin compound was bound. The water contact angle was measured by dropping water droplets on the printed image area and the non-image printed area on the fabric. Experimental results show that the printed image area is superhydrophobic with a WCA of 150°, and the remaining fabric area is hydrophilic. It was confirmed that the silin compound of the present invention can be utilized as a material capable of implementing superhydrophobicity on the surface of a fabric by using digital printing.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.Although preferred embodiments of the present invention have 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
본 발명은 자기 세정용 조성물 및 이를 포함하는 자기 세정용 직물에 관한 것으로, 보다 구체적으로 초발수 표면을 구현하여 오염물의 부착을 방지할 수 있고, 부착된 오염물에 대한 분해를 통해 오염을 방지할 수 있는 자기 세정용 조성물 및 이를 포함하는 자기 세정용 직물에 관한 것이다.The present invention relates to a self-cleaning composition and a self-cleaning fabric comprising the same, and more particularly, it is possible to prevent adhesion of contaminants by implementing a super water-repellent surface, and to prevent contamination through decomposition of the attached contaminants. It relates to a self-cleaning composition and a self-cleaning fabric comprising the same.
Claims (10)
- TiO2;TiO 2 ;하기 화학식 1로 표시되는 포피린 화합물; 및a porphyrin compound represented by the following formula (1); and하기 화학식 2로 표시되는 실란 화합물을 포함하며, It contains a silane compound represented by the following formula (2),상기 포피린 화합물 및 실란 화합물은 TiO2와 결합하는The porphyrin compound and the silane compound are combined with TiO 2자기 세정용 조성물:Compositions for self-cleaning:[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,X1 및 X3는 서로 동일하거나 상이하며 각각 독립적으로 N(R13), C(R14)(R15), O 및 S로 이루어진 군으로부터 선택되며,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 13 ), C(R 14 )(R 15 ), O and S,X2 및 X4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R16)이며,X 2 And X 4 Are the same as or different from each other, each independently N or C (R 16 ),L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,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 An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, 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,R1 내지 R16은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환된 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며, 인접하는 기와 서로 결합하거나, 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,R 1 to R 16 are the same as or different from each other, and each independently represents a hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or Unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Arylalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 An aralkylamino group of 30, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or It is selected from the group consisting of an 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,L5는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기로 이루어진 군으로부터 선택되며,L 5 is a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 It is selected from the group consisting of a cycloalkylene group of to 20, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms,R17 내지 R19는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐기 또는 치환 또는 비치환된 탄소수 1 내지 30의 알킬기이며,R 17 to R 19 are the same as or different from each other, and each independently represents a halogen group or a substituted or unsubstituted C 1 to C 30 alkyl group,R20은 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 4의 알킬티오기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환된 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴알킬기 및 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기로 이루어진 군으로부터 선택되며,R 20 is hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted Or an unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C30 heteroarylalkyl group, and a substituted or unsubstituted C1-C30 heteroaryl group It is selected from the group consisting of an alkoxy group,상기 L1 내지 L5 및 R1 내지 R20이 치환되는 경우, 수소, 시아노기, 트리플루오로메틸기, 니트로기, 할로겐기, 히드록시기, 카복실기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 알킬티오기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 2 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되는 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When the L 1 to L 5 and R 1 to R 20 are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 4 carbon atoms of an alkylthio group, 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. group, heteroaryl group having 2 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, ar having 6 to 30 carbon atoms It is substituted with a substituent selected from the group consisting of an alkylamino group, 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. When substituted with a substituent, they are the same as or different from each other. - 제1항에 있어서,According to claim 1,상기 화학식 1로 표시되는 포피린 화합물은 하기 화학식 3으로 표시되는 화합물인The porphyrin compound represented by Formula 1 is a compound represented by Formula 3자기 세정용 조성물:Compositions for self-cleaning:[화학식 3][Formula 3]
여기서, here,R1 내지 R12 및 L1 내지 L4는 제1항에서 정의한 바와 같다. R 1 to R 12 and L 1 to L 4 are as defined in claim 1. - 제1항에 있어서,According to claim 1,상기 R1 내지 R8은 서로 동일하거나 상이하며, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로아릴기인wherein R 1 to R 8 are the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 30 aryl group or a substituted or unsubstituted C 2 to C 60 heteroaryl group자기 세정용 조성물.A composition for self-cleaning.
- 제1항에 있어서,According to claim 1,상기 L1 내지 L4는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기인Wherein L 1 To L 4 Are the same as or different from each other, and each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms자기 세정용 조성물.A composition for self-cleaning.
- 제1항에 있어서, According to claim 1,상기 L5는 탄소수 1 내지 30의 알킬기인The L 5 is an alkyl group having 1 to 30 carbon atoms자기 세정용 조성물. A composition for self-cleaning.
- 제1항에 있어서, According to claim 1,상기 R18 내지 R20은 탄소수 1 내지 30의 알킬기인wherein R 18 to R 20 are an alkyl group having 1 to 30 carbon atoms자기 세정용 조성물.A composition for self-cleaning.
- 제1항에 있어서, According to claim 1,상기 자기 세정용 조성물은 직물의 표면에 TiO2가 결합되고, The self-cleaning composition is TiO 2 bonded to the surface of the fabric,상기 직물에 결합된 TiO2에 포피린 화합물 및 실란 화합물이 결합되어 초발수성 및 가시광 감응 광촉매로 작용하는A porphyrin compound and a silane compound are combined with TiO 2 bonded to the fabric to act as a superhydrophobic and visible light-sensitive photocatalyst.자기 세정용 조성물.A composition for self-cleaning.
- 제1항 내지 제7항 중 어느 한 항에 따른 자기 세정용 조성물을 포함하는A self-cleaning composition comprising the self-cleaning composition according to any one of claims 1 to 7자기 세정용 직물.Self-cleaning fabric.
- 제8항에 있어서,9. The method of claim 8,상기 자기 세정용 직물은 표면에 TiO2가 결합되고, The self-cleaning fabric is TiO 2 is bonded to the surface,상기 TiO2에 포피린 화합물이 결합되어 가시광 감응 광촉매로 작용하며, A porphyrin compound is bound to the TiO 2 to act as a visible light-sensitive photocatalyst,상기 TiO2에 실란 화합물이 결합되어 초발수성을 나타내는A silane compound is bonded to the TiO 2 to exhibit superhydrophobicity자기 세정용 직물.Self-cleaning fabric.
- 제9항에 있어서,10. The method of claim 9,상기 실란 화합물은 잉크 조성물에 포함되어 디지털 프린터를 통해 직물의 표면에 인쇄면으로 출력되어 초발수성을 나타내는The silane compound is included in the ink composition and printed on the surface of the fabric through a digital printer to show super water repellency.자기 세정용 직물.Self-cleaning fabric.
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| KR1020210037347A KR102586077B1 (en) | 2020-12-30 | 2021-03-23 | Self-cleaning composition and self-cleaning fabric containing the same |
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| US5755867A (en) * | 1995-12-22 | 1998-05-26 | Shin-Etsu Chemical Co., Ltd. | Photocatalytic hydrophilic coating compositions |
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