KR102289355B1 - Novel oxazoliydin compound and dye compostion comprising the same - Google Patents

Abstract

The present invention relates to a novel oxazolidine-based dye compound and an oxazolidine-based dye composition comprising the same. When moisture is detected, visibility is excellent.
In addition, the water discoloration property does not deteriorate due to repeated use, the color lasts for a long time, and it may be provided as a water discoloration fabric including an oxazolidine-based dye composition that can utilize water as an ink.

Description

Novel oxazolidine-based dye compound and oxazolidine-based dye composition comprising the same

The present invention relates to a novel oxazolidine-based dye compound and an oxazolidine-based dye composition comprising the same, and to a novel dye compound having water discoloration properties and a dye composition including the same.

Water is a typical contaminant in most organic solvents and is usually treated as a hindrance in chemical reactions and industrial production processes where drying processes must be ensured.

Crucially, under the process conditions of chemical production plants, especially in the case of the refining industry, water can induce metal corrosion, quench metal-based samples, and cause deactivation and degradation of catalysts.

Therefore, the detection and quantification of water in organic media is very important.

Currently, traditional methods for the quantification of water content in gas streams or liquid phases are widely known, but there are many problems such as operating and equipment costs and their time-consuming nature.

A humidity sensor (hereinafter, also referred to as a “moisture sensor”) is an important sensor that is widely used in scientific research laboratories as well as automotive, biomedical, chemical and electronic industries.

These humidity sensors are generally applied to precision air conditioning controls for electronic devices, breathing air systems, and moisture alarms for pressurized telecommunications transmission cables.

Currently, most of the humidity sensors on the market use an inorganic- or organic-based humidity sink to precisely measure the moisture level of the surrounding environment.

)를 요구하는 바 마이크로칩 제작 산업에서의 활용성이 제한되어 반도체 제조 분야에는 적합하지 않은 단점이 있다.Among these, inorganic-based sensing materials (eg, Al ₂ O ₃ , In ₂ O ₃ , MnWO ₄ , SiO ₂ , SnO ₂ , TiO ₂ , WO ₃ and ZrTiO ₃ ) have excellent moisture sensitivity, but high process temperature (1000

) is required, and its applicability in the microchip manufacturing industry is limited, making it unsuitable for the semiconductor manufacturing field.

These inorganic materials are highly soluble organic or polymer-based sensing materials (eg, polyvinyl alcohol, poly(dimethyldiallylammonium chloride), poly(sodium p-styrene sulfonate), poly(vinylpyrrolidone), polyaniline and derivatives thereof), and these materials have the advantage that they can be solution-processed at low temperatures.

However, in some cases the high water solubility of these organic materials is a major disadvantage, especially when these polymeric materials have to be used in conditions of high humidity.

In addition, most conventional resistive sensors have a decisive weakness in that their response time (typically, in the range of 10 to 30 seconds) is relatively slow, and some low-cost humidity sensors have a long response time of more than 1 to 2 minutes. , which is practically impractical.

Therefore, these sensors have a problem of being unsuitable for integrated application to wearable and mobile electronic devices requiring high-sensitivity, fast response and high energy efficiency.

In order to solve this problem, it is necessary to develop a compound for a sensor capable of detecting moisture and exhibiting high-sensitivity and fast response speed.

KR 10-1796829 B1

An object of the present invention relates to a novel oxazolidine-based dye compound and an oxazolidine-based dye composition comprising the same.

Another object of the present invention relates to a novel oxazolidine-based dye compound capable of exhibiting high sensitivity and fast response speed due to excellent water discoloration properties, and an oxazolidine-based dye composition comprising the same.

Another object of the present invention relates to a novel oxazolidine-based dye compound and an oxazolidine-based dye composition comprising the same, which have high utility as a moisture sensor due to high sensitivity and fast response speed and excellent visibility when moisture is detected.

Another object of the present invention relates to a water discoloration fabric comprising an oxazolidine-based dye composition that does not deteriorate water discoloration characteristics due to repeated use, lasts a long time, and can utilize water as an ink.

In order to achieve the above object, the dye compound according to an embodiment of the present invention includes a compound represented by the following formula (1), and has excellent water discoloration properties:

[Formula 1]

here,

X ₁ is N or C(R ₇ ),

X ₂ is O, N(R ₈ ) or C(R ₉ )(R ₁₀ ),

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

R ₁ to R ₁₀ are the same as or different from each other, and each independently 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 C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstituted C6 to C30 hetero 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 can form a substituted or unsubstituted ring by bonding or bonding with adjacent groups to each other,

When Ar and R ₁ to R ₁₀ 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, an alkylthio group having 1 to 4 carbon atoms , C1-C30 alkyl group, C1-C20 cycloalkyl group, C2-C30 alkenyl group, C2-C24 alkynyl group, C7-30 aralkyl group, C6-C30 aryl group, C2 to 60 heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, carbon number substituted with a substituent selected from the group consisting of 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, substituted with a plurality of substituents In case they are the same or different from each other.

The oxazolidine-based dye composition according to another embodiment of the present invention includes the dye compound, and has excellent water discoloration properties.

The fiber according to another embodiment of the present invention is coated with the dye composition to have excellent water discoloration properties.

Water discoloration fabric according to another embodiment of the present invention is a first fabric layer; a water-changing coating layer formed on one surface of the fabric layer; and a second fabric layer formed on one surface of the water-changeable coating layer, wherein the water-changeable coating layer may include the dye composition.

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

In the present invention, the “halogen group” is fluorine, chlorine, bromine or iodine.

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

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

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

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

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

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

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

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

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

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.

In the present invention, "chromism" refers to a change in the absorption or emission spectrum of the entire molecule in response to an internal or external stimulus, and refers to a color transition phenomenon in which the color is reversibly changed.

The present invention relates to a novel oxazolidine-based dye compound and an oxazolidine-based dye composition comprising the same, and due to excellent water discoloration properties, high sensitivity and fast response speed can be exhibited, so that it has high utility as a moisture detection sensor, When moisture is detected, visibility is excellent.

In addition, the water discoloration property does not deteriorate due to repeated use, the color lasts for a long time, and it may be provided as a water discoloration fabric including an oxazolidine-based dye composition that can utilize water as an ink.

1 is a measurement result of water discoloration characteristics and UV-vis spectrum of a dye compound according to an embodiment of the present invention.
2 is a conceptual diagram of a method of manufacturing a fabric using a dye compound according to an embodiment of the present invention.
3 is an XPS measurement result of a fabric using a dye compound according to an embodiment of the present invention.
4 is an SEM measurement result of a fabric using a dye compound according to an embodiment of the present invention.
5 is a color change and diffuse reflectance spectra results of a fabric including a dye compound according to an embodiment of the present invention upon exposure to moisture.
6 is a conceptual diagram of a color change of a fabric including a dye compound according to an embodiment of the present invention.
7 relates to an example of inkjet printing and use of a fabric including a dye compound according to an embodiment of the present invention.
FIG. 8 relates to a change in the reflection value of a fabric including a dye compound according to an embodiment of the present invention with time when exposed to water and a reflection value when reused 10 times.
9 is an exemplary view when water ink is used on a fabric including a dye compound according to an embodiment of the present invention.

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

The present invention relates to a dye compound having excellent water discoloration properties, and the dye compound to a novel oxazolidine-based compound.

Chromism is a reversible process involving a change in the color of a chemical compound that is usually detectable using the human eye or a spectrophotometer.

Due to its numerous applications, chroma can be applied to light (Photo-), thermal (Thermo-), water (Hydro-), electricity (Electro-), piezoelectric (Piezo-), solvent (Solvato-), mechanics (Mechano-), gas It is divided into several categories such as (Gaso-), Ion (Iono-) and Chrono- chromochromic properties.

The hydrochromism is a phenomenon that represents a unique colorimetric reaction to water, and can be applied to a humidity sensor for a biological solvent and an apparatus for measuring the moisture content of an organic solvent, so it can be applied to various fields.

By using the characteristics of the dye composition as described above, it is possible to use a warning phrase or a specific image to appear when in contact with water. Accordingly, after dissolving the compound in a solvent, it can be used in a manner such as dyeing or coating, so that it can be used for purposes such as inks, paints, and indicators. This application can serve as a water detection sensor.

Some of the conventionally known oxazolidine-based compounds have water discoloration properties, but most of them have high selling prices, and have been used only for the application of paper-based water discoloration materials or non-fibrous materials, and it was impossible to utilize them as functional fiber materials.

Conventionally known oxazolidine-based compounds have an open ring and

This means that the conventionally known oxazolidine-based compound cannot be used as a functional fiber material. The application is very wide, such as printing.

More specifically, the dye compound according to an embodiment of the present invention may include a compound represented by the following Chemical Formula 1:

[Formula 1]

here,

X ₁ is N or C(R ₇ ),

X ₂ is O, N(R ₈ ) or C(R ₉ )(R ₁₀ ),

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

R ₁ to R ₁₀ are the same as or different from each other, and each independently 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 C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstituted C6 to C30 hetero 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 can form a substituted or unsubstituted ring by bonding or bonding with adjacent groups to each other,

When Ar and R ₁ to R ₁₀ 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, an alkylthio group having 1 to 4 carbon atoms , C1-C30 alkyl group, C1-C20 cycloalkyl group, C2-C30 alkenyl group, C2-C24 alkynyl group, C7-30 aralkyl group, C6-C30 aryl group, C2 to 60 heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, carbon number substituted with a substituent selected from the group consisting of 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, substituted with a plurality of substituents In case they are the same or different from each other.

The compound represented by Formula 1 may be a compound represented by Formula 2 below:

[Formula 2]

here,

Ar and R ₁ to R ₆ are as defined in Formula 1 above.

Ar may be a substituent represented by the following formulas 3 to 8:

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

here,

n, q and r are the same as or different from each other, and are each independently an integer of 0 to 5,

m and p are the same as or different from each other, and are each independently an integer of 0 to 4,

s is an integer from 0 to 9,

R ₁₁ 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 C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstituted C6 to C30 hetero 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 can form a substituted or unsubstituted ring by bonding or bonding with adjacent groups to each other,

When R ₁₁ to R ₁₆ are substituted, hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a carbon number 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, 2 to 60 carbon atoms of a heteroaryl group, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, 2 to carbon atoms They are substituted with a substituent selected from the group consisting of a 24 heteroarylamino group, 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, and when substituted with a plurality of substituents, these are same or different from each other

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

When the oxazolidine-based compound according to an embodiment of the present invention reacts with water, a color change appears, and the color change at this time is caused by the opening and bonding of a ring in the oxazolidine-based compound.

More specifically, when the oxazolidine-based compound reacts with water, the ring is opened and a color change occurs, and when dried again, the open ring is closed and the color is changed to colorless.

At this time, when the color is changed due to ring opening, the specific color is determined by the substituent substituted on the oxazolidine-based compound, and as the substituent that can improve cyan is combined, the usability as a water discoloration sensor will increase. .

The oxazolidine-based dye composition according to another embodiment of the present invention includes the dye compound and has excellent water discoloration properties.

The dye composition is coated on one surface of a substrate selected from the group consisting of a polymer film, paper, glass, metal, and stone, and can exhibit excellent water discoloration characteristics, so that it has a very high potential for use as a moisture sensor.

In addition, if a coating layer is formed on one surface of the base layer and a protective layer is additionally formed on one surface of the coating layer in order to maintain the water discoloration property for a long time, it prevents direct contact of the dye composition with the atmosphere and can be used for a long time. It can maintain the discoloration property.

The dye composition may include the dye compound and the solvent of the present invention, and is not limited to the above examples, and any configuration that can be used as a coating composition can be used.

The solvent is acetone (Acetone), acetonitrile (Acetonitrile), ether (ether), ene-methyl-2-pyrrolidone (NMP), dimethyl formamide (Dimethylfomamide), dimethyl acetamide (Dimethylacetamide), xylene ( Xylene), Benzene, Chloroform, Toluene, Tetrahydrofuran (THF), Glycerin, Ethylene glycol, Dimethylpyrrolydone, Cyclohexane ), dimethyl sulphoxide, 1,4-dioxane, N,N-dimethyl formamide, methanol, tertiary butyl alcohol butyl alcohol) and mixtures thereof, but is not limited to the above examples.

The dye composition may include an oxazolidine-based compound according to an embodiment of the present invention; menstruum; and high molecular weight compounds.

The polymer compound may be selected from the group consisting of PET, PEG, PVA, and mixtures thereof, and may preferably include both PEG and PVA.

In another embodiment of the present invention, the water-chromic fiber may be coated with the dye composition.

The fiber may be selected from the group consisting of PET (polyester), PEG (polyethylene glycol), PVA (polyvinyl alcohol), nylon, acrylic fiber, cotton fiber, and cellulose fiber, but is not limited thereto.

After preparing the oxazolidine-based compound of the present invention as a dye composition, it can be coated on the outer layer of the fiber to form a coating layer. A color change will appear.

In addition, when the fiber using the dye composition of the present invention is used as a fabric, it is also excellent in reusability according to repeated use.

Considering that it is common for fibers to be washed and used several times depending on the usage state, whether or not the water discoloration property can be maintained even after washing several times is a very important characteristic.

In the case of the fiber having the water discoloration property of the present invention, when manufactured into a fabric, the water discoloration property may be maintained even by repeated use.

As a method to increase such water discoloration characteristics, the fabric according to another embodiment of the present invention includes a first fabric layer; a water-changing coating layer formed on one surface of the fabric layer; and a second fabric layer formed on one surface of the water-changeable coating layer.

In one embodiment, the first fabric layer and the second fabric layer may use both fabrics made of fibers.

For example, the first fabric layer may be selected from the group consisting of PET (polyester), PEG (polyethylene glycol), PVA (polyvinyl alcohol), nylon, acrylic fibers, cotton fibers, cellulose fibers, and mixtures thereof. And, it is not limited to the above example, and any material that can be used as a textile material can be used.

A coating layer is formed on one surface of the first fabric layer, wherein the coating layer uses the dye composition according to an embodiment of the present invention, and the dye composition may include an oxazolidine-based compound.

Preferably, the dye composition is an oxazolidine-based compound represented by the following formula (1); It may include a solvent and a polymer compound, and the polymer compound may be selected from the group consisting of PET, PEG, PVA, and mixtures thereof, and preferably include both PEG and PVA:

[Formula 1]

here,

X ₁ is N or C(R ₇ ),

X ₂ is O, N(R ₈ ) or C(R ₉ )(R ₁₀ ),

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,

R ₁ to R ₁₀ are the same as or different from each other, and each independently 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 C1-C20 cycloalkyl group, substituted or unsubstituted C2-C30 alkenyl group, substituted or unsubstituted C2-C24 alkynyl group, substituted or an unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstituted C6 to C30 hetero 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 can form a substituted or unsubstituted ring by bonding or bonding with adjacent groups to each other,

When Ar and R ₁ to R ₁₀ 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, an alkylthio group having 1 to 4 carbon atoms , C1-C30 alkyl group, C1-C20 cycloalkyl group, C2-C30 alkenyl group, C2-C24 alkynyl group, C7-30 aralkyl group, C6-C30 aryl group, C2 to 60 heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, carbon number substituted with a substituent selected from the group consisting of 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, substituted with a plurality of substituents In case they are the same or different from each other.

A coating layer may be formed on one surface of the first fabric layer by using the dye composition, and the second fabric layer may be laminated.

In this case, the second fabric layer may be selected from the group consisting of PET (polyester), PEG (polyethylene glycol), PVA (polyvinyl alcohol), nylon, acrylic fiber, cotton fiber, cellulose fiber, and mixtures thereof, but preferably is PVA, but is not limited to the above example.

At this time, when a coating layer is formed on the first fabric layer using the dye composition according to an embodiment of the present invention, water discoloration characteristics may be exhibited by contact with water, but due to direct contact between the dye composition and the atmosphere, long-term There may be problems with durability.

Accordingly, preferably, if the second fabric layer is laminated to prevent direct contact between the dye composition and the atmosphere, repeated use according to reuse is possible, and the color change effect due to water discoloration can be maintained for a longer period of time.

The water discoloration fabric can be prepared by forming a coating layer on a fabric material using the dye composition of the present invention, and further laminating the fabric layer,

It can also be manufactured by forming a coating layer on one surface of the short fibers and additionally forming a second fiber layer.

That is, it is possible to form a water discoloration coating layer using a dye composition on one surface of the PET fiber in the form of short fibers, and then form a PVA coating layer on one surface of the water discoloration coating layer to produce a water discoloration fiber.

If the fabric is manufactured by using the water-changeable fiber thus prepared, it can be manufactured with the water-changeable fabric material of the present invention.

An embodiment of the present invention will be described in detail through an experimental example.

Preparation of oxazolidine-based compounds

Compound 1 (2.84 g, 10 mmol) and 4-(di-p-tolylamino)benzaldehyde 2 (3.6 g, 12 mmol) were mixed with ethanol (50 mL) under an inert atmosphere. ) was dissolved in 5 drops of methane sulfonic acid were added to the reaction mixture and reacted for 6 hours. Thereafter, the reaction was continued at room temperature, and when a precipitate was formed, it was washed with EtOAc. The synthesized compound 3 was basified to pH 8 using _{5% NaHCO 3 aqueous solution.}

Then, the mixture was extracted with dichloromethane, dried over sodium sulfate, and concentrated to prepare a colorless solid (80%, 3.88 g).

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.22 (d, J = 8.6, 2H), 7.06-7.10 (m, 1H), 6.96-7.02 (m, 5H), 6.84-6.94 (m, 7H), 6.70-6.74 (m, 2H), 6.07 (d, J = 15.9, 1H), 3.68-3.73 (m, 1H), 3.53-3.62 (m, 2H), 3.36-3.41 (m, 1H), 2.24 (s) , 6H), 1.37 (s, 3H), 1.09 (s, 3H).

¹³ C NMR (150 MHz, DMSO-d6): δ 150.6, 148.0, 145.1, 139.8, 132.7, 131.8, 129.9, 127.5, 127.4, 123.4, 122.4, 122.3, 121.6, 111.9, 110.1, 63.4, 50.1, 47.9, 28.4 , 20.8, 20.3.

IR (KBr tablet) ν _max /cm ^-1 : 3012, 3001, 1598, 1501, 1318, 1270, 1174, 1108, 974, 811, 745, 717.

ESI-MS: 487.5 [M+H] ⁺ .

Compound 1 (2.84 g, 10 mmol) and 9H-fluorene-2-carbaldehyde 2 (2.3 g, 12 mmol) were mixed in ethanol (50 mL) under an inert atmosphere to prepare a mixed reaction product did. 5 drops of methane sulfonic acid were added to the mixture and reacted for 6 hours. Then, the reaction proceeded at room temperature to form a precipitate, which was washed with EtOAc.

Compound 3 prepared by the above reaction _{was basified to pH 8 with 5% NaHCO 3} aqueous solution, separated with dichloromethane, dried over sodium sulfate, and concentrated to obtain Dye1 as a colorless solid (3.08 g, 80% yield).

Mp: 146.0 - 147.0°C;

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.75 (d, J = 8.6, 2H), 6.97-7.52 (m, 6H), 6.70-6.72 (m, 4H), 6.09 (d, J = 15.9, 1H) ), 3.60-3.75 (m, 3H), 3.51-3.62 (m, 2H), 3.36-3.42 (m, 1H), 1.38 (s, 3H), 1.09 (s, 3H).

¹³ C NMR (150 MHz, DMSO-d6): δ 149.6, 143.6, 142.3, 140.5, 138.7, 134.1, 131.5, 128.7, 124.8, 122.0, 110.9, 108.9, 62.5, 49.1, 46.9, 35.8, 27.4, 19.3.

IR (KBr tablet) νmax/cm ^-1 : 2959, 1681, 1605, 1453, 1292, 1172, 976, 919, 765, 731.

ESI-MS m/z 380.3 [M+H] ⁺ .

Compound 1 (2.84 g, 10 mmol) and 4- (diphenylamino) benzaldehyde (4- (diphenylamino) benzaldehyde) 2 (3.25 g, 12 mmol) was mixed in ethanol (50 mL) under an inert atmosphere to prepare a mixed reaction. 5 drops of methane sulfonic acid were added to the mixture and reacted for 6 hours. Then, the reaction proceeded at room temperature to form a precipitate, which was washed with EtOAc.

The crude compound 3 was _{basified to pH 8 with 5% NaHCO 3} aqueous solution, separated with dichloromethane, dried over sodium sulfate and concentrated to obtain Dye2 as a colorless solid (4 g, 85% yield).

Mp: 146.0 - 147.0 °C;

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.20 (d, J = 8.6, 2H), 7.06-7.11 (m, 1H), 6.95-7.02 (m, 5H), 6.85-6.94 (m, 7H), 6.70-6.75 (m, 2H), 6.06 (d, J = 15.9, 1H), 3.68-3.73 (m, 1H), 3.53-3.62 (m, 2H), 3.36-3.41 (m, 1H), 1.36 (s) , 3H), 1.09 (s, 3H).

¹³ C NMR (150 MHz, DMSO-d6): δ 152.3, 149.5, 146.5, 138.7, 130.6, 130.2, 129.5, 128.5, 128.2, 127.5, 124.8, 124.0, 123.4, 122.0, 118.0, 99.1, 75.9, 65.9, 61.8 , 49.0, 28.4, 20.8, 20.3.

IR (KBr tablet) νmax/cm ^-1 : 2921, 1583, 1485, 1269, 1169, 1108, 747, 693.

ESI-MS m/z 459 (M+H ⁺ ).

Compound 1 (2.84 g, 10 mmol) and 2-naphthaldehyde 2 (1.9 g, 12 mmol) were mixed in ethanol (50 mL) under an inert atmosphere to prepare a mixed reaction product. 5 drops of methane sulfonic acid were added to the mixture and reacted for 6 hours.

Thereafter, the reaction proceeded at room temperature to form a precipitate, which was washed with EtOAc to prepare crude compound 3.

The crude compound 3 was _{basified to pH 8 with 5% NaHCO 3} aqueous solution, separated with dichloromethane, dried over sodium sulfate, and concentrated to obtain Dye3 as a colorless solid (3.41 g, 84% yield). .

Mp: 141.0 - 142.0 ℃,

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.82 (m, 3H), 7.06-7.60 (m, 4H), 6.96-7.12 (m, 4H), 6.70-6.84 (m, 1H), 6.47 (d, J = 15.9, 1H), 3.68-3.73 (m, 1H), 3.53-3.62 (m, 2H), 3.36-3.41 (m, 1H), 1.37 (s, 3H), 1.09 (s, 3H).

¹³ C NMR (150 MHz, DMSO-d6): δ 149.5, 138.7, 132.9, 132.5, 132.0, 131.3, 127.6, 125.0, 121.3, 120.6, 111.0, 108.9, 62.5, 49.1, 46.9, 27.4, 19.3.

IR (KBr tablet) νmax/cm ^-1 : 2955, 1593, 1473, 1287, 1107, 1003, 964, 808, 767, 740, 695.

ESI-MS m/z calcd for 341.1 [M+H] ⁺ .

Manufacture of hydrochromic fabrics

A 10 wt% aqueous PEG solution (1 g PEG{M.W. 20,000}/10 mL distilled water) was dip-coated to prepare a layer, dried at 70 °C for 1 hour, and cooled at room temperature to prepare a PET fiber layer. Then, a 6Wt% PEG-PVA (1:1) solution in which distilled water containing OHC dye (2mmol/L) and ethanol (3:2) were dissolved was dip-coated on one side of the PET fiber layer, and then completely dried. Finally, a top layer was formed by coating with a 10 wt% aqueous PEG solution.

experimental conditions

All reagents and solvents used were spectroscopic grade, purchased from commercial sources, and prepared unless otherwise noted.

For proton and carbon NMR, AVANCE III 600 spectrum of 600 MHz and 150 MHz, Alice 4.0 software (Akishima Co., Japan) was used, respectively, and CDCl ₃ was used as a solvent.

δ values (chemical changes) are reported as internal standards (Me ₄ Si) and parts per million (ppm). ESI mass spectra were performed using a 4000 Q TRAP mass spectrometer. SEM analysis was performed using a LYRA3 XMU instrument. UV-Visible absorption spectra were performed using an Agilent 8453 instrument. For solid-state UV-Vis experiments, a Shimadzu Solid Spec-3700 instrument was used. XPS used a Multilab 2000 spectrometer. For FT-IR experiments, an ALPHA-P spectrometer was used.

Experimental evaluation

Confirmation of water discoloration properties in solution state

The water discoloration properties of OHC dyes in 1,4-dioxane were evaluated.

To confirm the rapid color change, OHC dye was added to a 1,4-dioxane (1 Х 10 ^-5 M) solution, and after the same amount of water (v/v) was added, the color change from colorless to magenta was observed. .

As shown in FIG. 1A , the oxazolidine compound exhibits a reversible water discoloration behavior due to the closed ring and the open ring (after adding water). Here, water molecules acted as proton sources.

In order to confirm the exact ratio of water when the color change of the water discoloration characteristic due to the reaction with water is completed ^{, water was slowly added to the 1,4-dioxane (1 Х 10 -5} M) solution to confirm the appropriate amount of the dye.

According to FIG. 1b, when the water ratio was increased, the peak (332 nm) of the UV region was gradually decreased, and the peak (545 nm) of the visible region was increased at the same time, and an isosbestic point was observed at 380 nm.

After adding the same amount of water (v/v), the 545 nm peak was completely increased, and the intensity of the visible region did not increase even if additional water was added.

Evaluation of water discoloration properties in PET fabrics

As shown in FIG. 2, a PET fabric layer was formed using a dip coating method, and then a coating layer was formed using a PEG/Dye/PVA solution, and finally, a PET fabric layer was formed on the uppermost layer.

The prepared PET fabrics were evaluated for water discoloration properties. The prepared dye is not soluble in water, but the PEG layer can react very quickly with water at the molecular level. Due to these properties, when water is sprayed on the PET fabric, it becomes pink, and after drying, it changes from pink to colorless.

In addition, the PET fabric was analyzed by XPS, SEM, and solid-state UV-Visible spectroscopy.

First, in order to confirm the surface of the PET fabric, an XPS experiment was performed on the PET fabric and the PET fabric in which the dye/PEG/PVA was laminated.

As shown in FIG. 3 , C and O were confirmed for the PET fabric, and C, O, and N peaks were confirmed for the PET/dye/PEG/PVA fabric, thereby confirming the presence of the dye composition of the present invention.

In the SEM analysis, a clear surface change was observed between PET and PET/dye/PEG/PVA as shown in FIG. 4, and it was confirmed that active surface aggregation occurred when the dye/PEG/PVA was deposited on PET. Additional changes were observed when the dye/PEG/PVA fabric was sprayed with water. In addition, the SEM image was reversibly changed during the drying process.

5 is a diffuse reflectance spectra result. When the PET fabric reacts with water, a new absorption band is formed at 560 nm, and the absorption before and after exposure to water is significantly changed.

The water discoloration phenomenon of the PET fabric is shown in FIG. 6 .

Waterjet printing of PET fabric may be performed in the same manner as in FIG. 7 . A Canon (MG2590) printer cartridge (CL-946) was obtained from a commercial source, the cartridge was completely removed and the cartridge was washed with ethanol. Thereafter, the cartridge was filled with distilled water.

The PET fabric was attached to A4 size paper with scotch tape, and waterjet printing was performed to confirm that 5.0 size magenta, high resolution and high contrast appeared.

Evaluation of water discoloration properties of water ink fountain pens on PET fabrics

After the ink was removed and washed with water, the fountain pen cartridge (153 NEO Fountain Pen) was washed with water and then used for the PET cloth prepared as shown in FIG. 9 .

It was confirmed that clear words were displayed on PET fabric while writing with a pen, and then the words disappeared when dried with a dryer.

In other words, after writing on PET fabric, heating it to 70°C can erase the word magenta. In addition, even after writing and erasing up to 100 times without shading, the writing remained on the fabric for 24 hours.

If the above characteristics are applied, it will be said that the possibility of use as a useful fabric banner and signboard is high. The dye composition of the present invention uses non-toxic oxazolidine derivatives, PEG and PVA, and the dye composition is insoluble in water. In addition, it was confirmed through experiments that the characteristics were maintained even after repeated use.

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

Claims (9)

It includes a compound represented by the following formula (2),
Excellent water discoloration properties
Dye compounds:
[Formula 2]

[Formula 6]

here,
* means the part to be joined,
q and r are the same as or different from each other, and are each independently an integer of 0 to 5,
R ₁ and R ₂ are an alkyl group having 1 to 30 carbon atoms,
R ₃ to R ₆ are hydrogen,
Ar is a compound represented by Formula 6,
R ₁₄ and R ₁₅ are the same as or different from each other, and are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 2 It is selected from the group consisting of an alkenyl group of 30, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms,
When R ₁₄ and R ₁₅ are substituted, a substituent selected from the group consisting of hydrogen, 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, and an alkynyl group having 2 to 24 carbon atoms. is substituted with, and when substituted with a plurality of substituents, they are the same or different from each other. delete delete According to claim 1,
The compound represented by Formula 2 is selected from the group of compounds represented by the following Formula
Dye compounds:

A dye compound comprising the dye compound according to any one of claims 1 to 4
Excellent water discoloration properties
An oxazolidine-based dye composition. 6. The method of claim 5,
The dye composition is coated on one surface of a substrate made of a polymer film, paper, glass, metal and stone,
capable of exhibiting excellent water discoloration properties
An oxazolidine-based dye composition. coated with the dye composition according to claim 5
Excellent water discoloration properties
fiber. 8. The method of claim 7,
The fiber is selected from the group consisting of PET (polyester), PEG (polyethylene glycol), PVA (polyvinyl alcohol), nylon, acrylic fiber, cotton fiber, and cellulose fiber.
fiber. a first fabric layer;
a water-changing coating layer formed on one surface of the fabric layer; and
It includes a second fabric layer formed on one surface of the water-changeable coating layer,
The water discoloration coating layer comprising the dye composition according to claim 5
Can be discolored fabric.

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