KR20200068915A - Novel fluoran compounds, compositions containing the same and articles using the same - Google Patents

Abstract

The present invention relates to a novel fluoran compound, a composition containing the same, and a product using the same. A fluoran compound according to the present invention exhibits thermochromic properties according to temperature change with high sensitivity, and has excellent light resistance and excellent thermal stability, so that the fluoran compound does not cause degradation of optical properties even in harsh process conditions, thereby being used in various fields. Therefore, the fluoran compound can be usefully used as a thermochromic material which can visually transmit temperature change information.

Description

New fluorane compound, composition containing the same, and product using the same{NOVEL FLUORAN COMPOUNDS, COMPOSITIONS CONTAINING THE SAME AND ARTICLES USING THE SAME}

The present invention relates to a novel floran compound, a composition comprising the same, and a product using the same.

Functional dyes are materials that have optical properties that change with chemical, electrical or thermal changes. Recently, the development of thermochromic materials has attracted attention due to applications applicable to clinical, biochemical and environmental fields as well as clothing, cosmetics, and medical fields.

The thermochromic material has a property of discoloration according to the modification of the structure of the compound within a specific temperature range, and these materials are utilized in various fields mentioned. For example, a cooking appliance that discolors at the boiling point of water; Baby spoons, water bottles or bastoys to show whether water or food is at the proper temperature for consumption; Or ink or developer of laser printing using the effect of discoloration by the heat of the laser; And the like. However, the thermal discoloration material applied to these products had to use an acidic lubricant such as bisphenol A. Another example is sportswear for athletes responding to the weather. However, these sportswear had a weak color development intensity, and it was somewhat unreasonable to embody information on the state of the human body within a narrow temperature range according to human activity. As another example, a cosmetic product including a thermochromic material that reacts with temperature changes, a pharmaceutically acceptable carrier, and the like. However, these cosmetics require more agents that interact with water to cause temperature changes, and it is difficult to react sensitively to temperature.

In addition, the thermochromic material, which has been known until recently, provides a discoloration characteristic that the color becomes dark or colorless depending on the ambient temperature, but when high temperature heat is applied, reversibility decreases and the intensity of discoloration decreases. have.

Accordingly, the present inventors do not require an acidic lubricant such as bisphenol A and devise a new flurane compound that exhibits excellent sensitivity and optical properties without an acidic lubricant, and can commercially use it as a thermochromic material applicable to various fields. Confirmed to complete the present invention.

It is an object of the present invention to provide a novel high-melting Floran compound.

It is also an object of the present invention to provide a dye-polymer integrated particles comprising the above-mentioned floran compound.

It is also an object of the present invention to provide a reversible thermochromic dispersion composition comprising the above-mentioned fluorane compound.

It is also an object of the present invention to provide a product comprising the flown compound or the dye-polymer integrated particles.

For the above-mentioned purpose, a compound of formula 1, that is, a novel floran compound is provided.

[Formula 1]

[In the above formula 1,

R ₁ and R ₂ are independently hydrogen, C _{1- 20} alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl with one another;

R ₃ to R ₅ are independently hydrogen, C _{1- 20} alkyl or hydroxyalkyl, at least one selected from the R ₃ and R ₄ each is a hydroxy.]

The compounds of the formula 1 according to one embodiment of the present invention, wherein R ₁ and R ₂ are independently hydrogen or C _{1- 20} alkyl each other; One of the R ₃ and R ₄ is hydroxy and the other is hydrogen or C _{1- 20} alkyl; Wherein R ₅ may be a hydrogen or C _{1- 20} alkyl.

The compounds of the formula 1 according to one embodiment of the present invention, wherein R ₁ and R ₂ are independently a C _{1- 7} alkyl and the other; One of the R ₃ and R ₄ is hydroxy and the other is hydrogen or C _{1- 7} alkyl; Wherein R ₅ may be a hydrogen or C _{1- 7} alkyl.

The compounds of the formula 1 according to one embodiment of the present invention, wherein R ₁ and R ₂ are independently C _{1- 7} alkyl, straight-chained with each other; One of R ₃ and R ₄ is hydroxy and the other is hydrogen; Wherein R ₅ may be a C _{1- 7} alkyl, hydrogen or a straight chain.

In addition, the present invention provides particles comprising a core layer comprising the compound of Formula 1 and a polymer layer that audits the surface of the core layer, that is, dye-polymerized integrated particles.

In the particle according to an embodiment of the present invention, the polymer layer may include a polymer derived from a monomer having an unsaturated double bond.

In the particles according to an embodiment of the present invention, the particles may have an average diameter of 5 μm or less.

In addition, the present invention provides a reversible thermochromic dispersion composition comprising the compound of Formula 1 and an aprotic solvent.

In the reversible thermochromic dispersion composition according to an embodiment of the present invention, the aprotic solvent is toluene, chloroform, dimethoxyethane, tetrahydrofuran, methylene chloride, butanone, acetone, acetonitrile, sulfolane, dimethyl It may be one or two or more mixed solvents selected from sulfoxide sites.

In the reversible thermochromic dispersion composition according to an embodiment of the present invention, the aprotic solvent is methyl stearate, ethyl stearate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl laurate, methyl Oleate, methyl adipate, methyl caprylate, methyl caproate, methyl anthranirate, methyl palmitate, methyl palmitoate, methyl oxalate, methyl-2-nonanoate, methyl benzoate, methyl benzophenone, Methyl behenate, methyl benzylate, methyl benzyl acetate, trimethyl borate, methyl caprate, methyl butylate, methyl detanoate, methyl cyclohexane carboxylate, methyl dimethoxy acetate, methyl diphenyl acetate, methyl enanthate, It may be one or two or more mixed solvents selected from methyl heptanoate, methyllinorate, and the like.

In the reversible thermochromic dispersion composition according to an embodiment of the present invention, the compound of Formula 1 may be included in 1 to 40% by weight based on the total weight.

The reversible thermochromic dispersion composition according to an embodiment of the present invention may be discolored at a temperature of 35°C or higher.

The reversible thermochromic dispersion composition according to an embodiment of the present invention may be substantially free of an acidic lubricant.

In addition, the present invention provides a compound of Formula 1, a dye-polymerized particles, or a product comprising them.

The product according to an embodiment of the present invention may be selected from cosmetics, ink, paint and indicators.

The product according to an embodiment of the present invention, the compound, dye-polymer integrated particles or they may include a coating, impregnated or molded substrate.

In the product according to an embodiment of the present invention, the substrate may be selected from fibers, wood, paper, metal and film.

The floran compound according to the present invention exhibits thermochromic properties according to temperature changes with high sensitivity. In addition, the floran compound according to the present invention has the advantage of exhibiting excellent sensitivity and optical properties without acidic lubricant such as bisphenol A, by inducing thermochromic properties through temperature-dependent binding and proton transfer in the molecule.

In addition, the fluorane compound according to the present invention is a dye compound having a thermochromic property, and can form dye-polymerized particles to improve the stability of the dye compound over time, and to maintain the desired optical properties stably for a long time.

In addition, the fluorane compound according to the present invention has excellent light resistance and excellent thermal stability, and does not cause deterioration of optical properties even under severe process conditions. Accordingly, it is expected that the fluorane compound and particles containing the same according to the present invention may be used in various fields and usefully used as a thermochromic material capable of visually transmitting temperature change information.

Figure 1 shows an image showing the discoloration of the reversible thermochromic dispersion composition according to the present invention,
Figure 2 shows the UV-vis and reflection spectra of the compounds according to Examples 1 to 8 of the present invention,
Figure 3 shows the UV-vis and reflection spectra of the compounds according to Examples 1 to 8 of the present invention,
Figure 4 shows the UV-vis and reflection spectrum of the compounds according to Examples 1 to 8 of the present invention,
Figure 5 shows the UV-vis and reflection spectra of the compounds according to Examples 1 to 8 of the present invention,
Figure 6 shows the UV-vis and reflection spectra of the compounds according to Examples 1 to 8 of the present invention,
Figure 7 shows the UV-vis and reflection spectrum of the compounds according to Examples 1 to 8 of the present invention,
Figure 8 shows the UV-vis and reflection spectrum of the compounds according to Examples 1 to 8 of the present invention,
Figure 9 shows the UV-vis and reflection spectra of the compounds according to Examples 1 to 8 of the present invention,
10 shows a method for producing particles according to the present invention,
Figure 11 shows the normal temperature SEM image (A: scale bar 2㎛) of the fiber containing the particles according to the present invention,
Figure 12 shows the SEM image (B: scale bar 2㎛, heating = 40 ℃) of the heated state of the fiber containing the particles according to the present invention,
Figure 13 shows an image showing the discoloration of the fiber containing particles according to the present invention.

The novel floran compound according to the present invention, the composition comprising the same and the product using the same will be described in detail below, but unless otherwise defined in the technical terms and scientific terms used at this time, those skilled in the art to which this invention belongs Descriptions of well-known functions and configurations that have meanings that one normally understands and may unnecessarily obscure the subject matter of the present invention are omitted in the following description.

As used herein, the term "thermochromism" refers to the reversible thermal deformation of a chemical species between two types of particle structures having different absorption spectra, and refers to a phenomenon in which the color reversibly changes with temperature. do.

In addition, the term "alkyl" used herein refers to a functional group derived from a straight-chain or pulverized hydrocarbon. In addition, the alkyl and alkyl-containing substituents according to the present invention is preferably a short chain having 1 to 7 carbon atoms, and may be preferably selected from methyl, ethyl, propyl and butyl, but is not limited thereto.

Also, the term "alkenyl" used herein refers to a functional group derived from a straight-chain or pulverized hydrocarbon containing one or more double bonds, and "alkynyl" is a straight-chain or pulverized form containing one or more triple bonds. It means a functional group derived from hydrocarbon.

Floran compounds have been used as solvent discoloration materials or thermochromic materials by realizing various colors according to their substituents and changing color according to changes in solvent or temperature.

Specifically, the conventional floran compound is used as a three-component mixture in which an acidic lubricant such as bisphenol A, acetic acid, etc. and a low-melting solvent are mixed, and the solvent discoloration property (solvent dissolving discoloration property only when used as such a three-component mixture) ) Or thermochromicity is realized. In addition, the conventional fluorane compound is vulnerable to heat, and when high-temperature heat is applied during the process, reversibility is lowered, and thus, the strength of discoloration is weakened, thereby limiting commercial application.

In view of these problems, the present inventors have devised a new fluorane compound having a high melting point and excellent light resistance and heat resistance. It is also noted that the fluorane compound of the present invention can induce temperature-dependent binding and proton transfer in the molecule by hydroxy introduced at a specific position. Accordingly, the fluorane compound according to the present invention has the advantage of exhibiting optical properties with excellent sensitivity even without acid lubricant in the realization of discoloration properties with temperature.

In addition, the floran compound of the present invention has a very small difference in energy gap (ΔE=E _LUMO -E _HOMO ), which can change from one steric structure to another steric structure for thermochromic discoloration, and can react sensitively to temperature changes. , Reversible thermochromic discoloration is possible through temperature-dependent bonding in the molecule.

Hereinafter, the floran compound of the present invention and its application will be described in detail.

The novel floran compound according to the present invention may be a compound represented by Formula 1 below.

[Formula 1]

[In the above formula 1,

R ₁ and R ₂ are independently hydrogen, C _{1- 20} alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl with one another;

R ₃ to R ₅ are independently hydrogen, C _{1- 20} alkyl or hydroxyalkyl, at least one selected from the R ₃ and R ₄ each is a hydroxy.]

As the hydroxyphenyl group is introduced into the ring (c) of the above formula 1, the temperature-dependent binding and proton transfer in the molecule are effectively induced. This effect corresponds to a specific effect as a 3-hydroxyphenyl group, 4-hydroxyphenyl group or 3,4-dihydroxyphenyl group is introduced, and a more surprising effect can be realized in the phenyl group containing one hydroxy group. Do. In addition, the above-described structural characteristics of the fluorane compound of the present invention have an important meaning, since the effect of intramolecular temperature-dependent bonding and proton transfer is insignificant or impossible in a compound in which a hydroxyphenyl group is introduced other than the position mentioned.

In addition, the compound of Formula 1 has a high melting point (mp 168°C or higher), and has excellent heat resistance.

From the side to allow the thermochromic properties implemented in high sensitivity, specifically, the compound of Formula 1 wherein R ₁ and R ₂ are independently hydrogen or C _{1- 20} alkyl each other; One selected from R ₃ and R ₄ is hydroxy, and the other is hydrogen or C _1-20 alkyl; Wherein R ₅ may be a hydrogen or C _{1- 20} alkyl.

In addition, in the compound of Formula 1, R ₁ and R ₂ are each independently hydrogen or C _1-20 alkyl; One of R ₃ and R ₄ is hydroxy and the other is hydrogen or C _1-20 alkyl; Wherein R ₅ may be a hydrogen or C _{1- 20} alkyl.

In addition, the compound of Formula 1 wherein R ₁ and R ₂ are independently C _{1- 7} alkyl and the other; One of the R ₃ and R ₄ is hydroxy and the other is hydrogen or C _{1- 7} alkyl; Wherein R ₅ may be a hydrogen or C _{1- 7} alkyl.

In addition, the compound of Formula 1 wherein R ₁ and R ₂ are independently C _{1- 7} alkyl, straight-chained with each other; One of R ₃ and R ₄ is hydroxy and the other is hydrogen; Wherein R ₅ may be a C _{1- 7} alkyl, hydrogen or a straight chain.

More specifically, the compound of Formula 1 may be at least one selected from compounds of the following structure, but is not limited thereto.

In the compound of the above structure according to an embodiment of the present invention, the difference in energy gap between the lactone form and the ring-opening form may be 3.0 or less, specifically 1.0 to 2.5, and more specifically 1.8 to 2.2.

For example, the lactone form of STC 1 may have an energy gap (ΔE=E _LUMO -E _HOMO ) of 3.9070, and an energy gap (ΔE′=E _LUMO -E _HOMO ) of the ring-opening form of STC 1 may be 1.8303.

The above-described floran compound of the present invention is a dye compound and exhibits reversible thermochromic properties. In addition, the floran compound of the present invention is capable of discoloration at a desired temperature despite the use of an acidic lubricant. Specifically, the floran compound of the present invention effectively induces structural denaturation in the molecule according to temperature, thereby realizing dramatic thermochromic properties.

As an example, the reversible thermochromic dispersion composition comprising the floran compound of the present invention exhibits a strong red color under a temperature lower than body temperature, and a white color (light yellow) under a temperature higher than body temperature.

Specifically, the reversible thermochromic dispersion composition according to the present invention may include a compound of Formula 1 and an aprotic solvent.

The aprotic solvent is not limited as long as it is a common one, and non-limiting examples thereof include toluene, chloroform, ethyl acetate, dimethoxyethane, tetrahydrofuran, methylene chloride, butanone, acetone, acetonitrile, sulfolane, and dimethyl It may be one or two or more mixed solvents selected from sulfoxide sites.

At this time, in the aspect that the reversible thermochromic dispersion composition is induced thermochromic at low temperature, the aprotic solvent is methyl stearate, ethyl stearate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl laur Rate, methyl oleate, methyl adipate, methyl caprylate, methyl caproate, methyl anthranirate, methyl palmitate, methyl palmitoate, methyl oxalate, methyl-2-nonanoate, methyl benzoate, methyl Benzophenone, methylbehenate, methylbenzylate, methylbenzyl acetate, trimethylborate, methylcaprate, methylbutylate, methyldetanoate, methylcyclohexanecarboxylate, methyldimethoxyacetate, methyldiphenylacetate, methyle It is preferable to include one or more mixed solvents selected from Nantate, methylheptanoate, and methyllinorate.

In addition, the reversible thermochromic dispersion composition according to an embodiment of the present invention may include 1 to 40% by weight of the compound of Formula 1 and a residual amount of an aprotic solvent based on the total weight of the composition. Specifically, the reversible thermochromic dispersion composition may include 5 to 40% by weight of the compound of Formula 1, and more specifically, 10 to 40% by weight of the compound of Formula 1, Most specifically, the compound of Chemical Formula 1 may be 20 to 40% by weight.

In addition, the reversible thermochromic dispersion composition according to an embodiment of the present invention may be substantially free of an acidic lubricant.

At this time, the acidic lubricant is not limited as long as it is capable of inducing a ring opening reaction of the floran compound by providing a proton, and non-limiting examples thereof include active clay, phenol resin, bisphenol A, etc.; Protonic solvents such as acetic acid, methane acid, etanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, methanol and ethanol; It may be selected from the like.

As described above, the reversible thermochromic dispersion composition according to an embodiment of the present invention implements colors of other aspects under a temperature lower than the body temperature and a temperature higher than the body temperature.

For example, the reversible thermochromic dispersion composition may be discolored from strong red to off-white under a temperature of 35°C or higher.

For example, the reversible thermochromic dispersion composition may be discolored from strong red to off-white under a temperature of 35°C to 120°C.

For example, the reversible thermochromic dispersion composition may be discolored from strong red to off-white under a temperature of 35°C to 80°C.

When the reversible thermochromic dispersion composition according to an embodiment of the present invention is reduced to a temperature lower than the above-mentioned discolored temperature range (low temperature), it immediately has a strong red color.

For example, the reversible thermochromic dispersion composition may have an absorption peak of 490 to 600 nm confirmed at a temperature of less than 35° C., and specifically an absorption peak of 490 to 550 nm.

For example, the reversible thermochromic dispersion composition may have an absorption peak of 300 to 400 nm confirmed at a temperature of 35° C. or higher, and specifically an absorption peak of 300 to 350 nm.

As described above, the reversible thermochromic dispersion composition is capable of realizing thermal discoloration even under high temperature, and also enables an instant reversible reaction according to temperature change.

In addition, the above-described floran compound of the present invention is a dye compound, which has high solubility in water, but is provided with the floran compound as a core at its inner center, and a polymer-coated polymer-encapsulated particle encapsulated on the outer peripheral surface of the core. That is, it is provided as insoluble particles and can be utilized in various applications.

Specifically, the dye-polymer integrated particles according to an embodiment of the present invention may include a core layer comprising the compound of Formula 1 and a polymer layer surrounding the surface of the core layer. As a result, the particles can completely conceal the color of the core layer at room temperature, and minimize the bleeding phenomenon of the dye compound during the process using the same, thereby increasing the productability of the desired product.

As an example, the fluorane compound of the present invention exhibits a red color at room temperature, but the above-described dye-polymerized particles may exhibit white at room temperature.

In addition, the dye-polymer-integrated particles according to an embodiment of the present invention have excellent barrier properties against external factors (eg, oxygen, water, etc.), and can further improve the lifespan of the floran compound of the present invention.

In the dye-polymer integrated particles according to an embodiment of the present invention, the polymer layer may include a polymer derived from a monomer having an unsaturated double bond.

At this time, the monomer having an unsaturated double bond is not limited as long as it is a common one, and non-limiting examples thereof include unsaturated monomers containing carboxyl groups such as acrylic acid, methacrylic acid, vinylbenzene acid, itaconic acid, maleic acid, and malic acid; C _{1- 20} alkyl acrylate, C _{1- 20} alkyl methacrylate, C _{3- 20} cycloalkyl acrylates, C _{3- 20} cycloalkyl methacrylate to other alkyl, C _{1- 20} alkoxy C _{1 - 20} alkyl acrylate, C _{1- 20} alkoxy C _{1- 20} alkyl methacrylate esters, hydroxy-C _{1 - 20} alkyl acrylate, hydroxy-C _{1 - 20} alkyl methacrylate ester, acrylonitrile, methacrylonitrile and trifluoro ethyl methacrylate Acrylate monomers such as acrylate; Styrene monomers, and the like, and one or two or more selected from them may be used during polymerization.

The dye-polymer integrated particles according to an embodiment of the present invention may have an average diameter of 10 μm or less.

For example, the average diameter of the dye-polymer integrated particles may be 1 to 5 μm.

For example, the average diameter of the dye-polymer integrated particles may be less than 100 to 1,000 nm, specifically 200 to 800 nm, and more specifically 300 to 500 nm.

The dye-polymer integrated particles according to an embodiment of the present invention may include 0.1 to 90% by weight of the compound of Formula 1 based on the total weight, specifically 10 to 80% by weight, more specifically 20 to 70% by weight.

In the dye-polymer integrated particles according to an embodiment of the present invention, the polymer layer may be formed to a thickness of 0.1 to 5,000 Å, specifically 5 to 3,000 ,, more specifically 50 to 2,000 Å It can be formed in the thickness of.

Hereinafter, the product containing the floran compound of the present invention will be described in detail.

Specifically, the present invention provides a compound of Formula 1, dye-polymerized particles, or a product comprising them. At this time, the product may be intended to use a discoloration characteristic according to temperature, and is not limited as long as it is for an immediate or visual monitoring of temperature change detection.

The product according to an embodiment of the present invention may be selected from cosmetics, ink, paint and indicators. At this time, the compound, the dye-polymerized particles, or the amount thereof may be changed in various ways depending on the purpose.

For example, when the compound, dye-polymer integrated particles, or these are applied to cosmetics, softening longevity, convergence longevity, nutrient longevity, eye cream, nutrition cream, massage cream, cleansing cream, cleansing foam, cleansing water, powder, essence, It may be formulated in a formulation selected from the group consisting of packs and the like.

For example, when the compound, the dye-polymer integrated particles, or these are applied to an indicator, it may be provided as a product such as a thermometer, a diagnostic kit, a patch, or a temperature sensor.

In addition, the product according to an embodiment of the present invention, the compound, dye-polymer integrated particles or they may be to include a coating, impregnated or molded substrate.

For example, the coating may be carried out by a method such as spin coating, spray coating, or the like, the compound, dye-polymer integrated particles, or the like.

For example, the impregnation may be performed through a method of dyeing or printing by adding a substrate to the compound, dye-polymer-integrated particles, or a solution containing them.

For example, the molding may be molded by injecting the compound, the dye-polymer-integrated particles, or the same when thermoforming or after injection molding the molding object after mixing the compound, the dye-polymer-integrated particles or a molding object with the compound. .

The substrate may be selected from fibers, wood, paper, metals and films.

The fiber is not limited as long as the dye compound is applicable, and non-limiting examples thereof include acrylic fiber, urethane fiber, polypropylene fiber, polyester fiber, polyarylene sulfide fiber, polyethylene fiber, polyamide fiber, and polylactic acid fiber. Synthetic fibers such as; Plant fibers such as cotton, wool, and rayon; Animal fibers such as silk and wool; Mineral fibers such as asbestos; And glass fibers; And the like.

The metal is not limited as long as the dye compound is applicable, and non-limiting examples thereof include iron, cobalt, molybdenum, niobium, copper, tantalum, silver, nickel, aluminum, tin, zinc, titanium, tungsten, or the like. And alloys.

The film is not limited as long as the dye compound is applicable, and as a non-limiting example thereof, cellulose-based resin, silicone resin, epoxy resin, acrylic resin, urethane resin, vinyl chloride resin, nylon resin, polyethylene, polypropylene, ABS resin , PET resin, polyacetal, polyvinyl chloride, polystyrene, polyethylene, polyester, polyamide, polyimide, polycarbonate, teflon resin, polystyrene and the like, and films formed from one or more mixtures.

The product according to an embodiment of the present invention, through the above-described method or formulation, clothing products such as sportswear, sports shoes, mountaineering clothes, hiking boots, gloves, masks, hats, helmets, gas masks, protective clothing, firefighting clothing; Medical products such as thermometers, syringes, stethoscopes, diagnostic kits or patches; Cosmetics such as mask packs; Electronic products such as sensors, batteries, boilers, cell phones, laptops, computers, refrigerators, air conditioners, heaters, electric blankets, and microwave ovens; Kitchen appliances such as gas stoves, gas ovens, kettles, cutlery, and dishes; Furniture such as beds and wardrobes; Accessories such as necklaces; Dyes used in inks, paints, paints, dyes, and the like; Interior or building materials such as insulating sheets, wallpaper, and windows; Lighting devices such as incandescent or led bulbs and stands; It can be used as a product in various fields such as, but is not limited thereto.

(Analysis method)

Structural analysis of the compounds prepared in Examples 1 to 8 was carried out using a hydrogen nuclear magnetic resonance ( ¹ H-NMR) using a Fourier transform nuclear magnetic resonance spectroscopy (Bruker, AVANCE III 400), the chemical shift is NMR solvent (CDCl ₃ - d ₁ :δ7.24, and DMSO- d ₆ :δ2.50) in ppm.

The product manufactured in Example was confirmed an applied image through a scanning electron microscope (SEM), and UV-Vis spectra for the compounds of Examples and Comparative Examples were measured with a SHIMADZU spectrometer (UV-2600).

(Assessment Methods)

1. Evaluation of thermochromic properties

To evaluate the thermochromic properties of the compounds of Examples and Comparative Examples, 5 mg of each compound of Examples and Comparative Examples was dispersed in 10 mg of methyl stearate and used as a sample. After each individual sample was individually stored at 20°C and 40°C, the color change of the sample was visually confirmed.

The results are shown in Figure 1 below.

2. Optical property evaluation

In order to evaluate the optical properties of the compounds of Examples and Comparative Examples, absorbance and light reflectance were measured using a UV-Vis spectrum (SHIMADZU spectrometer, UV-2600).

The results are shown in FIGS. 2 to 9 below.

(Examples 1 to 4)

STC 1 to STC 4, Manufacturing

2 eqv of potassium carbonate was added to a mixed solvent of toluene and ethanol (volume ratio 2:1, 15 ml), and the mixture was stirred at room temperature (25°C) for 20 minutes. Thereafter, the mixed solution was purged with nitrogen, and the compound 5-8 1 eqv, (3-hydroxyphenyl) boric acid 1 eqv (1.38 g) and tetrakis(triphenylphosphino) palladium 0.05 eqv were added to the reaction scheme at 80°C. Was stirred for 24 hours. After completion of the reaction, purification was performed through column chromatography (ethylacetate:petroleum ether=1:1) to obtain STC 1-4.

[ STC 1] Yield=70%; mp: 278°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 2.93 (s, 6H), 4.79 (s, 1H), 6.38 (m, 1H), 6.34 (dd, 1H, J=2.7, 9 Hz ), 6.45 (d, 1H, J=2.4 Hz), 6.55 (d, 1H, J=9 Hz), 6.65 (m, 1H), 6.74 (m, 1H), 6.85 (m, 2H), 7.1 (m , 2H), 7.16 (m, 1H), 7.23 (d, 1H, J=8.4 Hz), 7.48 (m, 3H), 7.94 (m, 1H); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 39.21, 97.52, 104.92, 108.02, 112.79, 113.16, 116.46, 118.51, 122.93, 124.05, 125.35, 125.72, 127.66, 128.24, 128.62, 128.96, 133.99 , 135.11, 140.66, 150.21, 151.17, 151.35, 152.44, 154.87, 168.79; ESI-MS (m/z) calcd. 434.4, found 435.15 (M + H+).

[ STC 2] Yield=67%; mp: 220°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 1.09 (t, 6H, J=14.1 Hz), 3.27 (m, 4H), 4.91 (bs, 1H), 6.29 (d, 1H, J =8.1 Hz), 6.42 (s, 1H), 6.51 (d, 1H, J=8.7 Hz), 6.66 (dd, 1H, J=2.1, 8.1 Hz), 6.74 (t, 1H, J=3.6 Hz), 6.842 (m, 2H), 7.1 (t, 2H, J=13.8 Hz), 7.23 (d, 1H, J=8.7 Hz), 7.47 (m, 3H), 7.95 (d, 1H, J=6.9 Hz); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 12.53, 44.51, 97.64, 104.89, 108.56, 113.84, 114.24, 117.45, 119.22, 119.50, 124.06, 125.07, 126.35, 128.90, 129.29, 129.66, 129.93 , 130.97, 135.02, 136.13, 141.60, 149.74, 151.30, 152.80, 153.23, 156.07, 170.05; ESI-MS (m/z) calcd. 463.18, found 462.0 (M-H+).

[ STC 3] Yield=69%; mp: 184°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 2.3 (d, 3H, J=42.6 Hz), 2.93 (s, 6H), 6.33 (m, 1H), 6.44 (m, 1H), 6.56 (m, 1H), 6.66 (d, 1H, J=7.8 Hz), 6.75 (m, 1H), 6.86 (m, 3H), 7.11 (m, 1H), 7.22 (d, 1H, J=8.7 Hz ), 7.29 (dd, 1H, J=20.1, 21 Hz), 7.46 (m, 1H), 7.74 (m, 1H); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 21.34, 22.09, 40.25, 83.42, 83.85, 98.51, 98.55, 106.10, 106.17, 109.03, 113.83, 113.86, 114.18, 114.21, 119.34, 119.37, 119.69 , 123.63, 124.06, 124.12, 124.81, 125.01, 126.40, 126.43, 126.99, 128.72, 128.77, 129.19, 129.21, 129.97, 130.89, 136.09, 136.11 136.25, 139.99, 141.66, 141.72, 146.43, 151.24 152.17, 152.25, 152.40, 154.23, 155.95, 155.98, 170.08; ESI-MS (m/z) calcd. 449.16, found 447.8 (M-H+).

[ STC 4] Yield=68%; mp: 175°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 1.09 (m, 6H), 2.29 (d, 3H, J=79.2 Hz), 3.27 (m, 4H), 6.28 (m, 1H), 6.4 (d, 1H, J=2.4 Hz), 6.52 (t, 1H, J=7.8 Hz), 6.66 (m, 1H), 6.76 (m, 1H), 6.81 (m, 2H), 6.89 (m, 1H ), 7.09 (m, 1H), 7.2 (d, 1H, J=8.4 Hz), 7.28 (dd, 1H, J=44.4, 45 Hz), 7.45 (m, 1H), 7.72 (m, 1H); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 12.73, 21.53, 22.28, 29.90, 44.70, 97.77, 105.25, 107.96, 108.71, 114.05, 114.07, 114.42, 117.60, 119.42, 119.82, 119.90, 123.93 , 124.41, 124.45, 124.99, 125.22, 126.59, 126.63, 127.41, 129.14, 129.17, 129.39, 129.43, 130.09, 130.13, 131.07, 136.25, 136.40, 140.18, 141.81, 146.59, 149.86, 149.86 , 156.27, 170.44; ESI-MS (m/z) calcd. 477.19, found 476.4 (M-H+).

(Examples 5 to 8)

STC 5 to STC 8, Manufacturing

2 eqv of potassium carbonate was added to a mixed solvent of toluene and ethanol (volume ratio 2:1, 15 ml), and the mixture was stirred at room temperature (25°C) for 20 minutes. Thereafter, the mixed solution was purged with nitrogen, and the compound 5-8 1 eqv, (3-hydroxyphenyl) boric acid 1 eqv (1.38 g) and tetrakis(triphenylphosphino) palladium 0.05 eqv were added to the reaction scheme at 80°C. Was stirred for 24 hours. After completion of the reaction, purification was performed through column chromatography (ethylacetate:petroleum ether=1:1) to obtain STC 5-8.

[ STC 5] Yield=72%; mp: 175°C; ¹ H-NMR (DMSO-d ₆ , 600 MHz), δ (ppm): 2.95 (s, 6H), 6.54 (s, 2H), 6.57 (m, 1H), 6.76 (d, 2H, J=8.4 Hz ), 6.81 (d, 1H, J=1.8 Hz), 7.21 (d, 2H, J=8.4 Hz), 7.3 (d, 1H, J=7.2 Hz), 7.41 (d, 1H, J=9 Hz), 7.67 (dd, 1H, J=8.4, 8.4 Hz), 7.72 (t, 1H, J=7.2 Hz), 7.78 (t, 1H, J=7.8 Hz), 8.03 (d, 1H, J=7.8 Hz), 9.53 (s, 1 H); ¹³ C-NMR (DMSO-d ₆ , 600 MHz), δ (ppm): 39.09, 39.92, 40.04, 83.03, 98.01, 105.27, 109.38, 115.78, 117.49, 123.98, 124.42, 124.75, 126.05, 127.44, 128.35, 128.72 , 129.53, 130.18, 135.64, 135.96, 149.82, 151.72, 152.06, 152.52, 157.11, 168.74; ESI-MS (m/z) calcd. 435.15, found 434.1 (M-H+).

[ STC 6] Yield=65%; mp: 265°C; ¹ H-NMR (CDCl ₃ , 300 MHz), (ppm): 1.09 (t, 6H, J=14.1 Hz), 3.27 (m, 4H), 4.91 (bs, 1H), 6.29 (d, 1H, J= 8.1 Hz), 6.42 (s, 1H), 6.51 (d, 1H, J=8.7 Hz), 6.66 (m, 1H), 6.747 (t, 1H, J=3.6 Hz), 6.84 (m, 2H), 7.1 (m, 2H), 7.23 (d, 1H, J=8.7 Hz), 7.47 (m, 3H), 7.94 (m, 1H) (Fig. S40); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 12.53, 44.49, 97.63, 104.88, 108.45, 115.64, 117.38, 119.47, 124.06, 124.99, 125,83, 126.90, 128.12, 128.88, 128.93, 129.57 , 130.93, 132.64, 134.96, 136.20, 149.68, 150.78, 152.79, 153.43, 155.23, 169.98; ESI-MS (m/z) calcd. 463.18, found 462.4 (M-H+).

[ STC 7] Yield=63%; mp: 168°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 2.29 (d, 3H, J=42.3 Hz), 2.92 (s, 6H), 6.33 (m, 1H), 6.44 (m, 1H), 6.55 (m, 1H), 6.66 (d, 1H, J=8.1 Hz), 6.75 (m, 1H), 6.84 (m, 3H), 7.1 (m, 1H), 7.22 (d, 1H, J=8.7 Hz ), 7.29 (dd, 1H, J=20.7, 20.4 Hz), 7.46 (m, 1H), 7.73 (m, 1H) (Fig. S43); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 20.31, 21.06, 39.22, 82.37, 82.79, 97.48, 97.52, 105.08, 105.14, 107.99, 112.80, 112.80, 113.14, 113.17, 116.40, 118.32, 118.36 , 118.61, 118.67, 122.59, 123.03, 123.08, 123.77, 123.97, 125.37, 125.40, 125.97, 127.69, 127.73, 128.15, 128.18, 128.91, 128.94, 129.85, 135.05, 135.07, 138.95, 140.145, 14069, 14069. , 150.22, 151.09, 151.13, 151.22, 151.37, 153.20, 154.90, 154.93, 169.02; ESI-MS (m/z) calcd. 449.16, found 448.5 (M-H+).

[ STC 8] Yield=64%; mp: 241°C; ¹ H-NMR (CDCl ₃ , 300 MHz), δ (ppm): 1.18 (t, 6H, J=13.8 Hz), 2.39 (d, 3H, J=39.6 Hz), 3.35 (m, 4H), 5 ( bs, 1H), 6.36 (m, 1H), 6.487 (d, 1H, J=2.4 Hz), 6.6 (m, 1H), 6.81 (m, 2H), 6.89 (m, 2H), 7.23 (m, 3H) ), 7.37 (m, 1H), 7.51 (m, 1H), 7.82 (m, 1H); ¹³ C-NMR (CDCl ₃ , 600 MHz), δ (ppm): 12.54, 21.34, 22.09, 44.49, 84.03, 84.47, 84.47, 97.57, 97.61, 104.98, 105.05, 108.43, 115.62, 115.65, 115.68, 117.33, 119.52 , 123.73, 124.19, 124.23, 124.74, 124.93, 125.86, 127.11, 127.89, 128.10, 128.12, 128.86, 128.90, 128.91, 128.96, 130.83, 132.50, 132.57, 136.20, 136.22, 139.91, 146.64, 150. , 150.83, 152.67, 152.82, 154.20, 155.36, 155.40, 170.35; ESI-MS (m/z) calcd. 477.19, found 476.5 (M-H+).

(Example 9)

dyes( STC 1)-Preparation of polymer-integrated particles

Step 1. SDS (Sodium dodecyl sulfate, 1.25Х10 ^-3 M) was added to 10 mL of distilled water and stirred at 60° C. for 1 hour to prepare an aqueous phase. Then, styrene (0.173 M), STC 1 (0.1 g) prepared in Example 1, n-hexadecane (2Х10 ^-3 M) and DVB (Divinyl Benzene, 2Х10 ^-3 M) were added to 5 ml ethyl acetate, and Dissolved to prepare an oil phase. The prepared oil phase was slowly added to the water phase, and stirred at 300 rpm for 1 hour at room temperature.

Step 2. The mixture of step 1 was emulsified at 20,000 rpm for 10 minutes using an emulsifying and dispersing machine (T25, IKA, Germany). Then, after degassing for 1 hour, the temperature was gradually increased (60°C).

Step 3. AIBN (Azobisisobutyronitrile, 2Х10 ^-3 M) was added to the mixture of step 2, and polymerization was performed under the same temperature. After the polymerization was completed, it was precipitated in methanol solution and left at 40°C for 8 hours. Thereafter, the precipitate was filtered and dried to obtain dye (STC 1)-polymer integrated particles (yield=90%).

The method of this is specifically shown in FIG. 10 below.

In addition, as a result of confirming the applied image through the scanning electron microscope (SEM) of the dye (STC 1)-polymer integrated particles obtained by the above method, the average diameter of the dye (STC 1)-polymer integrated particles was confirmed to be 2.2 μm.

(Example 10)

dyes( STC 1)-Preparation of fibers containing polymer-integrated particles

In the dye (STC 1)-polymer-integrated particle 10% by weight aqueous solution prepared in Example 9, the acrylic fiber material was immersed for 5 minutes and dried at room temperature to prepare a sample.

As a result of evaluating the thermochromic properties by sampling the thermochromic dispersion composition containing the fluorane compound according to the present invention, it exhibits a strong red color under a temperature of 20°C and an off-white color (light yellow) under a temperature of 40°C. It was confirmed that (see Figures 2 to 9 below). In addition, such a thermochromic property was confirmed to be the same color change even if it was repeatedly performed 10 or more times.

11 and 12, it was confirmed that the fibers obtained from Example 10 were stably coated with dye (STC 1)-polymer-integrated particles in the fibers, and turned white under a temperature of 40°C. It was confirmed that the dye (STC 1)-polymer integrated particles did not cause a state change even in a heat discolored state.

In addition, as shown in FIG. 13, it was confirmed that the fiber including the dye (STC 1)-polymer-integrated particles according to the present invention also exhibits extreme discoloration with temperature. Specifically, it was confirmed that one surface of the fiber maintaining a temperature of 20° C. or lower had a strong red color, and one surface of the fiber maintaining a temperature of 40° C. or higher had a colorless color.

From these results, the fluorane compound or dye-polymer integrated particles according to the present invention can realize thermochromic properties with high sensitivity and stably provide temperature change information, which is utilized in various fields to visually view temperature change information. It is expected to be useful as a thermochromic material that can be quickly transferred.

As described above, the present invention has been described by specific matters and limited embodiments, but it is provided only to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments, and the field to which the present invention pertains Those skilled in the art can make various modifications and variations from these descriptions.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims described below belong to the scope of the spirit of the invention. .

Claims (17)

Compound 1
[Formula 1]

In Chemical Formula 1,
R ₁ and R ₂ are independently hydrogen, C _{1- 20} alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl with one another;
R ₃ to R ₅ are independently hydrogen, C _{1- 20} alkyl or hydroxyalkyl, at least one selected from the R ₃ and R ₄ each is a hydroxy. According to claim 1,
The compound of Formula 1,
Wherein R ₁ and R ₂ are independently hydrogen or C _{1- 20} alkyl each other;
One of the R ₃ and R ₄ is hydroxy and the other is hydrogen or C _{1- 20} alkyl;
Wherein R ₅ is hydrogen or C _{1- 20} alkyl, compound. According to claim 1,
The compound of Formula 1,
Wherein R ₁ and R ₂ are independently a C _{1- 7} alkyl and the other;
One of the R ₃ and R ₄ is hydroxy and the other is hydrogen or C _{1- 7} alkyl;
Wherein R ₅ is hydrogen or C _{1- 7} alkyl, compound. According to claim 1,
The compound of Formula 1,
Wherein R ₁ and R ₂ are independently C _{1- 7} alkyl, straight-chained with each other;
One of R ₃ and R ₄ is hydroxy and the other is hydrogen;
Wherein R ₅ is C _{1- 7} alkyl, a compound of hydrogen or straight-chain. A core layer comprising the compound of claim 1 and
Particles comprising a polymer layer to thank the surface of the core layer. The method of claim 5,
The polymer layer,
A particle, a polymer derived from a monomer having an unsaturated double bond. The method of claim 5,
Particles having an average diameter of 5 µm or less. A reversible thermochromic dispersion composition comprising a compound of Formula 1 and an aprotic solvent:
[Formula 1]

In Chemical Formula 1,
R ₁ and R ₂ are independently hydrogen, C _{1- 20} alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl with one another;
R ₃ to R ₅ are independently hydrogen, C _{1- 20} alkyl or hydroxyalkyl, at least one selected from the R ₃ and R ₄ each is a hydroxy. The method of claim 8,
The aprotic solvent,
A reversible thermochromic dispersion composition comprising toluene, chloroform, dimethoxyethane, tetrahydrofuran, methylene chloride, butanone, acetone, acetonitrile, sulfolane, dimethylsulfoxide or a mixture thereof. The method of claim 8,
The aprotic solvent,
Methyl stearate, ethyl stearate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl laurate, methyl oleate, methyl adipate, methyl caprylate, methyl caproate, methyl anthranirate, methyl Palmitate, methyl palmitoate, methyl oxalate, methyl-2-nonanoate, methylbenzoate, methylbenzophenone, methylbehenate, methylbenzylate, methylbenzylacetate, trimethylborate, methylcaprate, methylbutylate , Methyldetanoate, methylcyclohexanecarboxylate, methyldimethoxyacetate, methyldiphenylacetate, methylenanthate, methylheptanoate, methyllinorate or mixed solvents thereof, reversible thermochromic dispersion composition. The method of claim 8,
The reversible thermochromic dispersion composition is based on the total weight,
It comprises a compound of Formula 1 in 1 to 40% by weight, reversible thermochromic dispersion composition. The method of claim 8,
The reversible thermochromic dispersion composition,
A reversible thermochromic dispersion composition that is discolored at a temperature of 35°C or higher. The method of claim 8,
The reversible thermochromic dispersion composition,
A reversible thermochromic dispersion composition that is substantially free of quantum materials. A product comprising the compound of claim 1 or the particles of claim 5. The method of claim 14,
The product,
Products selected from cosmetics, inks, paints and indicators. The method of claim 14,
The product,
The product, wherein the compound or particle comprises a coated, impregnated or molded substrate. The method of claim 16,
The above description,
Product selected from fiber, wood, paper, metal and film.

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