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WO2018143473A1 - Colorant sensible à la température - Google Patents

Colorant sensible à la température Download PDF

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Publication number
WO2018143473A1
WO2018143473A1 PCT/JP2018/003995 JP2018003995W WO2018143473A1 WO 2018143473 A1 WO2018143473 A1 WO 2018143473A1 JP 2018003995 W JP2018003995 W JP 2018003995W WO 2018143473 A1 WO2018143473 A1 WO 2018143473A1
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WIPO (PCT)
Prior art keywords
organic
compound
pigment
dye
acid
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Ceased
Application number
PCT/JP2018/003995
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English (en)
Japanese (ja)
Inventor
和之 石井
虎太郎 石田
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University of Tokyo NUC
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University of Tokyo NUC
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Publication date
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Priority to JP2018566168A priority Critical patent/JP7329229B2/ja
Publication of WO2018143473A1 publication Critical patent/WO2018143473A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/26—Thermosensitive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

Definitions

  • the present invention relates to a color material whose optical characteristics change with temperature.
  • thermochromism The change in optical characteristics, that is, absorption, reflectance, and transmittance at each wavelength depending on temperature is called thermochromism.
  • Many substances having thermochromic properties are known regardless of whether they are organic or inorganic compounds, and there are various types such as changes in molecular structure and changes in conformation.
  • the encapsulated leuco dye is known as a thermochromic material that changes its molecular structure in a certain temperature range (Non-Patent Document 1) and is commercially available.
  • Non-Patent Document 1 thermochromic material that changes its molecular structure in a certain temperature range
  • Non-Patent Document 2 thermochromic material that changes its molecular structure in a certain temperature range
  • materials of a type whose molecular structure changes such as an encapsulated leuco dye, fades when exposed to ultraviolet rays or high temperatures for a long time.
  • Non-patent Document 2 a temperature-variable heat shielding effect by a combination with a reflecting material.
  • the absorption band disappears at a high temperature, and further temperature rise is prevented by reflecting sunlight, while the absorption band appears at a low temperature and the temperature can be raised by absorbing sunlight.
  • changes in sunlight absorption rate, light resistance and heat resistance are important.
  • the phthalocyanine complex exists as a monomer in a low concentration solution and has a sharp Q absorption band in the vicinity of 700 nm.
  • the Q absorption band becomes broad due to the strong ⁇ - ⁇ interaction between the phthalocyanine complexes (FIG. 1). If such a dramatic spectral change can be achieved by a temperature change near room temperature, it can be expected to develop into a new temperature-variable heat shielding material. However, an effective color material that can be used for such a temperature-variable heat shielding material has not been developed.
  • An object of the present invention is to provide a novel temperature-responsive color material. More specifically, an object of the present invention is to provide a temperature responsive (thermochromic) coloring material using a change in light absorption due to association of molecules, not a type in which the molecular structure accompanying a chemical reaction changes. To do.
  • the present inventors focused on dyes such as phthalocyanine complexes whose light absorption changes due to changes in the association state of the molecules, and studied a method for controlling the change in light absorption. As a result, liquid crystals having a phase transition temperature near room temperature.
  • the present inventors have found that thermochromic properties of phthalocyanine complexes and the like can be controlled by mixing phthalocyanine complexes in organic molecules and organic solvents. That is, when a liquid crystal molecule or an organic solvent is in a solid state, a dye such as a phthalocyanine complex is also associated with a molecule, and thus has a broad Q absorption band.
  • the present inventors have conducted intensive studies and have found that pigments, organic dyes, or infrared rays whose light absorption changes due to changes in the association state of liquid crystal molecules or organic solvents having a phase transition temperature near room temperature and molecules such as phthalocyanine complexes.
  • the inventors have found that a colorant capable of efficiently controlling thermochromic properties can be provided by encapsulating a mixture with an absorbing dye, thereby completing the present invention.
  • the present inventors have examined that a phthalocyanine complex is mixed in an organic compound such as fatty acid, wax, fats and oils, ionic liquid, natural polymer, synthetic polymer, phospholipid having a phase transition temperature around room temperature.
  • thermochromic properties such as phthalocyanine complex can be controlled.
  • the thermochromic characteristics can be controlled efficiently by encapsulating a mixture of these organic compounds and pigments, organic dyes or infrared absorbing dyes whose light absorption changes due to changes in the association state of molecules such as phthalocyanine complexes.
  • the present inventors have found that a color material can be provided and completed the present invention. Furthermore, the present inventors have found that a poorly water-soluble color material can be obtained by adding a specific cation to the encapsulated color material.
  • the present invention [1] (i) at least one organic compound having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye, the organic compound, and the pigment,
  • An organic dye or an infrared absorbing dye is a coloring material encapsulated in a capsule.
  • the organic compound is selected from liquid crystal compounds, organic solvents, fatty acids, waxes, fats and oils, ionic liquids, natural polymers, synthetic polymers, phospholipids, or combinations thereof [1] or [2 ]
  • the coloring material as described in. [4] The color material according to any one of [1] to [3], wherein the capsule is made of a micelle or a lipid bilayer (liposome).
  • [5] (i) at least one fatty acid having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye, the fatty acid, and the pigment or organic dye Alternatively, the infrared absorbing dye is a coloring material that is encapsulated in micelles formed from a metal salt of the fatty acid.
  • [6] A solution containing the color material according to any one of [1] to [5].
  • [7] A dispersion containing the color material according to any one of [1] to [5].
  • the organic compound is selected from liquid crystal compounds, organic solvents, fatty acids, waxes, fats and oils, ionic liquids, natural polymers, synthetic polymers, phospholipids, or combinations thereof [8] or [9 ]
  • the coloring material as described in.
  • the liquid crystalline compound includes 4-cyano-4′-heptylbiphenyl, 4-cyano-4′-octyloxybiphenyl, 4-cyano-4′-pentylbiphenyl, 4-cyano-4′-hexylbiphenyl, 4-cyano-4′-n-octylbiphenyl, 4- (trans-4-amylcyclohexyl) benzonitrile, 4- (trans-4-ethylcyclohexyl) benzonitrile, (S) -4-cyano-4 ′-( 2-methylbutyl) biphenyl, 3,4,5-trifluoro-4 ′-(trans-4-propylcyclohexyl) biphenyl, 4′-ethoxybenzylidene-4-butylaniline, TK-LQ 3858, TK-LQ 2040, linole Made of acid cholesterol, cholesterol oleyl carbonate, phospholipids and mixtures of two or more
  • the organic solvent is cyclohexanol, glycerol, p-xylene, diphenylmethane, 1,3-dimethoxybenzene, diphenyl ether, acetophenone, propiophenone, benzyl benzoate, p-chlorotoluene, 1,2,4-tri
  • the color material according to [10] which is selected from the group consisting of chlorobenzene and a mixed solvent of two or more of these.
  • the fatty acid is octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, hexadec-9-enoic acid, (9Z) -octadece-9-enoic acid, (9E) -9-octadecenoic acid (9E, 11E, 13Z) -9,11,13-octadecatrienoic acid, (13Z) -13-docosenoic acid, (Z) -tetracoce-15-enoic acid and mixtures of two or more thereof.
  • the color material according to [10] which is selected.
  • the fats and oils are palm oil, palm oil, lard, beef tallow, cacao butter, palm butter, almond butter, macadamia butter, hemp seed butter, jojoba butter, coffee butter, shea butter, soybean butter, palm hardened oil, beef tallow
  • the coloring material according to [10] which is selected from the group consisting of hydrogenated oil, lard hardened oil, soybean hardened oil, rapeseed hardened oil, and a mixture of two or more thereof.
  • the organic dye is at least one selected from azo compounds, quinone compounds, triarylmethane compounds, cyanine compounds, phthalocyanine compounds, or indigo compounds, [8] to [16] The color material according to any one of the above.
  • the infrared absorbing dye is at least one selected from a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, an anthracocyanine compound, an azo compound, a quinone compound, or a squalium compound.
  • the coloring material according to any one of [17].
  • the infrared absorbing dye is a colorant that is encapsulated in micelles formed of a metal salt of the fatty acid, and a cation is bonded or adhered to the surface of the micelle.
  • a composition comprising an organic compound having a transition point such as a melting point near room temperature, and a pigment, an organic dye or an infrared absorbing dye whose light absorption changes due to a change in the association state of at least one molecule.
  • a coloring material is prepared, including the step of adding the composition and a surfactant or phospholipid to water to obtain an aqueous solution, and (3) adding a compound that generates a cation to the aqueous solution.
  • An organic compound having a transition point such as a melting point near room temperature, a pigment whose light absorption changes due to a change in the association state of at least one molecule, an organic dye or an infrared absorbing dye, and a surfactant or phosphorus A method of preparing a coloring material, comprising: adding a lipid to water to obtain an aqueous solution; and (2) adding a compound that generates a cation to the aqueous solution.
  • a dispersion comprising the color material according to any one of [8] to [22] and water, an organic solvent, or a mixture thereof.
  • a coating composition comprising the color material according to any one of [8] to [22]; water, an organic solvent or a mixture thereof; and a resin.
  • a heat shielding material comprising a reflective material and a layer containing the color material according to any one of [8] to [22] provided on the reflective material. Is provided.
  • thermochromic coloring material using a change in light absorption due to association of molecules, not a type in which the molecular structure accompanying a chemical reaction changes.
  • the thermochromic material of the present invention can suppress discoloration due to heat or light as compared with a chemical change type thermochromic material such as a conventional encapsulated dye.
  • SIPC (OH) diffuse reflectance spectra of the electronic absorption spectra and SIPC (OH) 2 powder 2 in toluene Schematic diagram of the method for preparing SiPc (OH) 2 / 8OCB mixed thin film (film) Measurement result of electronic absorption spectrum of SiPc (OH) 2 / (cyclohexanol + glycerol) film Measurement result of electronic absorption spectrum of SiPc (OH) 2 / 8OCB film Measurement result of diffuse reflection spectrum of capsule insolubilized with SiPc (OH) 2 / 8OCB mixture Evaluation results of heat shielding effect of SiPc (OH) 2 / 8OCB mixture and SiPc (OH) 2 / 7CB mixture which have been insolubilized Measurement result of diffuse reflection spectrum of SiPc (OH) 2 / 8OCB thin film SIPC (OH) energy diagram schematic view of a 2 / 8OCB thin Measurement result of electronic absorption spectrum of SiPc (OH) 2 / dodecanoic acid mixed
  • One embodiment of the present invention comprises (i) at least one organic compound having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye,
  • the compound, and the pigment or organic coloring matter are color materials encapsulated in capsules (hereinafter also referred to as “embodiment 1”).
  • the pigment, organic dye or infrared absorbing dye that can be used in the present invention is preferably a pigment, organic dye or infrared absorbing dye whose light absorption spectrum changes due to a change in the association state of molecules. Specifically, it is a pigment, organic dye or infrared absorbing dye whose absorption spectrum of light changes depending on whether the pigment, organic dye or infrared absorbing dye is in a solid state or in a solution.
  • the type of the pigment that can be used in the present invention is not particularly limited as long as it exhibits the above-mentioned characteristics.
  • the organic pigment include phthalocyanine pigments, and examples of the inorganic pigment include titanium oxide and carbon. Black, iron oxide, yellow lead, ultramarine, etc. are mentioned.
  • the phthalocyanine pigment any of those containing a metal in the center (phthalocyanine complex) and those containing no metal can be used.
  • t-BuSiPc (OH) 2 silicon 2,9,16,23-tetra-tert-butyl-29H, 31H-phthalocyanine dihydroxide having the following structure is particularly preferable.
  • the organic dye that can be used in the present invention is not particularly limited as long as it is an organic dye exhibiting the above-mentioned characteristics.
  • azo compounds, quinone compounds, triarylmethane compounds, cyanine Compounds, phthalocyanine compounds, indigo compounds and the like are examples of organic dye exhibiting the above-mentioned characteristics.
  • the infrared absorbing dye that can be used in the present invention is not particularly limited as long as it is an infrared absorbing dye exhibiting the above-mentioned characteristics.
  • cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, anthra Examples include cocyanine compounds, azo compounds, quinone compounds, squalium compounds, and the like.
  • the infrared absorbing dye includes a near infrared absorbing dye.
  • the color material of the present invention may contain two or more pigments, organic dyes or infrared absorbing dyes, or may contain two or more combinations arbitrarily selected from pigments, organic dyes or infrared absorbing dyes.
  • Organic compounds having a transition point such as a melting point near room temperature include liquid crystalline compounds having a transition point such as a melting point near room temperature, organic solvents, fatty acids, waxes, fats and oils, ionic liquids, natural polymers, synthetic polymers, phosphorus Selected from lipids or combinations thereof.
  • the transition point includes the melting point.
  • the liquid crystalline compound that can be used in the present invention is not particularly limited as long as it is a liquid crystalline compound that undergoes a phase transition near room temperature, specifically, a liquid crystalline compound having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • phospholipids examples include phosphatidic acid having a transition point such as a melting point at 0 ° C. to 50 ° C. (for example, dimyristoyl phosphatidylcholine, dipalmitoylphosphatidylcholine, distearyl phosphatidylcholine, etc.), phosphatidylethanolamine, phosphatidylcholine, phosphatidylserine, phosphatidylglycerol Etc.
  • phosphatidic acid having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • dimyristoyl phosphatidylcholine dipalmitoylphosphatidylcholine, distearyl phosphatidylcholine, etc.
  • phosphatidylethanolamine phosphatidylcholine
  • phosphatidylserine phosphatidylglycerol Etc.
  • the organic solvent that can be used in the present invention can be used without particular limitation as long as it is an organic solvent that undergoes a phase transition near room temperature, specifically, an organic solvent having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • examples include cyclohexanol, glycerol, p-xylene, diphenylmethane, 1,3-dimethoxybenzene, diphenyl ether, acetophenone, propiophenone, benzyl benzoate, p-chlorotoluene, 1,2,4-trichlorobenzene, and the like.
  • a mixed solvent composed of two or more of these can also be used.
  • a mixed solvent of cyclohexanol and glycerol can be suitably used.
  • the fatty acid that can be used in the present invention can be used without particular limitation as long as it undergoes a phase transition near room temperature, specifically, a fatty acid having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • Acid nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, hexadec-9-enoic acid, (9Z) -octadedec-9-enoic acid, (9E) -9-octadecenoic acid, (9E, 11E, 13Z) -9,11,13-octadecatrienoic acid, (13Z) -13-docosenoic acid, (Z) -tetracoce-15-enoic acid and mixtures of two or more thereof can be used.
  • the wax that can be used in the present invention can be used without particular limitation as long as it undergoes a phase transition near room temperature, specifically, a wax having a transition point such as a melting point at 0 ° C. to 50 ° C. It can be selected from the group consisting of wax, petrolatum, lanolin, wood wax, white wax, beeswax, spermaceti and mixtures of two or more thereof.
  • oils and fats that can be used in the present invention can be used without particular limitation as long as they are oils and fats that undergo a phase transition near room temperature, specifically oils and fats having a transition point such as a melting point at 0 ° C to 50 ° C.
  • palm oil, palm oil, lard, beef tallow, cacao butter, palm butter, almond butter, macadamia butter, hemp seed butter, jojoba, coffee butter, shea butter, soybean butter, palm hardened oil, beef fat cured Oil, lard hardened oil, soybean hardened oil, rapeseed hardened oil and a mixture of two or more thereof are easily available and can be suitably used.
  • the ionic liquid that can be used in the present invention can be used without particular limitation as long as it is an ionic liquid that undergoes a phase transition near room temperature, specifically, an ionic liquid having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • the natural polymer that can be used in the present invention is not particularly limited as long as it is a natural polymer that undergoes a phase transition near room temperature, specifically, a natural polymer having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • a natural polymer having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • polyamines, natural rubbers, polypeptides and the like having a transition point such as a melting point at 0 ° C. to 50 ° C. can be used.
  • the synthetic polymer that can be used in the present invention is not particularly limited as long as it is a synthetic polymer that undergoes a phase transition near room temperature, specifically, a synthetic polymer having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • synthetic resins (plastics) having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • polyvinyl chloride polyethylene, phenol resin, polytetramethylene oxide, polyethylene adipate, etc.
  • silicon resins silicon Oil
  • synthetic fibers nylon, vinylon, polyester, polyethylene terephthalate, etc.
  • synthetic rubber cis-1,4-polybutadiene, cis-1,4-polyisoprene
  • the phospholipid that can be used in the present invention can be used without particular limitation as long as it is a phospholipid that undergoes a phase transition near room temperature, specifically, a phospholipid having a transition point such as a melting point at 0 ° C. to 50 ° C.
  • a transition point such as a melting point at 0 ° C. to 50 ° C.
  • dimyristoyl phosphatidylcholine, dipalmitoyl phosphatidylcholine, distearyl phosphatidylcholine and the like can be used.
  • the capsule is preferably made of a micelle or a lipid bilayer (liposome).
  • the micelle is preferably formed of a surfactant.
  • a surfactant an anionic surfactant is preferable, and in particular, a surfactant having a sulfone group or a carboxyl group, specifically, a fat-soluble portion and a sulfo group, or a fat-soluble portion and a carboxyl group.
  • a surfactant is preferred.
  • the surfactant that can be used in the present invention include sodium lauryl sulfate and sodium laurate.
  • Lipid bilayers are usually formed from phospholipids.
  • the phospholipid include, but are not limited to, phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylglycerol, diphosphatidylglycerol, and sphingomyelin.
  • an absorption spectrum of light changes due to a change in an association state of an organic compound having a transition point such as a melting point near room temperature and at least one molecule.
  • organic dye or infrared absorbing dye for example, an organic compound such as a liquid crystalline compound having a transition point such as a melting point near room temperature, a pigment, an organic dye or Infrared absorbing dye is dissolved in an organic solvent (for example, chloroform), and the resulting solution is dropped on a substrate (glass plate, plastic film, etc.) and the solvent is evaporated by drying in a vacuum, etc. A cast film made of a composition containing a pigment, an organic dye or an infrared absorbing dye is obtained.
  • the concentration of an organic compound such as a liquid crystal compound, a pigment, an organic dye, or an infrared absorbing dye added to the organic solvent can be determined as appropriate depending on the type of the organic compound, the pigment, and the like to be used.
  • the cast film is removed from the substrate, added to an aqueous solution in which the surfactant or phospholipid is dissolved, and stirred to form the micelle or phospholipid formed by the surfactant.
  • an aqueous solution containing an encapsulated coloring material can be obtained.
  • Stirring can be performed by ultrasonic treatment, a mechanical homogenizer (colloid mill), a high-pressure homogenizer, or the like.
  • the concentration of the surfactant or phospholipid can be appropriately determined depending on the type of the surfactant used and the like, but is usually 0.1 mM to 10 3 mM.
  • the amount of cast film (that is, an organic compound such as a liquid crystal compound and a composition such as a pigment) can be appropriately determined, but is usually 0.1 to 1000 g / L.
  • the encapsulated colorant of the present invention comprises an organic compound having a transition point such as a melting point near room temperature, a pigment whose light absorption changes due to a change in the association state of at least one molecule, an organic dye or an infrared absorbing dye, and It can also be prepared by a production method comprising a step of adding a surfactant to water to obtain an aqueous solution.
  • the method for stirring the solution, the concentration of the surfactant and the like are the same as in the above production method.
  • the particle size of the encapsulated colorant (that is, micelle) varies depending on the organic compound, pigment, organic dye or infrared absorbing dye used, the type of surfactant, and the amount added, but usually 1 nm to 100 ⁇ m, preferably Is from 10 nm to 10 ⁇ m.
  • One aspect of the color material of the present invention is a solution containing the color material described above.
  • Another aspect of the color material of the present invention is a dispersion containing the color material described above.
  • One aspect of the colorant of Embodiment 1 includes (i) at least one fatty acid having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye,
  • the fatty acid, the pigment, the organic dye, or the infrared absorbing dye is a color material included in micelles.
  • the metal salt acts as a surfactant and forms micelles. That is, inside the micelle, a pigment, an organic dye, or an infrared absorbing dye is dissolved or dispersed in a fatty acid, and a metal salt (such as a sodium salt) of the fatty acid can provide a coloring material that forms a micelle.
  • Preferred examples of such a coloring material include lauric acid and at least one pigment, organic dye or infrared absorbing dye, and the lauric acid and the pigment, organic dye or infrared absorbing dye are formed of sodium laurate. It is a color material included in the micelle.
  • the encapsulated color material of Embodiment 1 is basically soluble in water, and is preferably insolubilized in water or an organic solvent for practical use as a color material.
  • a specific cation to the encapsulated color material, a color material hardly soluble in water can be provided.
  • another embodiment of the present invention includes (i) an organic compound having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye, , And the pigment, organic dye, or infrared absorbing dye is a colorant that is encapsulated by capsules made of micelles or liposomes, and a cation is bound or attached to the surface of the micelles or liposomes (hereinafter referred to as “embodiment 2”). ").
  • the color material of Embodiment 2 is preferably a poorly water-soluble color material.
  • the poorly water-soluble colorant includes a colorant that is slightly soluble in water (for example, less than 1 mM in solubility) in addition to a colorant that is not soluble in water at all.
  • the liquid crystal compound, organic solvent, pigment, organic dye, infrared absorbing dye, micelle, and liposome are the same as those described in the first embodiment.
  • the cation used in Embodiment 2 is barium ion, calcium ion, magnesium ion, zinc ion, lead ion, copper ion, mercury ion, silver ion or strontium ion.
  • the encapsulated coloring material is precipitated by binding to the anion on the micelle surface, and a poorly water-soluble coloring material can be provided.
  • the light absorption spectrum changes due to the change in the association state of the organic compound having a transition point such as the melting point and the at least one molecule near room temperature.
  • a step of forming a composition comprising a pigment, an organic dye or an infrared absorbing dye, (2) a step of adding the composition and a surfactant or phospholipid to water to obtain an aqueous solution, and (3) a cation in the aqueous solution. Adding a compound that yields.
  • the steps (1) and (2) of the method for producing a color material according to Embodiment 2 of the present invention are as described in the method for producing an encapsulated color material according to Embodiment 1.
  • an organic compound having a transition point such as a melting point in the vicinity of room temperature, and a micelle or liposome containing a pigment, an organic dye or an infrared-absorbing dye
  • a cation is added to the aqueous solution, whereby micelles or liposomes aggregate to form a poorly water-soluble colorant.
  • Examples of the cation include barium ion, calcium ion, magnesium ion, zinc ion, lead ion, copper ion, mercury ion, silver ion, and strontium ion.
  • Examples of the compound that generates these cations include barium chloride, chloride, Examples include calcium, magnesium chloride, zinc chloride, lead chloride, copper chloride, mercury chloride, silver chloride, and strontium chloride.
  • the color material of Embodiment 2 includes (1) an organic compound having a transition point such as a melting point near room temperature, a pigment, an organic dye, or an infrared absorbing dye whose light absorption changes due to a change in the association state of at least one molecule And a step of adding a surfactant or phospholipid to water to obtain an aqueous solution, and (2) adding a compound that generates a cation to the aqueous solution.
  • a transition point such as a melting point near room temperature
  • a pigment such as a pigment, an organic dye, or an infrared absorbing dye whose light absorption changes due to a change in the association state of at least one molecule
  • a step of adding a surfactant or phospholipid to water to obtain an aqueous solution
  • (2) adding a compound that generates a cation to the aqueous solution.
  • One aspect of the colorant of embodiment 2 includes (i) at least one fatty acid having a transition point such as a melting point near room temperature, and (ii) at least one pigment, organic dye or infrared absorbing dye,
  • the fatty acid, the pigment, the organic dye, or the infrared-absorbing dye is a colorant that is encapsulated in micelles, and a cation is bonded or adhered to the surface of the micelle.
  • the metal salt acts as a surfactant and forms micelles.
  • a pigment, an organic dye, or an infrared absorbing dye is dissolved or dispersed in a fatty acid, and a metal salt (such as a sodium salt) of the fatty acid can provide a coloring material that forms a micelle.
  • a coloring material include dodecanoic acid and at least one pigment, organic dye or infrared absorbing dye, and the dodecanoic acid and the pigment, organic dye or infrared absorbing dye are formed of sodium dodecanoate.
  • the coloring material is encapsulated in the micelle and has a cation bonded or attached to the surface of the micelle.
  • a cation a calcium ion is preferable.
  • One embodiment of the present invention is a dispersion containing the colorant of Embodiment 2 and water, an organic solvent, or a mixture thereof.
  • Another aspect of the present invention is a coating composition
  • a coating composition comprising the colorant of Embodiment 2, water, an organic solvent or a mixture thereof, and a resin. Since the color material of Embodiment 2 is hardly soluble in water and an organic solvent, the color material can be suitably used as a paint by dispersing the color material in water, an organic solvent, or the like.
  • the resin that can be used as the resin component and the resin that is formed from the resin component by curing at the time of coating are not particularly limited, and examples include resins that are usually used in the coating industry. be able to. Specifically, acrylic resin, silicone resin, acrylic silicone resin, styrene acrylic copolymer resin, polyester resin, fluorine resin, rosin resin, petroleum resin, coumarone resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin Cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, vinyl resin (polyvinylidene chloride, etc.), amine resin, ketimine resin and the like. These resins may be used alone or in combination of two or more.
  • organic solvent which can be used in the coating composition of this invention
  • the organic solvent normally used in a coating material can be illustrated.
  • alcohol isopropyl alcohol, ethanol, butanol, etc.
  • ketone solvents methyl ethyl ketone, acetone, etc.
  • ester solvents ethyl acetate, butyl acetate
  • toluene xylene
  • amide solvents dimethylacetamide, etc.
  • Two or more organic solvents can be mixed and used, and a mixture of water and an organic solvent can also be used.
  • the coating composition of the present invention may contain pigments other than the coloring material of Embodiment 2.
  • a pigment is not particularly limited, and a pigment usually used in the paint industry can be used. Specific examples include pigments such as titanium dioxide, iron oxide, and carbon black, extender pigments such as silica, talc, mica, calcium carbonate, and barium sulfate, zinc, zinc phosphate, aluminum phosphate, zinc molybdate, and metaboric acid. Examples thereof include rust preventive pigments such as barium and hydrocalumite, and bright pigments such as aluminum, nickel, chromium, tin, copper, silver, platinum, gold, stainless steel, and glass flakes.
  • pigment dispersants In the coating composition of the present invention, pigment dispersants, thickeners, surface conditioners, film-forming aids, UV absorbers, antioxidants, flame retardants, antistatic agents, rust inhibitors, etc. Various known ingredients can be included.
  • the coating means of the coating composition of the present invention is not particularly limited, and known coating means such as spray coating, roller coating, brush coating, trowel coating, spatula coating and the like can be used.
  • the coating composition of the present invention can be used as a functional coating because it has the property of absorbing sunlight at low temperatures and transmitting sunlight when the temperature rises.
  • it can be used as a building paint having the characteristics of absorbing sunlight and converting it into heat in winter and transmitting sunlight in summer to prevent temperature rise.
  • Another aspect of the present invention is a heat shielding material including a reflective material and a layer containing the poorly water-soluble color material of the present invention provided on the reflective material.
  • a heat shielding material mainly composed of aluminum, a heat shielding paint using a highly reflective pigment represented by titanium oxide, or the like can be used.
  • the layer containing the color material of Embodiment 2 can be formed, for example, by applying the above-described coating composition of the present invention on a reflective material.
  • the layer can also be formed by mixing the color material of Embodiment 2 with a resin to form a film and laminating the film on a reflective material.
  • an adhesive layer may be provided between the reflective material and the layer.
  • the color material of Embodiment 2 absorbs sunlight in winter and converts it into heat, and transmits sunlight in summer and reflects sunlight by the reflective material to prevent temperature rise. be able to.
  • FIG. 2 shows a schematic diagram of SiPc (OH) 2 / 8OCB film preparation, and encapsulation and insolubilized SiPc (OH) 2 / 8OCB mixed thin film (film) production method.
  • SiPc (OH) 2 (2.0 ⁇ 10 ⁇ 8 mol) and 8OCB (2.0 ⁇ 10 ⁇ 4 mol, 60 mg) were dissolved in toluene to prepare a mixed solution.
  • the mixed solution was dropped into a 0.5 mm-thick bonding cell, and the solvent toluene was removed by vacuum drying at 60 ° C. in which 8OCB became a liquid crystal phase. Then, the glass substrate was bonded together from the top, and the film with uniform thickness was obtained.
  • a film was prepared in a sample bottle, and then 0.5 mL of 2% SDS (sodium dodecyl sulfate) aqueous solution was added as a surfactant. The sample was sonicated for 3 hours to obtain an aqueous SDS micelle solution containing a SiPc (OH) 2 / 8OCB mixture.
  • SDS sodium dodecyl sulfate
  • the SiPc (OH) 2 / 8OCB film shows a broad absorption band at a sample temperature of 30 ° C., whereas it shows a sharp absorption band at 60 ° C. and 80 ° C., and the electron absorption spectrum Was observed to vary greatly around room temperature. From this, SiPc (OH) 2 is in an associated state near 30 ° C., whereas 8OCB becomes a liquid crystal and liquid state as the temperature increases to 60 ° C. and 80 ° C., and SiPc (OH) 2 is a monomer. It is thought that it exists as.
  • FIG. 6 shows the results of the xenon lamp irradiation experiments coating containing SiPc (OH) 2 / 7CB mixture
  • FIG. 6 xenon coating containing SiPc (OH) 2 / 8OCB mixture
  • the result of a lamp irradiation experiment is shown.
  • the coating containing SiPc (OH) 2 / 8OCB mixture rose to 34.4 ° C., whereas the coating containing SiPc (OH) 2 / 7CB mixture was 29.5 ° C. The temperature rose only up to.
  • the color of the coating film containing the SiPc (OH) 2 / 7CB mixture was changed with the naked eye after irradiation. Therefore, it is considered that the photothermal conversion by SiPc (OH) 2 in the coating film was suppressed by the change in the absorption spectrum of SiPc (OH) 2 accompanying the phase transition of 7CB.
  • FIG. 8 is an energy diagram conceptual view of SiPc (OH) 2 / 8OCB thin film.
  • Example 4 (1) Production of SiPc (OH) 2 / dodecanoic acid mixed thin film (film) SiPc (OH) 2 (1.2 ⁇ 10 ⁇ 8 mol) and dodecanoic acid (2.5 ⁇ 10 ⁇ 4 mol, 50 mg) in chloroform To prepare a mixed solution. The mixed solution was dropped into a bonding cell having a thickness of 0.5 mm and vacuum-dried at 40 ° C. to remove the solvent chloroform. Then, the glass substrate was bonded together from the top, and the film with uniform thickness was obtained.
  • Example 5 (1) Preparation of SiPc (OH) 2 / (13Z) -13-docosenoic acid mixed thin film (film) SiPc (OH) 2 (7.4 ⁇ 10 ⁇ 9 mol) and (13Z) -13-docosenoic acid (1 0.5 ⁇ 10 ⁇ 4 mol, 50 mg) was dissolved in chloroform to prepare a mixed solution. The mixed solution was dropped into a bonding cell having a thickness of 0.5 mm and vacuum-dried at 27 ° C. to remove the solvent chloroform. Then, the glass substrate was bonded together from the top, and the film with uniform thickness was obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Colloid Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un nouveau matériau sensible à la température. La solution apportée est un colorant comprenant (i) un composé organique ayant un point de transition tel qu'un point de fusion proche de la température ambiante, et (ii) au moins un pigment, un colorant organique ou un colorant absorbant les infrarouges, le composé organique et le pigment, le colorant organique ou le colorant absorbant les infrarouges étant encapsulés par des capsules.
PCT/JP2018/003995 2017-02-06 2018-02-06 Colorant sensible à la température Ceased WO2018143473A1 (fr)

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